KR20150095561A - 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 alignment agent for obtaining a liquid crystal display device having a variety of properties in a balanced manner. A polymer (P) is contained in a liquid crystal alignment agent wherein the polymer is obtained by using in a reaction at least one compound (C′) selected from a group comprising: a compound (C) containing the following structure (a) and the following structure (b); and a compound (C1) containing the following structure (a) and the following structure (b1) and not bound with a reactive group involved in polymerization of an aromatic ring group of the following structure (a). (a) is an aromatic amine structure formed as two or three aromatic ring groups are bound to a same nitrogen atom; and (b) is a chain structure such as a divalent chain hydrocarbon group having six or more carbon atoms. (b1) is a divalent chain hydrocarbon group having one to five carbon atoms, -O-, -S- structures and so on.

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, liquid crystal display devices have been developed in various driving methods 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 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.

In recent years, along with the high definition of liquid crystal display elements, there has been a demand for reduction of afterimage phenomenon and suppression of lowering of contrast, and various liquid crystal aligning agents have been proposed in order to satisfy such demands See, for example, Patent Documents 1 to 6). In these Patent Documents 1 to 6, introduction of a diphenylamine unit into a liquid crystal aligning agent has been aimed at reducing accumulated charges and suppressing lowering of contrast in a liquid crystal display element.

Specifically, Patent Document 1 discloses that a liquid crystal aligning agent contains a polyamic acid or polyimide obtained by reacting a diamine containing 4,4'-diaminodiphenylamine with a tetracarboxylic acid dianhydride. Patent Document 2 discloses a polyimide obtained by reacting a tetracarboxylic acid dianhydride with a diamine containing an oligoaniline such as (4-aminophenyl) (4 - ((4-aminophenyl) amino) phenylamine to a liquid crystal aligning agent Patent Document 3 discloses that a compound having two or more diphenylamine units is added separately from a polymer such as polyamic acid or polyimide, or a diamine having two or more diphenylamine units And tetracarboxylic acid dianhydride are reacted with each other to form a liquid crystal aligning agent.

Patent Document 4 discloses that a diamine containing 1,3-bis-4- (N, N- (4-aminophenyl) aminophenyl) propane as a compound having two diphenylamine structures in the molecule and a tetracarboxylic acid dianhydride Is contained in the liquid crystal aligning agent. In Patent Documents 5 and 6, a polyamic acid obtained by reacting a diamine containing N, N'-bis (4-aminophenyl) -N, N'-dimethylethylenediamine with a tetracarboxylic dianhydride is referred to as a liquid crystal Is contained in the alignment agent.

In addition, various optical materials are used for the liquid crystal display element. In particular, the retardation film is used for the purpose of eliminating the coloring of the display, the purpose of solving the viewing angle dependency such that the display color and the contrast ratio are changed according to 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, a photo alignment method has been used in which, when a liquid crystal alignment film is formed on a phase difference film, a liquid crystal aligning ability is imparted by irradiating polarized or unpolarized radiation to a radiation-sensitive organic thin film formed on the substrate surface, A liquid crystal aligning agent for a phase difference film for producing a liquid crystal alignment film by such a method has been proposed (see, for example, Patent Document 7).

Japanese Patent Publication No. 4052307 Japanese Patent Application Laid-Open No. 2000-44683 Japanese Patent Publication No. 4924832 Japanese Laid-Open Patent Publication No. 2011-207786 Japanese Laid-Open Patent Publication No. 2012-155311 Japanese Patent Publication No. 5130907 Japanese Laid-Open Patent Publication No. 2012-37868

However, when the liquid crystal aligning agent of Patent Document 1 is used, the DC residual relaxation in the liquid crystal display element is insufficient, and the time until the after-image disappears tends to be long. In the conventional liquid crystal aligning agent containing a polymer using a diamine having a plurality of diphenylamine units as monomers, although the performance of DC residual relaxation is improved, since the aromatic concentration is high, the disadvantage of low transmittance of the liquid crystal alignment film . In addition, the AC after-image performance, which is one of the characteristics that affect the contrast of the liquid crystal display element, is not sufficient, and various characteristics are not well balanced. Further, with the recent increase in the versatility of the liquid crystal display element, the liquid crystal display element is expected to be used in a more severe situation, and a liquid crystal display element is required to have excellent heat resistance.

A liquid crystal display is manufactured by disposing a pair of substrates on which a liquid crystal alignment film is formed and arranging the liquid crystal between a pair of substrates opposed to each other. At that time, the pair of substrates are bonded using a sealant such as an epoxy resin. Here, in a touch panel type display panel typified by a smart phone or a tablet PC, in order to make the movable area of the touch panel wider and to make the liquid crystal panel (element) smaller, Is attempted. As the liquid crystal panel is subjected to the dilution softening of the liquid crystal panel, display unevenness is visually observed in the vicinity of the sealant, which is not sufficiently satisfactory in terms of display quality. In order to make the liquid crystal display finer and more durable, there is a demand for a liquid crystal display element in which display unevenness around the seal is hardly visible (high bezel nonuniformity resistance).

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems and has an object to provide a liquid crystal display device having a liquid crystal alignment film with good transparency, less display unevenness around the sealant, and various characteristics such as afterimage characteristics, high contrast, It is an object to provide a liquid crystal aligning agent.

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

In one aspect, the present invention provides a compound (C) having the following structure (a) and the following structure (b), and a compound having the following structure (a) (P) obtained by using at least one kind of compound (C ') selected from the group consisting of a compound (C1) having no reactive group participating in polymerization in the reaction.

(a) an aromatic amine structure in which two or three aromatic rings are bonded to the same nitrogen atom;

(b) a bivalent chain hydrocarbon group having 6 or more carbon atoms and at least one methylene group in the chain hydrocarbon group is -O-, -S-, -CO-, -NR-, -NRCO-, -COO-, -COS - or -Si (CH ₃ ) ₂ - (R is a hydrogen atom or a monovalent organic group).

(b1) a divalent chain hydrocarbon having 1 to 5 carbon atoms, at least one methylene group in the art chain hydrocarbon groups ^{-O-, -S-, -CO-, -NR 3} -, -NR 3 CO-, -COO -, -COS- or -Si (CH ₃ ) ₂ -, -O-, -S-, -CO-, -NR ³ CO- (R ³ is a hydrogen atom or a monovalent organic group ), -COO-, -COS-, and -Si (CH ₃ ) ₂ -.

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 (1-1), a compound represented by the following formula (1-2), and a compound represented by the following formula (1-3) Also, at least one compound selected from the group consisting of a tetracarboxylic acid dianhydride, a tetracarboxylic acid diester compound and a tetracarboxylic acid diester dihalide, a compound represented by the following formula (1-1), a compound represented by the following formula A group consisting of a polyamic acid, a polyamic acid ester and a polyimide obtained by using a diamine containing at least one member selected from the group consisting of a compound represented by the following formula (1-3) and a compound represented by the following formula : ≪ / RTI >

(In the formula (1-1), A ¹ and A ³ each independently represent a hydrogen atom or a monovalent organic group; A ² and A ⁴ each independently represent a single bond or a divalent organic group; B ¹ and B ² are each independently a single bond or a divalent organic group, and; stage, B ¹ in this case, a single bond is, a ¹ and a ² at least one of is and bonded to the nitrogen atom in the aromatic ring, B ¹ is 2 At least two of A ¹ , A ² and B ¹ are bonded to a nitrogen atom as an aromatic ring, and when B ² is a single bond, at least one of A ³ and A ⁴ is an aromatic ring, When B ² is a divalent organic group, at least two of A ³ , A ⁴ and B ² are bonded to a nitrogen atom as an aromatic ring; L ¹¹ represents a divalent straight chain hydrocarbon group having 6 or more carbon atoms; (Wherein R is a hydrogen atom or a methylene group having 1 to ₃ carbon atoms), and R < ₂ > Is the organic component of A divalent group comprising a group is formed, and; stage, L ¹¹ is the case having the alkanediyl group having a carbon number of 1~5, A ¹ and A ³ is at least any one of a hydrogen atom, or B ¹ and B ^2, at least one of One is a bivalent organic group);

(Wherein (1-2), L ¹² is a divalent group having a carbon number of 6 or more comprising a divalent chain hydrocarbon, and; A ^1, A ^2, A ^3, A ^4, B ¹ and B ² has the formula (1 -1), provided that when L ¹² is an alkanediyl group having 6 to 10 carbon atoms, at least one of A ¹ and A ³ is a monovalent organic group, or at least one of B ¹ and B ² Is a bivalent organic group);

Wherein A ⁷ is a hydrogen atom or a monovalent organic group, A ⁸ and A ⁹ are each independently a single bond or a divalent organic group, with the proviso that A ⁷ , A ⁸ and A ⁹ At least two of them are bonded to a nitrogen atom through an aromatic ring; L ⁴ is the above structure (b1); and L ⁵ is a single bond or a divalent organic group.

According to the liquid crystal aligning agent containing the polymer (P) as a polymer component, it is possible to obtain a liquid crystal display element having less display unevenness around the sealant and having various characteristics such as low image retention, high contrast and heat resistance in a well balanced manner. In addition, a liquid crystal alignment film having good transparency can be obtained. Furthermore, the solubility of the polymer (P) in a solvent is good, and the storage stability of the liquid crystal aligning agent is also good.

1 is a schematic configuration diagram of an FFS type liquid crystal cell.
Fig. 2 is a schematic plan view of a top electrode used in the manufacture of a liquid crystal display element by a photo alignment method. Fig. 2 (a) is a top view of a top electrode, and Fig. 2 (b) is an enlarged view of a top electrode.
Fig. 3 is a diagram showing four types of driving electrodes.
4A is a top view of a top electrode, and FIG. 4B is an enlarged view of a top electrode. FIG. 4A is a schematic plan view of a top electrode used for manufacturing a liquid crystal display device by rubbing treatment. FIG.

(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 (P) >

The liquid crystal aligning agent of the present invention is a liquid crystal aligning agent which comprises, as a polymer component, a compound (C) having the structure (a) and the structure (b) (P) obtained by using at least one kind of compound (C ') selected from the group consisting of a compound (C1) in which a reactive group participating in polymerization is not bonded to an aromatic ring group in the reaction. Hereinafter, the structure (a) is referred to as an "aromatic amine structure (a)" and the structure (b) is referred to as a "chain structure (b)".

Compound (C)

(Aromatic amine structure (a))

The aromatic amine structure (a) of the compound (C) is a structure in which two or three aromatic ring groups are bonded to the same nitrogen atom. The aromatic ring may be a group obtained by removing the hydrogen atom from the ring part of the aromatic ring. Specific examples thereof include an aromatic hydrocarbon ring such as a benzene ring, a toluene ring, a naphthalene ring, and an anthracene ring; Aromatic heterocyclic rings such as pyridine ring, pyrimidine ring, pyrazine ring, pyridazinyl ring and triazine ring; Or a group obtained by removing a hydrogen atom from a ring part in an aromatic ring such as a benzene ring or the like. Of these, benzene rings are preferred from the viewpoint of good affinity with liquid crystals.

The number of aromatic amine structures (a) in the molecule of the compound (C) is one or more than two, preferably two or more from the viewpoint of enhancing the performance of residual DC relaxation. From the viewpoints of the transmittance of the liquid crystal alignment film and the solubility of the polymer, it is more preferably 2 to 4, and still more preferably 2 or 3.

(Chain structure (b))

The chain structure (b) of the compound (C) is a bivalent chain hydrocarbon group having 6 or more carbon atoms, or at least one methylene group in the bivalent chain hydrocarbon group having 6 or more carbon atoms is -O-, -S-, CO-, -NR-, -NRCO-, -COO-, -COS- or -Si (CH ₃ ) ₂ - (R is a hydrogen atom or a monovalent organic group).

The bivalent chain hydrocarbon group in the chain structure (b) means a hydrocarbon group which does not contain a cyclic structure in the main chain but consists of a straight chain or branched chain structure only. The bivalent chain hydrocarbon group in the above chain structure (b) may have 6 or more carbon atoms, and specific examples thereof include a hexanediyl group, a heptanediyl group, an octanediyl group, a nonanediyl group, a decanediyl group, a dodecanediyl group , Tetradecanediyl group, eicosanediyl group and the like; a saturated hydrocarbon group having 6 to 30 carbon atoms; And an unsaturated hydrocarbon group having 6 to 30 carbon atoms in which at least one carbon-carbon bond among the capped hydrocarbon groups having 6 to 30 carbon atoms is a double bond or a triple bond. These may be linear or branched, but are preferably straight-chain.

When the above chain structure (b) is a bivalent straight chain hydrocarbon group having 6 or more carbon atoms, the number of carbon atoms of the chain hydrocarbon group is preferably 6 to 30, more preferably 6 to 20.

The chain structure (b) is a structure in which at least one methylene group in the bivalent hydrocarbon group having 6 or more carbon atoms is replaced with -O-, -S-, -CO-, -NR-, -NRCO-, -COO-, -COS - or -Si (CH ₃ ) ₂ - (R is a hydrogen atom or a monovalent organic group), the number of substitution may be one or more, and may be suitably set in accordance with the number of carbon atoms. The number of carbon atoms before the substitution of the methylene group by the functional group is preferably 6 to 30, more preferably 7 to 20.

Examples of the monovalent organic group of R include a straight chain hydrocarbon group having 1 to 5 carbon atoms such as an alkyl group or an alkenyl group and a straight chain hydrocarbon group having 1 to 5 carbon atoms such as -O-, A protecting group for an amino group, and the like. Specific examples of the protecting group of the amino group include a t-butoxycarbonyl group, a benzyloxycarbonyl group, a 1,1-dimethyl-2-haloethyloxycarbonyl group, a 1,1-dimethyl-2-cyanoethyloxycarbonyl group , A 9-fluorenylmethyloxycarbonyl group, an allyloxycarbonyl group, a 2- (trimethylsilyl) ethoxycarbonyl group, and the like, preferably a t-butoxycarbonyl group.

The number of the chain structures (b) in the molecule of the compound (C) may be one, or two or more. Preferably 1 to 5, and more preferably 1 to 3. The compound (C) is obtained by reacting the aromatic amine structure (a) and the chain structure (b) with the main chain of the compound (C), specifically the longest carbon chain among the compounds ) Carbon chain).

The molecular weight of the compound (C) is preferably 1,200 or less in view of reducing the surface roughness of the liquid crystal alignment film. Therefore, it is preferable to set the number of the aromatic amine structure (a) and the chain of the chain structure (b) such that the molecular weight of the compound (C) falls within the above range. The molecular weight is more preferably 1,000 or less, and still more preferably 800 or less.

Compound (C1)

The compound (C1) has the aromatic amine structure (a) and the structure (b1). However, in the compound (C1), the aromatic group in the aromatic amine structure (a) is not bonded to the reactive group involved in the polymerization. The reactive group differs depending on the main skeleton of the polymer (P). For example, when the main skeleton of the polymer (P) is a polyamic acid or a polyimide, the reactive group is an acid anhydride group or a primary amino group, , The reactive group is a hydroxyl group or a carboxyl group, and when the reactive group is a polyamide, the reactive group is a carboxyl group or a primary amino group.

The description of the aromatic ring of the aromatic amine structure (a) of the compound (C1) can be applied to the description of the compound (C). The aromatic amine structure (a) in one molecule of the compound (C1) is preferably one.

Compound (C1) having the structure (b1) is an at least one of the methylene groups in the divalent chain hydrocarbon group, a hydrocarbon chain having a carbon number of art 1~5 -O-, -S-, -CO-, -NR 3 - , -NR ³ CO-, -COO-, -COS- or -Si (CH ₃ ) ₂ -, -O-, -S-, -CO-, -NR ³ CO-, -COO -, -COS-, and -Si (CH ₃ ) ₂ - (R ³ is a hydrogen atom or monovalent organic group). Further, the compound (C1) may have only one of these compounds in the molecule, or two or more compounds may be contained in the molecule.

Specific examples of the monovalent hydrocarbon group having 1 to 5 carbon atoms in the structure (b1) include a methylene group, an ethylene group, a propanediyl group, a butane diyl group, a pentanediyl group, a vinylene group, Quot ;, " Butendi diary ", and " Pentendi diary ". These may be linear or branched, but are preferably straight-chain.

The structure (b1) is, at least one methylene group in groups a divalent chain hydrocarbon group of a carbon number of 1~5 -O-, -S-, -CO-, -NR 3 -, -NR 3 CO-, -COO- , -COS- or -Si (CH ₃ ) ₂ -, the number of the substitution may be one or more, and may be suitably set in accordance with the number of carbon atoms. For the explanation of the monovalent organic group of R ³ , the description of R in the compound (C) can be applied.

The number of the structures (b1) in the molecule of the compound (C1) may be one, or two or more. Preferably two or more, and particularly preferably two. The description of the compound (C) can be applied to the molecular weight of the compound (C1).

Examples of the main skeleton of the polymer (P) include polyamic acid, polyimide, polyamic acid ester, polyester, polyamide, polysiloxane, polyorganosiloxane, cellulose derivative, polyacetal derivative, polystyrene derivative, Phenylmaleimide) derivatives, poly (meth) acrylate derivatives, and the like. As the polymer (P), one or more kinds of polymers selected therefrom can be appropriately selected and used according to the use of the liquid crystal aligning agent and the like. Further, (meth) acrylate means that it includes acrylate and methacrylate. The polymer (P) may have the aromatic amine structure (a) and the chain structure (b) or the structure (b1) in any of the main chain and side chain of the polymer and preferably has the main chain of the polymer.

The main skeleton of the polymer (P) is preferably at least one selected from the group consisting of polyamic acid, polyimide and polyamic ester, and the aromatic amine structure (a) and the above chain structure (b) more preferably at least one member selected from the group consisting of polyamic acid, polyimide and polyamic acid ester having (b1) in the main chain. The polymer (P) is preferably a polymer obtained by using the compound (C ') as a monomer.

Here, the " main chain " of the polymer in the present invention means a portion of a " stem " composed of a chain of the longest atoms among the polymers. In addition, it is permitted that the portion of this " stem " includes a ring structure. Thus, "having the aromatic amine structure (a), the chain structure (b) or the structure (b1) in the main chain of the polymer" means that these structures constitute a part of the main chain. However, in the polymer (P), the aromatic amine structure (a), the chain structure (b) and the structure (b1) may also be bonded to a part other than the main chain such as a side chain It does not exclude what exists.

[Polyamic acid (P)]

When the polymer (P) is a polyamic acid (hereinafter also referred to as "polyamic acid (P)"), for example, it can be obtained by reacting a tetracarboxylic dianhydride with a diamine.

(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 Acid dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, ethylenediamine tetraacetic acid dianhydride, cyclopentanetetracarboxylic acid dianhydride, ethylene glycol bis Anhydrotrimellitate), 1,3-propylene glycol bis (anhydrotrimellitate), and the like;

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

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, ethylene di At least one compound selected from the group consisting of acetic acid dianhydride, cyclopentanetetracarboxylic acid dianhydride, 1,3-propylene glycol bis (anhydrotrimellitate) and pyromellitic acid dianhydride (hereinafter, Quot; tetracarboxylic acid dianhydride "). 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 in the synthesis of the polyamic acid, And particularly preferably 20 mol% or more.

(Diamine)

The diamine used for the synthesis of the polyamic acid (P) is a diamine having the aromatic amine structure (a) and the chain structure (b) (hereinafter also referred to as "diamine (C)") And at least one compound (C ') selected from the group consisting of a compound (C1) having the structure (b1).

Diamine (C)

The diamine (C) preferably has a structure capable of introducing the aromatic amine structure (a) and the chain structure (b) into the main chain of the polymer (P), and more specifically, a compound represented by the following formula Is preferred:

Wherein A ¹ and A ³ are each independently a hydrogen atom or a monovalent organic group; A ² and A ⁴ are each independently a single bond or a divalent organic group; B ¹ and B ² Provided that when B ¹ is a single bond, at least one of A ¹ and A ² is an aromatic ring bonded to a nitrogen atom, and B ¹ is a divalent organic At least two of A ¹ , A ² and B ¹ are bonded to a nitrogen atom as an aromatic ring; and when B ² is a single bond, at least one of A ³ and A ⁴ is an aromatic ring, At least two of A ³ , A ⁴ and B ² are bonded to a nitrogen atom as an aromatic ring when B ² is a divalent organic group; L ¹ is a divalent group comprising the structure (b) ).

Examples of monovalent organic groups represented by A ¹ and A ³ in the formula (1) include monovalent hydrocarbon groups, monovalent hydrocarbon groups having -O-, -COO-, -COO-, CO-, -NHCO-, -S-, -NH-, or the like, and a protecting group for an amino group. The hydrogen atom bonded to the carbon atom of the hydrocarbon group in A ¹ and A ³ may be substituted with a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.) or a hydroxyl group . Concrete examples of the protecting group of the amino group include the groups exemplified in the description of R in the chain structure (b). Preferably a t-butoxycarbonyl group.

Examples of the hydrocarbon group include a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. In the present specification, the term "chain hydrocarbon group" is as defined above. 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 is not always necessary to be constituted by only the structure of alicyclic hydrocarbons, and some of them include those having 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 groups represented by A ¹ and A ³ include linear hydrocarbon groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, An alkyl group having 1 to 30 carbon atoms such as an acyl group, a dodecyl group, a tetradecyl group and an eicosanyl group; An alkenyl group having 2 to 30 carbon atoms such as an ethynyl group, a propenyl group, and a butenyl group; And an alkynyl group having 2 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, a norbornyl group, an adamantyl 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.

Examples of the divalent organic groups in A ² , A ⁴ , B ¹ and B ² include, for example, bivalent hydrocarbon groups, carbon-carbon bonds in the divalent hydrocarbon groups, -O-, -COO-, -CO -, -NHCO-, -S-, -NH-, and the like, and even when a hydrogen atom bonded to the carbon atom of each of these groups is substituted with a halogen atom or a hydroxyl group good. Specific examples of the divalent hydrocarbon group include groups in which one hydrogen atom has been removed from each of the groups exemplified in the monovalent hydrocarbon group. In the compound represented by the formula (1), the structure surrounding the nitrogen atom in the formula (1) corresponds to the aromatic amine structure (a).

B ¹ and B ^2, it is preferable that the at least one side is a single bond is preferable, and, B ¹ and B ² are both a single bond.

L ¹ is a divalent group comprising the above chain structure (b). Specific preferred examples of L ¹ include, for example, groups represented by the following formula (2):

(2), L ² and L ³ are each independently the structure (b), Q is a divalent group represented by the following formula (3) or (4), n is 0 to 4 Integer " and " * " denotes a combined hand);

(In the formula (3), A ⁵ is a hydrogen atom or a monovalent organic group; R ¹ and R ² are substituents and may be the same or different;

(In the formula (4), A ⁶ is a hydrogen atom or a monovalent organic group; "*" indicates a bonding hand).

As the monovalent organic group of A ⁵ and A ⁶ in the formulas (3) and (4), the description of the monovalent organic group of A ¹ and A ³ can be applied. N in the formula (2) is preferably 0 or 1.

Specific examples of the group represented by the formula (2) include, for example, groups represented by the following formulas (2-1) to (2-25) and the like:

(Where " * " represents a combined hand).

Specific preferred examples of the compound represented by the above formula (1) include, for example, a compound represented by the following formula (1-1) and a compound represented by the following formula (1-2)

(In the formula (1-1), L ¹¹ represents at least one methylene group in the bivalent chain hydrocarbon group having 6 or more carbon atoms, -O-, -S-, -CO-, -NR-, -NRCO-, -COO- , -COS- or _{-Si (CH 3) 2 - (} R is a hydrogen atom or a monovalent organic group being) comprising a divalent group which is substituted by ^{a; a 1, a 2, a} 3, a 4, B 1 And B ² have the same meanings as in the formula (1), provided that when L ¹¹ has an alkanediyl group having 1 to 5 carbon atoms, at least one of A ¹ and A ³ is a hydrogen atom, or B ¹ and B < ² > is a divalent organic group);

(In formula (1-2) of, L ¹² is a divalent group having a carbon number of 6 or more comprising a divalent chain hydrocarbon, ^{and; A 1, A 2, A} 3, A 4, B 1 and B ^2, the formula ( 1)).

L ¹¹ in the above formula (1-1) represents at least one methylene group in the divalent straight chain hydrocarbon group having 6 or more carbon atoms, with -O-, -S-, -CO-, -NR-, -NRCO-, -COO -, -COS- or -Si (CH ₃ ) ₂ -, or may have a plurality of groups. As a preferable specific example of L ¹¹ , a group represented by the above formula (2) (wherein L ² and L ³ represent at least one methylene group in the divalent chain hydrocarbon group having 6 or more carbon atoms, -O-, -S-, -CO -, -NR-, -NRCO-, -COO-, -COS- or -Si (CH ₃ ) ₂ -.

When L ¹¹ contains an alkanediyl group having 1 to 5 carbon atoms, it is preferable that at least one of A ¹ and A ³ is a hydrogen atom, and A ¹ and A ³ are both hydrogen atoms.

L ¹² in the formula (1-2) may have only one bivalent chain hydrocarbon group having 6 or more carbon atoms, or may have a plurality of groups. Specific preferred examples of L ¹² include a group represented by the above formula (2) (wherein L ² and L ³ are divalent chain hydrocarbon groups having 6 or more carbon atoms).

In the compound represented by the above formula (1-2), when the alkanediyl group of L ¹² has 6 to 10 carbon atoms, at least one of A ¹ and A ³ is a monovalent organic group, or B ¹ and B ² It is preferable that at least one of them is a divalent organic group. When A ¹ and A ³ in the formula (1-1) are hydrogen atoms, L ¹² is preferably a divalent straight chain hydrocarbon group having a carbon number of 7 or more, in which L ² and L ³ of the group represented by the formula (2) More preferably a bivalent straight chain hydrocarbon group having a carbon number of 11 or more.

Specific examples of the diamine (C) include compounds represented by the following formulas (DA-1) to (DA-10) and (DA-41), respectively. The diamine (C) may be used singly or in combination of two or more.

(Wherein Ph represents a phenyl group).

Diamine (C1)

The diamine (C1) preferably has a structure capable of introducing the aromatic amine structure (a) and the structure (b1) into the main chain of the polymer (P). Specifically, the diamine Is preferably a compound:

Wherein A ⁷ is a hydrogen atom or a monovalent organic group, A ⁸ and A ⁹ are each independently a single bond or a divalent organic group, with the proviso that A ⁷ , A ⁸ and A ⁹ At least two of them are bonded to a nitrogen atom through an aromatic ring; L ⁴ is the above structure (b1); and L ⁵ is a single bond or a divalent organic group.

As the monovalent organic group of A ⁷ with respect to the above formula (1-3), the description of the monovalent organic group of A ¹ and A ^{3 in} the above formula (1) can be applied. As the divalent organic group of A ⁸ and A ⁹ , the description of A ² and A ^{4 in} the above formula (1) can be applied. Examples of the divalent organic group represented by L ⁵ include a divalent chain hydrocarbon group having 1 to 20 carbon atoms, at least one methylene group in the chain hydrocarbon group is -O-, -S-, -CO-, -NR ⁴ - , -NR ⁴ CO-, -COO-, -COS- or -Si (CH ₃ ) ₂ -, -O-, -S-, -CO-, -NR ⁴ CO-, -COO -, -COS-, and -Si (CH ₃ ) ₂ - (R ⁴ is a hydrogen atom or a monovalent organic group). Among them, L ⁵ is preferably a structure (b1).

Preferable specific examples of the diamine (C1) include compounds represented by the following formulas (DA-22) to (DA-40). The diamine (C1) may be used singly or in combination of two or more.

The diamine (C ') used in the synthesis of the polyamic acid (P) may be only the diamine (C'), but other diamines other than the above diamine may be used together with the diamine (C ').

Examples of other diamines usable 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, 1,7-bis (4-aminophenoxy) heptane, 1,5-diaminonaphthalene, 2,2'-dimethyl- Diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 4,4'- Bis (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoro 4,4'- (p-phenylenediisopropylidene) bisaniline, 4,4 '- (m-phenylenediisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) benzene , 4,4'-bis (4-aminophenoxy) biphenyl, 2,6-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminocarbazole, N, N'-bis 4-aminophenyl) -benzidine, 1,4-bis- (4 -Aminophenyl) -piperazine, 3,5-diaminobenzoic acid, dodecaneoxy-2,4-diaminobenzene, tetradecanoxy-2,4-diaminobenzene, pentadecaneoxy-2,4-diamino Benzene, hexadecaneoxy-2,4-diaminobenzene, octadecanoxy-2,4-diaminobenzene, dodecaneoxy-2,5-diaminobenzene, tetradecanoxy- Pentadecaneoxy-2,5-diaminobenzene, hexadecaneoxy-2,5-diaminobenzene, octadecaneoxy-2,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, Stearyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestenyloxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholestanyl, 3 , 5-diaminobenzoic acid cholestenyl, 3,5-diaminobenzoic acid ranostanyl, 3,6-bis (4-aminobenzoyloxy) cholestane, 3,6-bis , 4- (4 ' -trifluoromethoxybenzoyloxy) cyclohexyl-3,5-diaminobenzoate, Bis (4 - ((aminophenyl) methyl) phenyl) -4-butylcyclohexane, 1 (4'-trifluoromethylbenzoyloxy) cyclohexyl-3,5-diaminobenzoate, Heptylcyclohexane, 1,1-bis (4 - ((aminophenoxy) methyl) phenyl) -4-heptylcyclohexane, Diamino-N, N-diallylaniline, 4-aminobenzylamine, 3-aminobenzylamine, 3-aminobenzylamine, -Aminobenzylamine, 1- (2,4-diaminophenyl) piperazine-4-carboxylic acid, 1,3-bis (N- (4-aminophenyl) piperidinyl) propane, Aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-inden-5-amine, 1- (4- Dihydro-1,3,3-trimethyl-1H-inden-6-amine, 4-aminophenyl-4'- aminobenzoate, 4,4 '- [ (Piperidin-1, 4-diyl)] dianiline, 4- (4-aminophenoxycarbonyl) -1- Carbonyl) piperidine, the formula (DA-18):

And a compound represented by the following formula (D-1):

(Formula (D-1) of, X and X ^{Ⅰ Ⅱ} are, each independently, a single bond, -O-, * -COO- or * -OCO - (* the formula indicates the bonding hand bonded to the benzene ring of the ), with a, R ^ⅰ is alkanediyl group having a carbon number of 1~3, R ^ⅱ is alkanediyl group of a single bond or a carbon number of 1~3, a is 0 or 1, b is an integer of 0~2, c is And d is 0 or 1, provided that a and b are not 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 ) _d -" 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 diamines used in the synthesis of the polyamic acid, one of these compounds may be used alone or two or more of them may be appropriately selected and used.

The diamine (C ') used in the synthesis of the polyamic acid (P) of the present invention is preferably 0.5 mol% or more based on the total amount of the diamine used in the synthesis. If it is less than 0.5 mol%, the effect of the present invention can not be sufficiently obtained. More preferably 2 mol% or more, still more preferably 5 mol% or more, and particularly preferably 10 mol% or more. The upper limit of the use ratio of the diamine (C ') can be arbitrarily set within a range of 100 mol% or less based on the total amount of the diamine used in the synthesis. It is preferable to set the use ratio of the diamine (C ') to 95 mol% or less in order to improve the effect (for example, printing property, voltage preservation rate, liquid crystal orientation, etc.) by adding other diamine.

When the liquid crystal aligning agent of the present invention is used for the production of liquid crystal display devices of the TN type, the STN type or the vertically aligned type, at least a part of the polymer (P) contained in the liquid crystal aligning agent is mixed with the pretilt angle- (Hereinafter, also referred to as " pretilt angle-expressing group "). Examples of the pretilt angular expression group include an alkyl group having 4 to 20 carbon atoms, a fluoroalkyl group having 4 to 20 carbon atoms, an alkoxy group having 4 to 20 carbon atoms, a group having a steroid skeleton having 17 to 51 carbon atoms, And the like.

In order to obtain a polyamic acid (P) having a pretilt angular expression group, it is preferable to carry out polymerization by incorporating a diamine having a pretilt angular expression group into the monomer composition, from the viewpoint of ease of introduction of the pretilt angular expression group. Specifically, it can be synthesized by using a diamine having a pretilt angular expression group as other diamine.

When a diamine having a pre-tilt angle-generating group is used in the synthesis of the polyamic acid (P), the amount of the diamine to be used is preferably 5 to 5 Mol% or more, and more preferably 10 mol% or more.

When the liquid crystal aligning ability is imparted to the coating film produced by using the liquid crystal aligning agent of the present invention by the photo alignment method, at least a part of the polymer (P) contained in the liquid crystal aligning agent is converted into a polymer having a photo- Maybe. 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 optical isomerization, optical dimerization, photolysis or the like can be employed, and for example, an azobenzene-containing group containing azobenzene or a derivative thereof as a 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 A polyimide-containing structure containing a coumarin-containing group, a polyimide or a derivative thereof as a skeleton as a basic skeleton, and the like.

For example, when the polyamic acid, the polyimide and the polyamic acid ester as the polymer (P) have a photo-alignment structure, it is preferable that the photo-alignment structure has a decomposition type photo-alignment portion. 2] octene skeleton or a cyclobutane skeleton. By having such a specific skeleton, the liquid crystal alignability of the coating film can be further improved. For example, a polyamic acid (P) having a bicyclo [2.2.2] octene skeleton or a cyclobutane skeleton may be a bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid Can be obtained by the reaction of a tetracarboxylic acid dianhydride containing at least one of dianhydrides and cyclobutanetetracarboxylic dianhydrides with diamines containing diamine (C ').

[Molecular Weight Regulator]

At the time of synthesizing the polyamic acid (P), a terminal modifier type polymer may be synthesized by using a suitable molecular weight modifier together with the tetracarboxylic dianhydride and the diamine 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.

The diamine (C) and the diamine (C1) can be synthesized by appropriately combining the stereochemistry of organic chemistry. As an example thereof, it is possible to synthesize a dinitro intermediate having a nitro group in place of the primary amino group in the formula for the compound represented by the formula (1), and then to react the nitro group of the obtained dinitro intermediate with a suitable reducing system Followed by amination.

The method for synthesizing the dinitro intermediate may be appropriately selected depending on the desired compound. As an example thereof, a method of reacting a secondary amine compound having a corresponding A ¹ , A ² and L ¹ with a halogenated nitrobenzene, for example, by referring to the compound represented by the formula (1) above; A method of reacting a halide having a corresponding A ¹ , A ² and L ¹ with a secondary amine compound containing a nitrophenyl group; A method of reacting a corresponding carboxylic acid having an aminophenyl group and a nitro group with a corresponding diol having L &^lt; ^{1 &} gt ;; A method of reacting a diamine compound having a corresponding A ¹ , A ² and L ¹ with halogenated nitrobenzene having a corresponding B ¹ ; A method of reacting a corresponding hydroxyl group-containing compound having an aminophenyl group and a nitro group with a corresponding halide having L ¹ ; 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 dinitro 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 synthesizing the diamine (C) and the diamine (C1) is not limited to the above method.

[Synthesis of polyamic acid (P)] [

The ratio of the tetracarboxylic dianhydride and the diamine to be used in the synthesis reaction of the polyamic acid (P) of the present invention is preferably such that the proportion of the acid anhydride group of the tetracarboxylic acid dianhydride to the equivalent of 0.2 to 2 equivalents , More preferably from 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 use ratio of the organic solvent of the second group is preferably 50% by weight or less, more preferably 40% by weight or less, relative to the total amount of the organic solvent of the first group and the organic solvent of the second group By weight, and more preferably 30% by weight or less. The amount (?) Of the organic solvent is preferably such that the total amount (?) Of the tetracarboxylic acid dianhydride and the diamine is 0.1 to 50% by weight based on the total amount (? +?) Of the reaction solution.

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 subjected to dehydration cyclization to form a 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.

[Polyamic acid ester (P)]

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- An epoxy group-containing compound, etc., [II] a method of reacting a tetracarboxylic acid diester with a diamine, and [III] a method of reacting a diamine with a tetracarboxylic acid diester dihalide.

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

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, 1,1,1-trifluoro-2-iodoethane and the like, and the epoxy group-containing compound For example, propylene oxide. 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 diamines used in the methods [II] and [III] preferably contain the diamine (C '), and other diamines as described above may be used if 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.

[Polyimide (P)]

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 imide cargo which is dehydrated and closed by all of the arboric acid structure of the polyamic acid (P) which is the precursor thereof, and only a part of the arboric 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 expressed as 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 ring-closing catalyst, for example, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used. The amount of the dehydration ring-closing catalyst to be used is preferably 0.01 to 10 mol based on 1 mol of the dehydrating agent to be used. Examples of the organic solvent used in the dehydration ring-closure reaction include the organic solvents exemplified for use in the synthesis of polyamic acid. The reaction temperature of the dehydration ring-closing reaction is preferably 0 to 180 캜, more preferably 10 to 150 캜. The reaction time is preferably 1.0 to 120 hours, more preferably 2.0 to 30 hours.

In this way, a reaction solution containing polyimide (P) can be 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, the polyimide (P) may be obtained by imidization of the polyamic acid ester (P).

The polyamic acid, the polyamic acid ester and the polyimide as the polymer (P) obtained as described above preferably have a solution viscosity of 20 to 1,800 mPa · s and a viscosity of 50 to 1,500 It is more preferable to have a solution viscosity of mPa 占 퐏. The solution viscosity (mPa 占 퐏) of the polymer was determined by using a solution of the polymer in a good solvent (for example,? -Butyrolactone, N-methyl-2-pyrrolidone, etc.) % Of the polymer solution at 25 占 폚 using an E-type rotational viscometer.

The weight average molecular weight (Mw) of the polyamic acid, the polyamic ester and the 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. Examples of such other components include a polymer other than the polymer (P), a compound having at least one epoxy group in the molecule (hereinafter referred to as "epoxy group-containing compound"), a functional silane compound, a metal chelate compound , A hardening accelerator, a surfactant, and the like.

[Other Polymers]

The other polymer may be used for improving solution characteristics and electrical properties. Examples of such another polymer include polymers obtained without using the above compound (C '), and the main skeleton thereof is not particularly limited. Specific examples thereof include polyamidic acid, polyimide, polyamic acid ester, polyorganosiloxane, polyester, polyamide, cellulose derivative, polyacetal, polystyrene derivative, poly (styrene-phenylmaleimide) ) Acrylate and the like in the main skeleton.

When the other polymer is added to the liquid crystal aligning agent, the blending ratio thereof is preferably 50 parts by weight or less, preferably 0.1 to 40 parts by weight, relative to 100 parts by weight of the total amount of the polymers contained in the liquid crystal aligning agent And more preferably 0.1 to 30 parts by weight or less.

When the liquid crystal aligning ability is imparted to the coating film formed using the liquid crystal aligning agent of the present invention by the photo alignment method, a polymer having a photo-orientable structure may be used as the other polymer. For example, in the case of a liquid crystal aligning agent for a retardation film, a polymer having a photo-orientable group as a photo-orientable structure can be preferably used, and specifically, a polymer into which a group having a cinnamic acid structure (cinnamic acid or a derivative thereof) . Among them, a polyorganosiloxane having a cinnamic acid structure can be preferably used because it is easy to introduce a photo-orientable group into the 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 liquid crystal aligning ability is imparted to the coating film by the photo alignment method, the use ratio of the polymer having the photo-orientable structure (the total amount of the polymer (P) and the other polymers when they have a photo-orientable structure) Is preferably 3% by weight or more, more preferably 5 to 100% by weight, and further preferably 10 to 100% by weight based on the total amount of the polymer used for preparing the liquid crystal aligning agent.

[Epoxy group-containing compound]

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

When 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 based on 100 parts by weight of the total amount of the polymers contained in the liquid crystal aligning agent More preferable.

[Functional silane compound]

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

When these functional silane compounds are 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 polymers contained in the liquid crystal aligning agent Is more preferable.

[Metal chelate compound]

The metal chelate compound is preferably used as a liquid crystal aligning agent (in particular, a liquid crystal aligning agent for a retardation film) for the purpose of ensuring the mechanical strength of a film formed by a 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. When the metal chelate compound is added, the use 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, per 100 parts by weight of the total amount of the components including the epoxy structure Is 1 to 30 parts by weight.

[Curing accelerator]

When the polymer component in the liquid crystal aligning agent has an epoxy structure, the curing accelerator is preferably added to a liquid crystal aligning agent (in particular, liquid crystal alignment for a retardation film . 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. When the curing accelerator is added, the use ratio thereof is preferably 50 parts by weight or less, more preferably 0.1 to 40 parts by weight, per 100 parts by weight of the total amount of the components including the epoxy structure, 1 to 30 parts by weight.

[Surfactants]

The surfactant may be contained in a liquid crystal aligning agent (particularly, a liquid crystal aligning agent for a retardation film) for the purpose of improving the application 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.

As other components, other than the above, a compound having at least one oxetanyl group in the molecule and an antioxidant may be mentioned.

<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 that are optionally used are dispersed or dissolved in an appropriate solvent.

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

The solid concentration 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 is heated to form a coating film which becomes 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 is 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. With respect to the liquid crystal aligning agent for the retardation film, it is preferable that the solid concentration of the liquid crystal aligning agent is 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 suitable, , And more preferably 3 to 10 wt%.

Further, according to the liquid crystal aligning agent containing the above-mentioned polymer (P), it has been found by the inventor of the present invention that a coating film having a flat surface (good surface irregularity) can be formed. The reason for this is not necessarily clear, but I guess the following. It is conceivable that incorporation of the aromatic amine structure (a) in order to improve the performance of DC residual relaxation makes it easy for the polymer to coagulate (crystallize) by becoming rigid in addition to the increase in crystallinity. In this case, it is assumed that the polymer chains are intertwined with each other at the time of forming the coating film, resulting in a decrease in surface irregularity of the coating film. On the other hand, in the polymer (P) obtained by using the compound (C) in the reaction, the chain structure (b) having a sufficiently long chain length is introduced as the spacer unit together with the aromatic amine structure (a) It is considered that the entanglement of the polymer chains with each other is released by heating (post-baking), and the surface irregularity is improved in the coated film after heating. It is also presumed that the above effect is obtained for the same reason for the polymer (P) obtained by using the compound (C1) in the reaction.

<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 element 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. 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 or the like is added to the surface of the substrate surface on which the coating film is to be formed in advance in order to improve the adhesion between the substrate surface and the transparent conductive film and the coating film The pre-treatment for coating may be performed.

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

(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, a treatment for imparting liquid crystal alignment ability to the coating film formed in the above step (I-1) is performed. Accordingly, the alignment ability of the liquid crystal molecules is imparted to the coating film to form a liquid crystal alignment film. Examples of the treatment include a rubbing treatment in which the coating film is rubbed in a predetermined direction with a roll formed of fibers such as nylon, rayon, and cotton, and a photo-alignment treatment of irradiating the coating film with polarized or unpolarized radiation. On the other hand, when the VA type liquid crystal display element is produced, the coating film formed in the above step (I-1) can be directly used as a liquid crystal alignment film, but the coating ability may be imparted to the coating film.

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

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

Further, it is also possible to use a 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 After the rubbing treatment is performed in a direction different from the rubbing treatment, a treatment for removing the resist film may be performed so that the liquid crystal alignment film has 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. A liquid crystal alignment film suitable for a VA type liquid crystal display device can be suitably used for a liquid crystal display device of a PSA (polymer sustained alignment) type.

[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 mentioned. 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 injected 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 place on one of the two substrates on which the liquid crystal alignment film is formed, and liquid crystal is further dripped onto a predetermined number of places on the liquid crystal alignment film surface, The liquid crystal cell can be manufactured by joining the other substrate so as to face the alignment film and spreading the liquid crystal on the entire surface of the substrate and then curing the sealant by irradiating ultraviolet light to the entire surface of the substrate. Regardless of the method, it is preferable to further heat the liquid crystal cell manufactured as described above to a temperature at which the liquid crystal used becomes an isotropic phase, and then gradually cool to room temperature to remove the flow alignment at the time of filling the liquid crystal Do.

As the sealing agent, for example, an epoxy resin containing a curing agent and an aluminum oxide spheres 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 agent sold under the trade names "C-15" and "CB-15" (Merck); p-decyloxybenzylidene-p-amino-2-methylbutyl cinnamate and the like may be added and used.

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 called a "H film" in which iodine is absorbed while polyvinyl alcohol is oriented in a stretched polyvinyl alcohol, a polarizing plate sandwiched by a cellulose acetate protective film, .

[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. Thus, 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, and a step of joining the retardation film on 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 perform 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-axis reverse roll coater method, a four-axis 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, the description of the optical alignment treatment in the step (I-2) can be applied to the wavelength of light to be irradiated, the kind of light, and the explanation of the light source to be used. The dose of light is preferably 0.1 to 1,000 mJ / cm 2, more preferably 1 to 500 mJ / cm 2, and still more preferably 2 to 200 mJ / cm 2.

[Process (II-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 further contain a known polymerization initiator, a suitable solvent, or 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 performed 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 half-wave plate in visible light having a wavelength of 540 nm, a thickness is selected so that the retardation of the formed retardation film becomes 240 to 300 nm. If the retardation film is a quarter- A thickness of 120 to 150 nm is selected. 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, when RMS03-013C manufactured by Merck is used, 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 device to which the retardation film manufactured using the liquid crystal aligning agent of the present invention is applied is not limited to the driving method thereof and may be various kinds of known various types such as TN type, STN type, IPS type, FFS type, . 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 viewer 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.

Here, as a method of producing the retardation film on an industrial scale, there is a roll-to-roll method. This method includes a process of winding a film from a rolled material of a long base material film and forming a liquid crystal alignment film on the wound film, a process of applying a polymerizable liquid crystal on the liquid crystal alignment film and curing the film, And a process of laminating a protective film as necessary is carried out in successive processes, and the film after the above processes is recovered as a rolled film. The retardation film formed by using the liquid crystal aligning agent of the present invention has good adhesion to the substrate, and even when it is stored as a winding, the liquid crystal alignment film and the substrate are difficult to peel off. Therefore, it is possible to suppress the decrease in the product yield when the retardation film is produced by the roll-to-roll method.

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 GPC under the following conditions.

Column: TSKgelGRCXLII, manufactured by Tosoh Corporation

Solvent: tetrahydrofuran, or N, N-dimethylformamide solution containing lithium bromide and phosphoric acid

Temperature: 40 ° C

Pressure: 68kgf / ㎠

[Imidization Rate of Polymer]

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

Imidization rate (%) = {(1-E ¹ ) / (E ² × α)} × 100 (EX-1)

(In the formula (EX-1), E ¹ is the peak area derived from the proton of the NH group appearing near the chemical shift of 10 ppm, E 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 the number of protons of the NH group in the polymer).

[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 Compound (C) &gt;

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

Compound (DA-1) was synthesized according to Reaction Scheme 1 below. In the formulas, Bn represents a benzyl group (hereinafter the same).

The reaction of the first step was synthesized by Williamson reaction. First, 83.7 g (0.2 mol) of N-benzyl-4-hydroxyaniline, 46 g (0.42 mol) of 1,5-dibromopentane and 121.5 g (0.8 mol) of cesium fluoride were added to a 2 L three-necked flask equipped with a dropping funnel ) And 800 mL of dimethylformamide were mixed and dissolved, and the reaction was carried out at 60 ° C for 4 hours with stirring. After the reaction, 2000 mL of ethyl acetate was added to extract, and 200 mL of distilled water was added to carry out liquid separation and purification. After repeating the extraction and purification five times, the solvent was removed from the organic layer by distillation under reduced pressure to obtain 76.4 g (0.16 mol) of a dibenzyl intermediate (compound represented by the formula (DA-1-1)).

The reaction in the second step was synthesized by the Ullmann condensation reaction. (0.16 mol) of the dibenzyl intermediate (DA-1-1), 81.5 g (0.33 mol) of 4-iodonitrobenzene and 59 g (0.33 mol) of phenanthroline were added to a 2 L three- ), 139 g (0.65 mol) of tripotassium phosphate, 9.4 g (0.05 mol) of copper iodide and 600 mL of dimethylacetamide were added, mixed and dissolved, and the reaction was carried out with stirring for 24 hours under reflux. After completion of the reaction, the reaction solution was filtered, the catalyst was removed, and the filtrate was poured into 2000 mL of distilled water to precipitate crystals. The precipitated solid was collected by filtration, sufficiently washed with ethanol, and recrystallized from tetrahydrofuran to obtain 35 g (0.05 mol) of a nitro intermediate (compound represented by the above formula (DA-1-2)).

The reaction in the third step was synthesized by hydrogen reduction reaction. 35 g of the above nitro intermediate (DA-1-2), 3 g of 5% Pd / C, 50 mL of ethanol, 50 mL of tetrahydrofuran and 35 mL of hydrazine monohydrate were added to a 500 mL three- Substituted again, and reacted in the presence of hydrogen at room temperature. The reaction was followed by HPLC and filtration was performed after confirming the progress of the reaction. To the filtrate, 1000 mL of ethyl acetate was added, and 100 mL of distilled water was added, followed by liquid separation and purification. After the extraction and purification were repeated five times, the solvent was removed from the organic layer by vacuum distillation to precipitate a solid. The precipitated solid was recrystallized from a mixed solvent of tetrahydrofuran and ethanol to obtain 18.5 g (0.04 mol) of the compound (DA-1).

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

Compound (DA-2) was obtained according to the following Reaction Scheme 2 using the same synthesis reaction prescription as Compound (DA-1).

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

Compound (DA-3) was obtained according to the following Reaction Scheme 3 using the same synthesis reaction prescription as Compound (DA-1). Also, the reaction of the second step was synthesized using the technique described in Non-Patent Document 2 (The Journal of Organic Chemistry, 2002, 67, 6479).

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

Compound (DA-4) was obtained according to the following Reaction Scheme 4 using the same synthesis reaction prescription as Compound (DA-1). The reaction in the second step was synthesized by a hydrolysis reaction, and the third step was synthesized by a condensation reaction with 1-ethyl-3- (3-dimethylaminopropyl) carboxyimide hydrochloride.

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

Compound (DA-5) was obtained according to the following Reaction Scheme 5 using the same synthesis reaction prescription as Compound (DA-1).

[Synthesis Examples 1-6; Synthesis of compound (DA-6)

Compound (DA-6) was obtained according to the above reaction scheme 6 using the same synthesis reaction prescription as compound (DA-1).

[Synthesis Examples 1-7; Synthesis of Compound (DA-7)

Compound (DA-7) was obtained according to the following Reaction Scheme 7 using the same synthesis reaction prescription as Compound (DA-1).

[Synthesis Examples 1-8; Synthesis of DA-8]

Compound (DA-8) was obtained according to the following Reaction Scheme 8 using the same synthesis reaction prescription as that of Compound (DA-1). Further, the first step in the synthesis of the mononitromonoiodide intermediate (the compound represented by the formula (DA-8-1)) is synthesized by a Friedel-Crafts reaction, Was synthesized by using a reduction reaction of a silanecarbonyl group with triethylsilane in the presence of trifluoromethanesulfonic acid.

[Synthesis Examples 1-9; Synthesis of compound (DA-9)

Compound (DA-9) was obtained according to the following Reaction Scheme 9 using the same synthesis reaction prescription as Compound (DA-1).

[Synthesis Example 1-10; Synthesis of Compound (DA-10)

Compound (DA-10) was obtained according to the following Reaction Scheme 10 using the same synthesis reaction prescription as Compound (DA-1). Further, the first step in the synthesis of the mononitromonohydroxy intermediate (compound represented by the formula (DA-10-1)) is synthesized by the Friedel-Crafts reaction, and the second step is the synthesis of the methoxy group , And the third step was synthesized by using a reduction reaction of silanecarbonyl group with triethylsilane in the presence of trifluoromethanesulfonic acid as a strong acid.

&Lt; Synthesis of Compound (C1) &gt;

[Synthesis Example 1-11; Synthesis of Compound (DA-22)

Compound (DA-22) was obtained according to Reaction Scheme 11 below. In the synthesis of the first step, an intermediate (a compound represented by the following formula (DA-22-1)) was obtained by a Krunnerbaagel reaction. The second step was reduction by the same method as that of the compound (DA-1).

[Synthesis Example 1-12; Synthesis of Compound (DA-23)

Compound (DA-22-1) was obtained by reducing the compound (DA-22-1) with water as a catalyst in the presence of zinc according to the following Reaction Scheme 12.

&Lt; Synthesis of Polymer &

Synthesis of polyamic acid

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

Tetracarboxylic acid dianhydride and diamine were added to the reaction vessel so that the total weight was 30 g at the mixing ratio (molar ratio) shown in the following Table 1, and further 170 g of N-methyl-2-pyrrolidone And the reaction was carried out at 60 占 폚 for 6 hours. The reaction mixture obtained 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 polymer (PAm-1). The values in Table 1 indicate the ratio (molar%) of the tetracarboxylic acid dianhydride to the total amount of the tetracarboxylic dianhydride used in the reaction, and the diamine was determined by the total amount of the diamine used in the reaction (% By mol) of the polymer. Then, the polymer (PAm-1) obtained above was dissolved in NMP so as to be 15% by weight, and the solution viscosity of each solution was measured. The measurement results are shown in Table 1 below. Further, the polymer solution obtained above was allowed to stand at 20 占 폚 for 3 days, and as a result, gelation did not occur, and storage stability was good.

[Synthesis Examples 2-2 to 2-18; Synthesis of polymer (PAm-2) to polymer (PAm-18)

(PAm-2) to polymer (PAm-18) were obtained in the same manner as in Synthesis Example 2-1 except that the mixing ratio of tetracarboxylic acid dianhydride and diamine was changed to the values shown in the following Tables 1 and 2 Respectively. The solution viscosities of the respective polymers were measured in the same manner as in Synthesis Example 2-1, and the results are shown in Table 1 and Table 2 below. Further, each of the polymer solutions obtained above was allowed to stand at 20 占 폚 for 3 days. As a result, none of the polymers except for the polymer (PAm-14) was gelated and storage stability was good. The polymer (PAm-14) was gelated and had no fluidity.

· Synthesis of polyimide

[Synthesis Example 3-1; Synthesis of Polymer (PIm-1)

A tetra-carboxylic acid dianhydride and diamine were added in the mixing ratio (molar ratio) shown in Table 2 so that the total weight was 30 g, and further 170 g of NMP was added thereto to synthesize a polyamic acid in the same manner as in Synthesis Example 2-1 . Subsequently, 200 g of NMP was added, and pyridine and acetic anhydride were added in amounts shown in the following Table 2 (the molar amount was expressed in terms of molarity relative to the total 100 parts by mol of the acid dianhydride), and the dehydration ring-closure reaction was carried out at 80 DEG C for 6 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 polymer (PIm-1).

Then, the polymer (PIm-1) obtained above was dissolved in NMP so as to be 15% by weight, and the solution viscosity of each solution was measured. The imidization rate was also measured. The measurement results are shown in Table 2 below. Further, the polymer solution obtained above was allowed to stand at 20 占 폚 for 3 days, and as a result, gelation did not occur, and storage stability was good.

[Synthesis Example 3-2; Synthesis of polymer (PIm-2)

(PIm-2) was obtained in the same manner as in Synthesis Example 3-1 except that the mixing ratio of the tetracarboxylic acid dianhydride and the diamine was changed to the values shown in Table 2 below. The solution viscosity of the polymer (PIm-2) was measured in the same manner as in Synthesis Example 3-1, and the measurement results of the imidization rate were also shown in Table 2 below. Further, the polymer solution obtained above was allowed to stand at 20 占 폚 for 3 days, and as a result, gelation did not occur, and storage stability was good.

The abbreviations of the compounds in Tables 1 and 2 have the following meanings. In Table 2, the numerical values of pyridine and acetic anhydride represent molar parts relative to the total 100 moles of the tetracarboxylic acid dianhydrides used in the reaction.

(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; Ethylenediaminetetraacetic acid dianhydride

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

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

AN-7; Propylene glycol bis (anhydrotrimellitate)

AN-8; 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride

(Diamine)

DA-11; 1,7-bis (4-aminophenoxy) heptane

DA-12; 4,4'-diaminodiphenylamine

DA-13; The compound represented by the following formula (DA-13)

DA-14; The compound represented by the following formula (DA-14)

DA-15; The compound represented by the following formula (DA-15)

DA-16; 4,4'-diaminodiphenylmethane

DA-17; 4-aminophenyl-4'-aminobenzoate

DA-18; The compound represented by the above formula (DA-18)

DA-19; 4- (4-aminophenoxycarbonyl) -1- (4-aminophenyl) piperidine

DA-20; 4- (tetradecanoxy) benzene-1,3-diamine

DA-21; 3,5-diaminobenzoic acid cholestanyl

· Synthesis of polyorganosiloxane containing photo-alignment group

[Synthesis Example 4-1; Synthesis of Polymer (PSi-1)

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, it was found that a peak based on the oxiranyl group was obtained in the vicinity of the chemical shift (?) = 3.2 ppm as the theoretical intensity and the side reaction of the oxiranyl group It is confirmed that this is not happening. 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 (PSi-1) as a white powder. The weight average molecular weight Mw of the polyorganosiloxane (PSi-1) in terms of polystyrene measured by GPC was 3,500.

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

(1) Preparation of liquid crystal aligning agent

50 parts by weight of the polymer (PAm-4) obtained in Synthesis Example 2-4 and 50 parts by weight of the polymer (PAm-11) obtained in Synthesis Example 2-11 as a polymer were dissolved in 50 parts by weight of? -Butyrolactone (GBL) Was dissolved in a mixed solvent (GBL: NMP: BC = 40:40:20 (weight ratio)) consisting of pyrrolidone (NMP) and butyl cellosolve (BC) to prepare a solution having a solid concentration of 3.5% by weight. This solution was filtered with a filter having a pore diameter of 0.2 mu m to prepare a liquid crystal aligning agent.

(2) Evaluation of surface roughness of the coating film

The liquid crystal aligning agent prepared above was coated on a glass substrate using a spinner, pre-baked on a hot plate at 80 DEG C for 1 minute, heated (post baking) in an oven at 200 DEG C in which the inside of the tube was replaced with nitrogen, Thereby forming a coating film having an average film thickness of 1,000 ANGSTROM. This coating film was observed with an atomic force microscope (AFM), and the center average roughness (Ra) was measured. The evaluation was made with the surface roughness "good" for Ra less than 2.0 nm, "possible" for case of less than 2.0 nm and less than 5.0 nm, and "defective" for case of 5.0 nm or more. In the present embodiment, Ra = 0.8 nm, and the surface roughness was &quot; good &quot;.

(3) Evaluation of transmittance

The coating film obtained above was evaluated for the light transmittance (%) at a wavelength of 400 nm using a spectrophotometer (150-20 type double beam manufactured by Hitachi, Ltd.). The evaluation was made as "good" when the light transmittance was 97% or more, "possible" when the light transmittance was less than 97% and "bad" when the light transmittance was less than 95%. As a result, the coating film was 99.0%, and the permeability was &quot; good &quot;.

(4) Evaluation of orientation

The thus obtained coating film was subjected to alignment treatment by irradiating polarized ultraviolet ray 300 K / m 2 containing a bright line of 313 nm from the normal direction of the substrate using an Hg-Xe lamp and Gantry prism. This alignment film glass substrate was measured for refractive index anisotropy (nm) using a liquid crystal alignment film inspection apparatus (LayScan) manufactured by MORITEX. The evaluation was made as "good" for the case of 0.020 nm or more, "possible" for the case of less than 0.020 nm and 0.010 nm or more, and "poor" for cases of less than 0.010 nm. As a result, the refractive index anisotropy of this substrate was 0.037 nm and the orientation was "good".

(5) Fabrication of FFS type liquid crystal display device using photo alignment method

An FFS type liquid crystal display element 10 shown in Fig. 1 was produced. First, a glass substrate 11a having a bottom electrode 15 having no pattern, a silicon nitride film as an insulating layer 14, and a comb electrode having a comb electrode pattern 13 formed in this order on one side are formed in this order. And the opposing glass substrate 11b on which the electrodes are not formed are formed on the glass substrate 11a and the liquid crystal alignment Was applied by using 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 13 used here is shown in Fig. 2 (a) is a top view of the top electrode 13, and Fig. 2 (b) is an enlarged view of a portion C1 surrounded by a broken line in Fig. 2 (a). In this embodiment, a substrate having a top electrode having a line width d1 of 4 mu m and a distance d2 between electrodes is 6 mu m. As the top electrode 13, driving electrodes of four lines of electrode A, electrode B, electrode C and electrode D were used. Fig. 3 shows the configuration of the driving electrode of this liquid crystal display element. In this case, the bottom electrode 15 functions as a common electrode acting on all four drive electrodes, and each of the four drive electrode regions becomes a pixel region.

Subsequently, polarizing ultraviolet rays of 300 J / m &lt; 2 &gt; containing a bright line of 313 nm were irradiated from the normal direction of the substrate to each surface of these coated films using a Hg-Xe lamp and a Glane Taylor prism, &Lt; / RTI &gt; At this time, the irradiation direction of the polarized ultraviolet ray was set from the normal direction of the substrate, and the light irradiation process was performed after setting the polarization plane direction such that the direction of the line segment projecting the polarizing plane of the polarized ultraviolet ray on the substrate was the direction of both arrows in Fig. 2 .

Subsequently, an epoxy resin adhesive containing an aluminum oxidephere having a diameter of 5.5 占 퐉 was applied to the periphery of the surface having one liquid crystal alignment film in the above substrate by screen printing, and then the liquid crystal alignment film faces of the pair of substrates were opposed to each other, The polarizing surfaces of ultraviolet rays were superimposed on each other so as to be parallel to the direction of projection onto the substrate, and the adhesive was thermally cured at 150 DEG C for 1 hour. Subsequently, a liquid crystal "MLC-6221" manufactured by Merck Ltd. was filled in the gap between the substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an epoxy resin adhesive. Thereafter, in order to remove the flow orientation at the time of injecting the liquid crystal, it was heated to 150 캜 and then slowly cooled to room temperature.

Next, a polarizing plate was bonded to both outer sides of the substrate to produce an FFS type liquid crystal display element. At this time, one of the polarizing plates is adhered so that the polarizing direction thereof is parallel to the projection direction of the polarizing plane of the polarized ultraviolet ray of the liquid crystal alignment film to the substrate surface, and the other polarizing direction is orthogonal to the polarizing direction of the preceding polarizing plate Bonded.

A total of five FFS type liquid crystal display devices were produced by repeating the above-described method, and one was provided for evaluating the liquid crystal orientation property, the heat resistance evaluation, the bezel nonuniformity resistance, the afterimage property and the contrast property described below. In either case, ultraviolet irradiation was not performed under voltage application. The polarizing plate was not bonded to the liquid crystal cell used for evaluating the contrast characteristics.

(6) 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;.

(7) 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 , And the voltage holding ratio was 99.4%. As a measuring apparatus, VHR-1 (manufactured by Toyotecnica Co., Ltd.) was used.

(8) Evaluation of heat resistance

(7) The voltage holding ratio was measured in the same manner as in the evaluation of the voltage holding ratio, and the value was regarded as the initial VHR (VHR _BF ). Subsequently, the liquid crystal display element after the initial VHR measurement was left in an oven at 100 캜 for 500 hours. Thereafter, the liquid crystal display was allowed to stand at room temperature and allowed to cool to room temperature. Then, the voltage holding ratio was measured in the same manner as described above, and the value was set as VHR _AF . Further, the rate of change (? VHR (%)) of the voltage holding ratio before and after application of thermal stress was determined by the following formula (EX-2).

? VHR (%) = ((VHR _BF - VHR _AF ) / VHR _BF ) 100 ... (EX-2)

The evaluation of the heat resistance was carried out under the conditions that the change rate? VHR was less than 4% and the heat resistance was &quot; acceptable &quot; when the change rate? VHR was less than 4% and less than 5%, respectively. As a result,? VHR was 2.9%, and the heat resistance of this liquid crystal display element was "good".

(9) Nonuniform resistance around the sealant (bezel nonuniformity resistance)

The FFS type liquid crystal display device manufactured as described above was stored for 30 days under the conditions of 25 DEG C and 50% RH, and then driven at an alternating voltage of 5 V to observe the lighting state. In the evaluation, if the luminance difference (mower black or mower white) is not observed in the vicinity of the sealant, the result is &quot; excellent &quot;, but if the luminance difference is lost within 5 minutes after lighting, the luminance difference disappears within 5 minutes and within 20 minutes , &Quot; Possible &quot;, and a case where the luminance difference is visible even after 20 minutes has elapsed is &quot; bad &quot;. As a result, the luminance difference of this liquid crystal display element was not visually recognized, and it was judged as &quot; good &quot;.

(10) Evaluation of after-image characteristic (DC after image evaluation)

The photo alignment type liquid crystal display device prepared above was placed under an environment of 25 캜 and 1 atm. The bottom electrode was used as a common electrode for all four driving electrodes, and the potential of the bottom electrode was set at 0V (ground potential). The electrode B and the electrode D were short-circuited with the common electrode and 0 V was applied, and a composite voltage consisting of an AC voltage of 3.5 V and a DC voltage of 1 V was applied to the electrode A and the electrode C for 2 hours. After a lapse of 2 hours, a voltage of 1.5 V was applied to all of the electrodes A to D immediately. When the voltage of 1.5 V AC is applied to all the driving electrodes, the luminance of the driving stress application areas (the pixel areas of the electrodes A and C) and the driving stress non-coverage areas (the pixel areas of the electrodes B and D) The time until the car can not be visually confirmed was measured, and this was defined as the afterimage erasing time. Also, the shorter the time, the less likely the afterimage to occur. The case where the afterimage erase time was less than 30 seconds was evaluated as &quot; good &quot;, the case where it was less than 120 seconds and less than 120 seconds as &quot; The erase time was 1 second, and the afterimage characteristic was evaluated as &quot; good &quot;.

(11) Evaluation of contrast characteristics after driving stress (AC residual image evaluation)

Using a device in which the polarizing plate and the analyzer were disposed between the light source and the light amount detector after driving the FFS type liquid crystal cell (the polarizing plate not bonded) manufactured above with an AC voltage of 10 V for 30 hours, -3) was measured: &lt; RTI ID = 0.0 &gt;

Minimum relative transmittance (%) = {(? - B ₀ ) / (B _{100 -} B ₀ )} × 100 (EX-3)

(Formula (EX-3) of the, B ₀ is a permeation amount of light under Cross-Nicol in the blank B ₁₀₀ is, the permeation amount of p-Nicol under the light as a blank; β, the liquid crystal between the under Cross-Nicol polarizer and analyzer's The minimum amount of light transmittance with the display element sandwiched therebetween).

The black level in the dark state is represented by the minimum relative transmittance of the liquid crystal display element, and the smaller the black level in the dark state is, the better the contrast characteristic is. The minimum relative transmittance of less than 0.5% was evaluated as &quot; good &quot;, and those having a relative transmittance of less than 0.5% and less than 1.0% were evaluated as &quot; feasible &quot; As a result, the minimum relative transmittance of this liquid crystal display element was 0.2%, and the contrast characteristic was judged as &quot; good &quot;.

[Examples 1-2, 1-3, and Comparative Example 1-1]

A liquid crystal aligning agent was prepared in the same manner as in Example 1-1 except that the kind and amount of the polymer used in the preparation of the liquid crystal aligning agent were changed as shown in Table 3 respectively, Respectively. The evaluation results are shown in Table 3 below.

[Example 2-1: Rubbing FFS type liquid crystal display element]

(1) Preparation of liquid crystal aligning agent

The polymer (PAm-1) obtained in Synthesis Example 2-1 as a polymer was dissolved in a mixed solvent consisting of? -Butyrolactone (GBL), N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (GBL: NMP: BC = 40: 40: 20 (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.

(2) Evaluation of surface roughness of the coating film

The liquid crystal aligning agent prepared above was coated on a glass substrate using a spinner, pre-baked on a hot plate at 80 DEG C for 1 minute, heated (post baking) in an oven at 200 DEG C in which the inside of the tube was replaced with nitrogen, Thereby forming a coating film having an average film thickness of 1,000 ANGSTROM. This coating film was evaluated in the same manner as in (2) of Example 1-1 to evaluate the surface roughness of the coating film. As a result, the Ra of the coating film was 0.9 nm, and the surface roughness was "good".

(3) Evaluation of transmittance

The coating film obtained above was evaluated in the same manner as in (3) of Example 1-1. As a result, the transmittance of this coating film was 98.5%, and the permeability was &quot; good &quot;.

(4) Evaluation of rubbing resistance

The coating film obtained above was subjected to rubbing treatment seven times at a roll rotation speed of 1000 rpm, a stage moving speed of 20 cm / sec, and a hair embroidering length of 0.4 mm by a rubbing machine having a roll covered with a cotton cloth. The foreign matter (piece of coating film) caused by the rubbing abrasion on the obtained substrate 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, "possible" when the number was 4 or more and 7 or less, and "rubbing resistance" when the number was 8 or more. As a result, foreign matter was not observed, and the rubbing resistance of this coating film was &quot; good &quot;.

(5) Evaluation of orientation

The glass substrate with an alignment film subjected to the rubbing alignment treatment obtained above was subjected to the same evaluation as in (4) of Example 1-1. As a result, the substrate had a refractive index anisotropy of 0.031 nm and was &quot; good &quot;.

(6) Fabrication of FFS type liquid crystal display device using rubbing method

An FFS type liquid crystal display element shown in Fig. 1 was produced in the same manner as (5) of Example 1-1. A schematic plan view of the top electrode 13 used here is shown in Fig. 4 (a) is a top view of the top electrode 13, and Fig. 4 (b) is an enlarged view of a portion C1 surrounded by a broken line in Fig. 4 (a). In this embodiment, a substrate having a top electrode whose line width d1 is 4 mu m and whose distance d2 between electrodes is 6 mu m is used.

Then, each surface of the coated film formed on the glass substrate was subjected to rubbing treatment with cotton to obtain a liquid crystal alignment film 12. In Fig. 4 (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 11a and 11b were anti-parallel, and liquid crystal MLC-6221 (manufactured by Merck Ltd.) . A polarizing plate (not shown) was bonded to the outer sides of the substrates 11a and 11b so that the polarizing directions of the two polarizing plates were orthogonal to each other, thereby producing the liquid crystal display element 10. [

(7) Evaluation of liquid crystal orientation

The liquid crystal alignability of the rubbing FFS type liquid crystal display device manufactured as described above was evaluated in the same manner as in item (6) of Example 1-1. As a result, in this liquid crystal display element, the liquid crystal alignment property was "good".

(8) Evaluation of voltage holding ratio and heat resistance

The rubbing FFS type liquid crystal display device manufactured as described above was measured for the voltage holding ratio (VHR _BF ) in the same manner as in (7) of Example 1-1, In the same manner, the heat resistance of the liquid crystal display element was evaluated by the rate of change of the voltage holding ratio before and after application of heat stress. As a result, the VHR _BF was 99.4%. Further, the? VHR was 1.6%, and the heat resistance was judged as "good".

(9) Nonuniform resistance around the sealant (bezel nonuniformity resistance)

The bezel nonuniformity resistance was evaluated in the same manner as in (9) of Example 1-1. As a result, the luminance difference of the liquid crystal display element was not visually recognized, and the bezel nonuniformity resistance was judged as &quot; good &quot;.

(10) Evaluation of after-image characteristic (DC after image evaluation)

Evaluation of the DC afterimage was carried out in the same manner as (10) of Example 1-1. As a result, the after-image erasing time of this liquid crystal display element was 2 seconds and evaluated as &quot; good &quot;.

(11) Evaluation of contrast characteristics after driving stress (AC residual image evaluation)

Evaluation of AC residual image was performed in the same manner as (11) in Example 1-1. Also in this case, evaluation was performed using a liquid crystal cell to which a polarizing plate was not bonded. As a result, the minimum relative transmittance was 0.1%, and the contrast characteristic was judged as &quot; good &quot;.

[Examples 2-2 to 2-15 and Comparative Examples 2-1 to 2-5]

A liquid crystal aligning agent was prepared in the same manner as in Example 2-1 except that the kind and amount of the polymer used in the preparation of the liquid crystal aligning agent were changed as shown in Table 4, I appreciated. However, in Comparative Example 2-4, the liquid crystal alignability was poor and no evaluation was made on the liquid crystal cell. The evaluation results are shown in Tables 4 and 5 below.

As shown in Tables 3 to 5, in the liquid crystal aligning agent containing the polymer obtained by using the compound (C '), good results were obtained for the surface irregularity, permeability, rubbing resistance and orientation of the coating film. The liquid crystal display device manufactured using these liquid crystal aligning agents exhibited good results in both the alignment properties of the liquid crystal molecules, the voltage holding ratio, the heat resistance, the bezel nonuniformity resistance, the afterimage characteristic (DC afterimage) and the contrast characteristic (AC afterimage) It was able to combine various characteristics well.

On the contrary, in Comparative Example 2-1 using a diamine having only an aromatic amine structure but no aromatic amine structure, the afterimage characteristic was "poor" and the bezel nonuniformity resistance and heat resistance were inferior to those in Examples. It was not enough to achieve the purpose.

In Comparative Examples 1-1, 2-2 and 2-3 using diamines having only an aromatic amine structure, the heat resistance, bezel non-uniformity resistance and contrast characteristics of the liquid crystal display element were "poor". Further, Comparative Example 2-4 using PAm-14 was not suitable for use as a liquid crystal display element, because the storage stability of the polymer, the surface roughness and the transmittance of the coating film were poor, and the orientation of the liquid crystal was poor. In Comparative Example 2-5, the heat resistance and the bezel nonuniformity resistance were &quot; defective &quot;. In addition, when the transmittance, the rubbing resistance and the orientation of the coating film, the orientation of the liquid crystal, the voltage holding ratio, the heat resistance, the bezel nonuniformity resistance, the afterimage resistance and the contrast characteristic of the liquid crystal display device are collectively examined, .

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

(1) Preparation of liquid crystal aligning agent

50 parts by weight of the polymer (PAm-3) obtained in Synthesis Example 2-3 and 50 parts by weight of the polymer (PAm-16) obtained in Synthesis Example 2-16 as a polymer were dissolved in a mixed solvent of NMP and BC (NMP: BC = 50: (Weight ratio)) to obtain a solution having a solid content 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.

(2) Evaluation of printability

The liquid crystal aligning agent prepared in (1) above was applied to the transparent electrode surface of a glass substrate with a transparent electrode made of an ITO film using a liquid crystal alignment film printing machine (manufactured by Nippon Sha Sein Insights Co., Ltd.) After the solvent was removed by heating (prebaking) for 1 minute, it was heated on a hot plate at 200 ° 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) Evaluation of transmittance

The coating film obtained above was evaluated in the same manner as in (3) of Example 1-1. As a result, the transmittance of this coating film was 98.4%, which was &quot; good &quot;.

(4) Preparation of TN type liquid crystal cell

The liquid crystal aligning agent prepared in (1) above was applied to the transparent electrode surface of a glass substrate with a transparent electrode made of an ITO film using a liquid crystal alignment film printing machine (manufactured by Nippon Sha Sein Insights Co., Ltd.) After the solvent was removed by heating (prebaking) for 1 minute, it was heated on a hot plate at 200 ° 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 spring at a roll rotation speed of 500 rpm, a stage moving speed of 3 cm / sec, and a piercing length of 0.4 mm to give a liquid crystal aligning ability. 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, an epoxy resin adhesive containing an aluminum oxide spheres having a diameter of 5.5 mu m was applied to the outer edge of the surface having the liquid crystal alignment film on one of the pair of substrates, and then the pair of substrates was laminated on the liquid crystal alignment film surface Are superimposed on each other so as to be opposed to each other, and the adhesive is cured. Next, a nematic liquid crystal (MLC-6221, manufactured by Merck Ltd.) was filled between a pair of substrates from a 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.

(5) Evaluation of alignment of liquid crystal

With respect to the liquid crystal cell prepared in (4) above, the presence or absence of an abnormal domain when a voltage of 5 V was turned on / off under Cross-Nicol was observed under a microscope at a magnification of 50 times. Evaluation was carried out in the same manner as in (6) of Example 1-1. As a result, in this liquid crystal display element, the liquid crystal alignment property was "good".

(6) Evaluation of pre-tilt angle stability

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 for the liquid crystal cell manufactured in (4), and this value was set as the initial pretilt angle? _IN . The crystal rotation method is disclosed in Non-Patent Document 3 (TJ Scheffer et al., J. Appl. Phys. Vol. 48, p. 1783 (1977)) and Non-Patent Document 4 (F. Nakano et al., JPN.J.Appl.Phys.vol.19 , p2013 (1980)).

Subsequently, an AC voltage of 5 V was applied to the liquid crystal cell 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 expression (EX-4), and the amount of change (?? (°)) of the pretilt angle before and after voltage application was obtained.

_{Δθ = | θ AF -θ IN |} ... (EX-4)

The pretilt angle stability was evaluated as "good" when Δθ was less than 3%, the pretilt angle stability "possible" was defined as 3% or more and less than 4%, and the pretilt angle stability was evaluated as "defective" As a result, the change rate of the pretilt angle of this liquid crystal display element was 1.6%, and it was judged that the pretilt angle stability was "good".

(7) Evaluation of voltage holding ratio and heat resistance

(VHR _BF ) was measured in the same manner as in (7) of Example 1-1, and in the same manner as in (8) of Example 1-1, the rate of change of the voltage holding ratio To evaluate the heat resistance of the liquid crystal display element. As a result, the VHR _BF was 98.6%. The? VHR was 2.1%, and the heat resistance was judged as "good".

(8) Nonuniform resistance around the sealant (bezel nonuniformity resistance)

The bezel nonuniformity resistance was evaluated in the same manner as in (9) of Example 1-1. As a result, the luminance difference of this liquid crystal display element was not visually recognized, and it was judged as &quot; good &quot;.

(9) Evaluation of afterimage characteristic (DC afterimage evaluation)

Evaluation of the DC afterimage was carried out in the same manner as (10) of Example 1-1. As a result, the after-image erasing time of this liquid crystal display element was 12 seconds and evaluated as &quot; good &quot;.

[Example 4-1: VA type liquid crystal display device]

(1) Preparation of liquid crystal aligning agent

20 parts by weight of the polymer (PIm-2) obtained in Synthesis Example 3-2 and 80 parts by weight of the polymer (PAm-3) obtained in Synthesis Example 2-3 were mixed in a mixed solvent of NMP and BC (NMP: BC = 50: (Weight ratio)) to obtain a solution having a solid content 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.

(2) Evaluation of printability

Using the liquid crystal aligning agent prepared in (1) above, the printability was examined in the same manner as in (2) of Example 3-1. As a result, both print unevenness and pinholes were not observed and the printability was "good" .

(3) Evaluation of transmittance

The coating film obtained above was evaluated in the same manner as in (3) of Example 1-1. As a result, the coating film was 99.2%, and the permeability of the coating film was &quot; good &quot;.

(4) Production of VA type liquid crystal cell

The liquid crystal aligning agent prepared above was applied to a transparent electrode surface of a glass substrate (1 mm thick) having a transparent electrode made of an ITO film by using a liquid crystal alignment film printing machine (manufactured by Nippon Sha Shingen Co., Ltd.). Subsequently, the substrate was heated (prebaked) on a hot plate at 80 占 폚 for 1 minute and further heated (post baking) for 60 minutes on a hot plate at 200 占 폚 to form a coating film (liquid crystal alignment film) with an average film thickness of 800 占. 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 Pressed to each other, 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.

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

The liquid crystal cell prepared in (4) above was evaluated for liquid crystal alignability in the same manner as in (6) of Example 1-1, and as a result, the liquid crystal alignability of this liquid crystal cell was "good". The voltage holding ratio (VHR _BF ) was measured in the same manner as in (7) of Example 1-1, and in the same manner as in (8) of Example 1-1, the heat resistance ) Was evaluated. As a result, the VHR _BF was 99.0%. The? VHR was 2.3%, and the heat resistance was judged as "good".

(6) Nonuniform resistance around the sealant (bezel nonuniformity resistance)

The bezel nonuniformity resistance was evaluated in the same manner as in (9) of Example 1-1. As a result, the difference in luminance of the liquid crystal cell was not visually recognized, and it was judged as &quot; good &quot;.

[Example 5-1: retardation film]

(1) Preparation of liquid crystal aligning agent

100 parts by weight of the polymer (PAm-1) obtained in Synthesis Example 2-1 and 10 parts by weight of the polymer (PSi-1) obtained in Synthesis Example 4-1 were mixed in a mixed solvent of NMP and BC (NMP: BC = 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.

(2) Production of retardation film

On one side of the TAC film as the substrate, the liquid crystal aligning agent prepared above was applied using a bar coater and baked in an oven at 120 deg. C for 2 minutes 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 light irradiation to form a coating film of a polymerizable liquid crystal . 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 to produce a retardation film.

(3) Evaluation of liquid crystal orientation

The liquid crystal alignability (optical alignment property) of the retardation film prepared in (2) above was evaluated 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 ideal domain was not observed by a polarizing microscope, the liquid crystal alignability was evaluated as &quot; good &quot;, and when the abnormal domain was not observed visually, , 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;

(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. First, using a gap spacer with a guide, insertion was made from the side of the liquid crystal layer side of the retardation film by a cutter knife, and 10 x 10 grid patterns were formed in the range of 1 cm x 1 cm. The depth of each infeed was set to reach the middle of the thickness of the substrate from the liquid crystal layer surface. 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 cut-out portion of the grid pattern after peeling was observed by naked eye under Cross Nicol to evaluate the adhesion. In the evaluation, when the peeling was not confirmed at the portion along the cut-off line and at the intersection of the lattice patterns, the adhesion was evaluated as &quot; good &quot;, and the number of lattice planes in which the peeling was observed was less than 15% , And adhesion was evaluated as &quot; possible &quot;. When the number of the lattice planes in which the peeling was observed was 15% or more of the total number of lattice patterns, the adhesion was evaluated as &quot; poor &quot;. As a result, the retardation film had good adhesion.

10: Liquid crystal display element
11a and 11b: glass substrate
12: liquid crystal alignment film
13: Top electrode
14: Insulating layer
15: bottom electrode
16: liquid crystal layer

Claims (19)

A compound (C) having the following structure (a) and the following structure (b) and a reactive group having the following structure (a) and the following structure (b1) (P) obtained by using at least one kind of compound (C ') selected from the group consisting of a compound
(a) an aromatic amine structure in which two or three aromatic rings are bonded to the same nitrogen atom;
(b) a bivalent chain hydrocarbon group having 6 or more carbon atoms and at least one methylene group in the chain hydrocarbon group is -O-, -S-, -CO-, -NR-, -NRCO-, -COO-, -COS - or -Si (CH ₃ ) ₂ - (R is a hydrogen atom or a monovalent organic group).
(b1) a divalent chain hydrocarbon having 1 to 5 carbon atoms, at least one methylene group in the art chain hydrocarbon groups ^{-O-, -S-, -CO-, -NR 3} -, -NR 3 CO-, -COO -, -COS- or -Si (CH ₃ ) ₂ -, -O-, -S-, -CO-, -NR ³ CO- (R ³ is a hydrogen atom or a monovalent organic group ), -COO-, -COS-, and -Si (CH ₃ ) ₂ -. The method according to claim 1,
The compound (C) is a compound having two or more aromatic amine structures (a) in the molecule. The method according to claim 1,
Wherein the polymer (P) is at least one selected from the group consisting of polyamic acid, polyamic acid ester and polyimide. The method according to claim 1,
The compound (C) is a liquid crystal aligning agent which is a compound represented by the following formula (1)

Wherein A ¹ and A ³ are each independently a hydrogen atom or a monovalent organic group; A ² and A ⁴ are each independently a single bond or a divalent organic group; B ¹ and B ² Provided that when B ¹ is a single bond, at least one of A ¹ and A ² is an aromatic ring bonded to a nitrogen atom, and B ¹ is a divalent organic At least two of A ¹ , A ² and B ¹ are bonded to a nitrogen atom as an aromatic ring; and when B ² is a single bond, at least one of A ³ and A ⁴ is an aromatic ring, At least two of A ³ , A ⁴ and B ² are bonded to a nitrogen atom as an aromatic ring when B ² is a divalent organic group; L ¹ is a divalent group comprising the structure (b) ). 5. The method of claim 4,
Wherein at least any one of B ¹ and B ² is a single bond. 5. The method of claim 4,
Wherein L &lt; ¹ &gt; is a liquid crystal aligning agent represented by the following formula (2)

(2), L ² and L ³ are each independently the structure (b), Q is a divalent group represented by the following formula (3) or (4), n is 0 to 4 Integer &quot; and &quot; * &quot; denotes a combined hand);

(In the formula (3), A ⁵ is a hydrogen atom or a monovalent organic group; R ¹ and R ² are substituents and may be the same or different;

(In the formula (4), A ⁶ is a hydrogen atom or a monovalent organic group; "*" indicates a bonding hand). 5. The method of claim 4,
The compound (C) is a liquid crystal aligning agent which is a compound represented by the following formula (1-1)

(In the formula (1-1), L ¹¹ represents at least one methylene group in the bivalent chain hydrocarbon group having 6 or more carbon atoms as -O-, -S-, -CO-, -NR-, -NRCO-, -COO -, -COS-, or _{-Si (CH 3) 2 - (} R is a hydrogen atom or a monovalent organic group Im) group and the divalent group containing a ^{substituted; a 1, a 2, a} 3, a 4, B ¹ and B ² have the same meanings as in the formula (1), provided that when L ¹¹ has an alkanediyl group having 1 to 5 carbon atoms, at least one of A ¹ and A ³ is a hydrogen atom or B ¹ And B &lt; ^{2 &gt;} is a divalent organic group). 5. The method of claim 4,
The compound (C) is a liquid crystal aligning agent which is a compound represented by the following formula (1-2)

(In formula (1-2) of, L ¹² is a divalent group having a carbon number of 6 or more comprising a divalent chain hydrocarbon, ^{and; A 1, A 2, A} 3, A 4, B 1 and B ^2, the formula ( 1)). The method according to claim 1,
The compound (C1) is a liquid crystal aligning agent which is a compound represented by the following formula (1-3)

Wherein A ⁷ is a hydrogen atom or a monovalent organic group, A ⁸ and A ⁹ are each independently a single bond or a divalent organic group, with the proviso that A ⁷ , A ⁸ and A ⁹ At least two of them are bonded to a nitrogen atom through an aromatic ring; L ⁴ is the above structure (b1); and L ⁵ is a single bond or a divalent organic group. The method according to claim 1,
The polymer (P) is at least one member selected from the group consisting of a polyamic acid, a polyamic ester and a polyimide obtained by reacting a tetracarboxylic acid dianhydride with a diamine containing the compound (C '),
Wherein the tetracarboxylic acid dianhydride is selected from the group consisting of 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, Oxacyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic dianhydride, ethylenediamine 4 acetic acid dianhydride, cyclopentanetetracarboxylic acid dianhydride, 1,3-propylene glycol bis (anhydrotrimel Tate) and a liquid crystal alignment containing at least one fatigue selected from the group consisting of pyromellitic acid dianhydride. The method according to claim 1,
Wherein the compound (C ') has a molecular weight of 1,000 or less. A liquid crystal alignment film formed using the liquid crystal aligning agent according to any one of claims 1 to 11. A liquid crystal display element comprising the liquid crystal alignment film according to claim 12. A retardation film comprising the liquid crystal alignment film according to claim 12. A method for manufacturing a liquid crystal display device, comprising the steps of: applying a liquid crystal aligning agent according to any one of claims 1 to 11 on a substrate to form a coated film; irradiating the coated film with light; And then curing the film. A polymer selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide,
At least one compound selected from the group consisting of a tetracarboxylic acid dianhydride, a tetracarboxylic acid di-ester compound and a tetracarboxylic acid diester dihalide, a compound represented by the following formula (1-1) 2) and a diamine including at least one member selected from the group consisting of compounds represented by the following formula (1-3) in the reaction:

(In formula (1-1) of, A ¹ and A ³ are each independently a hydrogen atom or a monovalent organic group, A ² and A ⁴ are each independently a single bond or a divalent organic group, and; B ¹ and B ² are each independently a single bond or a divalent organic group, and; stage, B ¹ in this case, a single bond is, a ¹ and a ² at least one of is and bonded to the nitrogen atom in the aromatic ring, B ¹ is 2 At least two of A ¹ , A ² and B ¹ are bonded to a nitrogen atom as an aromatic ring, and when B ² is a single bond, at least one of A ³ and A ⁴ is an aromatic ring, When B ² is a divalent organic group, at least two of A ³ , A ⁴ and B ² are bonded to a nitrogen atom as an aromatic ring; L ¹¹ represents a divalent straight chain hydrocarbon group having 6 or more carbon atoms; (Wherein R is a hydrogen atom or a methylene group having 1 to ₃ carbon atoms), and R &lt; ₂ &gt; Is the organic component of A divalent group comprising a group gt; stage, in this case ¹¹ L having a alkanediyl group having a carbon number of 1~5, A ¹ and A ³ is at least any one of a hydrogen atom, or at least one of B ¹ and B ^2, Is a bivalent organic group);

(Wherein (1-2), L ¹² is a divalent group having a carbon number of 6 or more comprising a divalent chain hydrocarbon, and; A ^1, A ^2, A ^3, A ^4, B ¹ and B ² has the formula (1 -1), provided that when L ¹² is an alkanediyl group having 6 to 10 carbon atoms, at least one of A ¹ and A ³ is a monovalent organic group, or at least one of B ¹ and B ² Is a bivalent organic group);

Wherein A ⁷ is a hydrogen atom or a monovalent organic group, A ⁸ and A ⁹ are each independently a single bond or a divalent organic group, with the proviso that A ⁷ , A ⁸ and A ⁹ L ⁴ represents a divalent straight chain hydrocarbon group having 1 to 5 carbon atoms, at least one methylene group in the chain hydrocarbon group is bonded to -O-, -S-, - -CO-, -NR ³ -, -NR ³ CO-, -COO-, -COS- or -Si (CH ₃ ) ₂ -, -O-, -S-, NR ³ CO- wherein R ³ is a hydrogen atom or a monovalent organic group, -COO-, -COS-, or -Si (CH ₃ ) ₂ -; and L ⁵ is a single bond or a divalent organic group. A compound represented by the following formula (1-1):

(In formula (1-1) of, A ¹ and A ³ are each independently a hydrogen atom or a monovalent organic group, A ² and A ⁴ are each independently a single bond or a divalent organic group, and; B ¹ and B ² are each independently a single bond or a divalent organic group, and; stage, B ¹ in this case, a single bond is, a ¹ and a ² at least one of is and bonded to the nitrogen atom in the aromatic ring, B ¹ is 2 At least two of A ¹ , A ² and B ¹ are bonded to a nitrogen atom as an aromatic ring, and when B ² is a single bond, at least one of A ³ and A ⁴ is an aromatic ring, When B ² is a divalent organic group, at least two of A ³ , A ⁴ and B ² are bonded to a nitrogen atom as an aromatic ring; L ¹¹ represents a divalent straight chain hydrocarbon group having 6 or more carbon atoms; (Wherein R is a hydrogen atom or a methylene group having 1 to ₃ carbon atoms), and R &lt; ₂ &gt; Is the organic component of Divalent group by including a group consisting gt; However, in this case ¹¹ L having an alkanediyl group having a carbon number of 1~5, A ¹ and A ³ is at least any one of a hydrogen atom, or B ¹ and B ^2, at least one of One is a bivalent organic group). A compound represented by the following formula (1-2):

(In formula (1-2) of, A ¹ and A ³ are each independently a hydrogen atom or a monovalent organic group, A ² and A ⁴ are each independently a single bond or a divalent organic group, and; B ¹ and B ² are each independently a single bond or a divalent organic group, and; stage, B ¹ in this case, a single bond is, a ¹ and a ² at least one of is and bonded to the nitrogen atom in the aromatic ring, B ¹ is 2 At least two of A ¹ , A ² and B ¹ are bonded to a nitrogen atom as an aromatic ring, and when B ² is a single bond, at least one of A ³ and A ⁴ is an aromatic ring, When B ² is a divalent organic group, at least two of A ³ , A ⁴ and B ² are bonded to a nitrogen atom as an aromatic ring; L ¹² is a divalent straight chain hydrocarbon group having 6 or more carbon atoms; , Provided that when L ¹² is an alkanediyl group having 6 to 10 carbon atoms, at least one of A ¹ and A ³ is a monovalent organic group, or Is at least one of B &lt; ^{1 &gt;} and B &lt; ^{2 &gt;} is a divalent organic group). A compound represented by the following formula (1-3):

Wherein A ⁷ is a hydrogen atom or a monovalent organic group, A ⁸ and A ⁹ are each independently a single bond or a divalent organic group, with the proviso that A ⁷ , A ⁸ and A ⁹ L ⁴ represents a divalent straight chain hydrocarbon group having 1 to 5 carbon atoms, at least one methylene group in the chain hydrocarbon group is bonded to -O-, -S-, - -CO-, -NR ³ -, -NR ³ CO-, -COO-, -COS- or -Si (CH ₃ ) ₂ -, -O-, -S-, NR ³ CO- wherein R ³ is a hydrogen atom or a monovalent organic group, -COO-, -COS-, or -Si (CH ₃ ) ₂ -; and L ⁵ is a single bond or a divalent organic group.

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