KR20170105059A - Liquid crystal alignment agent using non-photoreactive hydrogen-bonding polymer liquid crystal, and liquid crystal alignment film - Google Patents

Abstract

According to the present invention, even when a polymer composition that does not exhibit photoreactivity is used, a liquid crystal alignment film having orientation control ability with high efficiency and a wide range of an optimal amount of irradiated polarized ultraviolet rays is provided. The present invention relates to a liquid crystal composition containing a component (A) and a component (B), wherein the component (B) contains a photoreactive group and the components (A) and (A) a polymer having a side chain containing a carboxylic acid group structure, and (B) a polymer represented by the following formula (1): wherein the definition of symbols in the formula is as described in the specification. And aromatic compounds, the above problems are solved.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a liquid crystal aligning agent and a liquid crystal alignment film,

The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film, a liquid crystal display element using the same, and a polymer film suitable for producing an optical element in which molecular orientation of a retardation film or a polarizing diffraction element is controlled.

BACKGROUND ART A liquid crystal display device is known as a lightweight, thin and low power consumption display device, and recently it has been used for a large-sized television and has achieved remarkable progress. The liquid crystal display element is constituted by sandwiching the liquid crystal layer by a pair of transparent substrates having electrodes, for example. In the liquid crystal display element, an organic film made of an organic material is used as a liquid crystal alignment film so that the liquid crystal is in a desired alignment state between the substrates.

That is, the liquid crystal alignment film is a constituent member of a liquid crystal display element and is formed on the surface of the substrate which holds the liquid crystal in contact with the liquid crystal, and plays a role of orienting the liquid crystal in a certain direction between the substrates. In addition to the role of aligning the liquid crystal in a certain direction such as a direction parallel to the substrate, for example, the liquid crystal alignment film may be required to control the pretilt angle of the liquid crystal. The ability to control the alignment of the liquid crystal in such a liquid crystal alignment film (hereinafter referred to as orientation control ability) is given by subjecting the organic film constituting the liquid crystal alignment film to an alignment treatment.

Conventionally, a rubbing method is known as an alignment treatment method of a liquid crystal alignment film for imparting alignment control ability. The rubbing method is a method of rubbing (rubbing) the surface of an organic film such as polyvinyl alcohol, polyamide, or polyimide on a substrate with a cloth such as a cotton, nylon, or polyester in a predetermined direction, To orient the liquid crystal. This rubbing method has been used in a manufacturing process of a conventional liquid crystal display element since a relatively stable liquid crystal alignment state can be realized easily. As an organic film used for a liquid crystal alignment film, a polyimide-based organic film having excellent reliability and electrical characteristics such as heat resistance has been mainly selected.

However, in the rubbing method of rubbing the surface of the liquid crystal alignment film made of polyimide or the like, generation of oscillation or static electricity is a problem in some cases. In addition, since the liquid crystal display element of recent years has a high definition, and the surface of the liquid crystal alignment film can not be uniformly rubbed with the cloth due to unevenness caused by the electrode on the substrate or the switching active element for liquid crystal driving, uniform alignment of liquid crystal can be realized There was no case.

Therefore, as another method of aligning the liquid crystal alignment film without rubbing, a photo alignment method is actively studied.

There are various methods for the photo alignment method, but anisotropy is formed in the organic film constituting the liquid crystal alignment film by linearly polarized light or collimated light, and the liquid crystal is oriented in accordance with the anisotropy. As the main alignment method, there is a method in which a "photodegradation type" or a polyvinyl cinnamate which causes anisotropic decomposition in a molecular structure is irradiated with polarized ultraviolet rays, and polarized ultraviolet rays are irradiated to form two side chains (For example, refer to Patent Document 1) which causes a dimerization reaction (cross-linking reaction) at the double bond portion of the azobenzene moiety (see, for example, Patent Document 1) and a side chain type polymer having azobenzene as a side chain, Quot; isomerization type " (see, for example, Non-Patent Document 2) for causing an isomerization reaction in the azobenzene moiety of a side chain parallel to polarized light and orienting the liquid crystal in a direction orthogonal to the polarization direction.

On the other hand, a new photo alignment method (hereinafter also referred to as an orientation amplification method) using a photosensitive side chain type polymer capable of exhibiting liquid crystallinity has been studied. This is because the alignment treatment is performed on the film having the photosensitive side chain type polymer capable of manifesting liquid crystallinity by the irradiation of polarized light and then the side chain type polymer film is heated, . At this time, a slight anisotropy expressed by the polarized light irradiation becomes a driving force, and the liquid crystalline side chain type polymer itself is efficiently rearranged by self-organization. As a result, a highly efficient alignment treatment can be realized as a liquid crystal alignment film, and a liquid crystal alignment film with high alignment control capability can be obtained (see, for example, Patent Document 2).

Since the polymer film obtained by this orientation amplification method exhibits birefringence due to molecular orientation, it can be used as various optical elements such as a retardation film in addition to the use of a liquid crystal alignment film.

Japanese Patent No. 3893659 International Publication WO2014 / 054785

 M. Shadt et al., Jpn. J. Appl. Phys. 31, 2155 (1992)  K. Ichimura et al., Chem. Rev. 100, 1847 (2000)

The irradiation amount of the polarized ultraviolet ray most suitable for introduction of high-efficiency anisotropy into the liquid crystal alignment film used in the orientation amplification method corresponds to the irradiation amount of polarized ultraviolet ray that optimizes the amount of photo-reaction of the photosensitive group in the coating film. As a result of irradiating polarized ultraviolet rays to the liquid crystal alignment film used in the orientation amplification method, a sufficient amount of photoreactivity can not be obtained if the number of photosensitive groups in the photoreactive side chain is small. In that case, sufficient self-organization does not proceed even after heating. On the other hand, if the photosensitive group of the photoreactive side chain becomes excessive, the resultant film becomes rigid, which may interfere with the progress of self-organization by the subsequent heating.

At present, there are some liquid crystal alignment films used in the orientation amplification method because of the high sensitivity of the photoreactive groups in the polymer being used or the region of the irradiation amount of the above-mentioned optimal polarized ultraviolet ray is narrow. As a result, the manufacturing efficiency of the liquid crystal display element is lowered.

Further, in the conventional alignment amplification method, it is necessary to have a photoreactive group in the polymer skeleton used, and when the polymer does not contain a photoreactive group, it forms a chemical bond with the polymer by heat or light It is necessary to perform chemical modification by adding an additive having a polymerizable group having a functional group capable of reacting with a polymerizable group. Therefore, it has been difficult to obtain a highly uniaxially oriented thin film made of a polymer having only a polymer having no photoreactive group.

Further, when the firing temperature of the liquid crystal alignment film is low, the reliability of the liquid crystal display element may be lowered due to the effect of residual solvent or the like. However, the liquid crystal aligning agent obtained by the orientation amplification method is preferably at a temperature It can not be fired. Therefore, the firing temperature is generally low, which is a cause for lowering the reliability of the residual solvent and the like.

It is therefore an object of the present invention to provide a liquid crystal alignment film having a high controllability of orientation with high efficiency and a large process margin which can be adjusted to an optimum amount of irradiated polarized ultraviolet light or an optimum firing temperature.

Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above object, and as a result, have found the following inventions.

<1> A liquid crystal composition comprising (A) a component and (B) component, wherein the component (B) contains a photoreactive group and the components (A) and &Lt; / RTI &gt;

(A) a polymer having a side chain containing a carboxylic acid group structure, and

(B) at least one compound selected from compounds represented by the following formula (1).

[Chemical Formula 1]

[Wherein,

Q represents a single bond, an alkylene having 1 to 12 carbon atoms, a disubstituted alkene or a disubstituted alkyne in which the hydrogen atom on the carbon atom may be substituted with a monovalent organic group,

T may be an arbitrary carbon atom other than Q or X and may be substituted with an oxygen atom, a nitrogen atom or a sulfur atom, and a hydrogen atom on any carbon atom other than Q or X may be substituted with a monovalent organic group An aromatic ring having 5 or 6 carbon atoms or a heterocyclic ring or a structure in which 2 to 4 of the rings are bonded or condensed,

X represents a single bond, alkylene of 1 to 12 carbon atoms, disubstituted alkene which may be substituted with a monovalent organic group on the carbon atom, or disubstituted alkyne,

Y represents a single bond, an ether, an azo, a thioether, or an ester,

Z represents an alkylene group of 1 to 36 carbon atoms in which arbitrary hydrogen atoms may be substituted with fluorine and arbitrary non-adjacent carbon atoms may be substituted by oxygen atoms,

a represents 1 or 2,

When X and Y are both a single bond and a is 1, Z represents a hydrogen atom, a fluorine atom, an iodine atom, a bromine atom, a chlorine atom, a hydroxyl group, a nitro group, An amino group which may be substituted with an alkyl group of 1 to 36 carbon atoms, or a cyano group,

At least one of Q and X includes a disubstituted alkene or a disubstituted alkyn which may be substituted with a monovalent organic group on the carbon atom.

<2> The optically active composition according to <1>, wherein T in formula (1) is a group selected from the group consisting of benzene and biphenyl, which may be substituted with monovalent organic groups on any carbon atom other than Q or X, , An aromatic ring having any structure of terphenyl, naphthalene, anthracene, pyrene, pyridine, furan, pyrrole, or thiophene.

<3> The optically active composition according to <1> or <2>, wherein T in formula (1) may be a monovalent organic group in which a hydrogen atom on any carbon atom other than Q, Benzene, biphenyl, terphenyl, naphthalene, anthracene, or pyrene.

&Lt; 4 &gt; The optically active composition according to any one of &lt; 1 &gt; to &lt; 3 &gt;, wherein the component (A) does not contain a photoreactive group in its structure.

<5> The optically active composition according to any one of <1> to <4>, wherein the component (B) is contained in an amount of 0.5% by weight to 70% by weight based on the weight of the polymer of the component (A) .

<6> The optically active composition according to any one of <1> to <5>, wherein the component (A) is a polymer having a side chain containing a carboxylic acid group structure represented by the following formula (2).

(2)

[In the formula (2)

A represents a group selected from a single bond, -O-, -COO-, -CONH-, and -NH-,

B represents a group selected from a single bond, -O-, -COO-, -CONH-, -NH-, and -CH = CH-COO-,

Ar ₁ and Ar ₂ each independently represent a phenyl group or a naphthyl group,

and l and m are each independently an integer of 0 to 12.

<7> The optically active composition according to any one of <1> to <6>, wherein the component (B) is at least one compound selected from the following.

(3)

[Chemical Formula 4]

[Wherein,

R represents an alkyl group having 1 to 36 carbon atoms in which any non-adjacent carbon atom may be substituted with an oxygen atom,

n represents an integer of 2 to 5,

R 'represents a nitrogen atom which may be substituted with a monovalent organic group of oxygen, sulfur, or nitrogen on the nitrogen atom, and the monovalent organic group in R' is a carbon atom in which any carbon atom may be substituted with an oxygen atom An alkyl group having 1 to 10 atoms, or a phenyl group.

<8> A liquid crystal aligning agent comprising the optically active composition according to any one of <1> to <7>.

<9> A liquid crystal alignment film obtained from the liquid crystal aligning agent described in <8> above.

<10> A liquid crystal display element comprising the liquid crystal alignment film according to <9>.

According to the present invention, even when a polymer composition that does not exhibit photoreactivity is used, it is possible to provide a liquid crystal display device having a high controllability of orientation with a high efficiency and a wide range of the amount of irradiated polarized ultraviolet rays, , An optically active composition, a liquid crystal aligning agent containing the composition, a liquid crystal alignment film obtained from the liquid crystal aligning agent, a substrate having the liquid crystal alignment film, and a transverse electric field driven liquid crystal display device having the substrate. Further, by using the optically active composition, it is possible to provide a polymer film having a large process margin (polarized ultraviolet radiation amount and baking temperature) in production of an optical element, such as a retardation film.

BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a graph showing the change in absorbance with respect to an exposure amount at 262 nm when the optically active composition (B2-10) prepared in Example 2 is used. FIG.
2 is a graph showing a change in dichroism (dichroism) with respect to an exposure amount at 262 nm when the optically active composition (B2-10) prepared in Example 2 is used.
3 is a graph showing the change in absorbance with respect to the exposure amount at 262 nm when the optically active composition (B4-10) is used.
4 is a graph showing the dichroism change with respect to the exposure amount at 262 nm when the optically active composition (B4-10) was used.
FIG. 5 is a graph showing the in-plane orientation parameter S in each irradiation dose (exposure dose) obtained from Example 11 and Comparative Example 3. FIG.
6 is a graph showing the in-plane orientation S before and after non-polarized UV irradiation obtained from Example 12 and Comparative Example 4. Fig.

Hereinafter, embodiments of the present invention will be described in detail.

&Lt; Optically active composition &gt;

The optically active composition of the present invention contains the following components (A) and (B), and contains a photoreactive group in the component (B), and the component (A) To form liquid crystalline supramolecules.

(A) a polymer having a side chain containing a carboxylic acid group structure, and

(B) at least one kind of compound selected from aromatic compounds represented by the following formula (1).

[Chemical Formula 5]

[Wherein,

Q represents a single bond, an alkylene having 1 to 12 carbon atoms, a disubstituted alkene or a disubstituted alkyne in which the hydrogen atom on the carbon atom may be substituted with a monovalent organic group,

T may be an arbitrary carbon atom other than Q or X and may be substituted with an oxygen atom, a nitrogen atom or a sulfur atom, and a hydrogen atom on any carbon atom other than Q or X may be substituted with a monovalent organic group An aromatic ring having 5 or 6 carbon atoms or a heterocyclic ring or a structure in which 2 to 4 of the rings are bonded or condensed,

X represents a single bond, alkylene of 1 to 12 carbon atoms, disubstituted alkene which may be substituted with a monovalent organic group on the carbon atom, or disubstituted alkyne,

Y represents a single bond, an ether, an azo, a thioether, or an ester,

Z represents an alkylene group of 1 to 36 carbon atoms in which arbitrary hydrogen atoms may be substituted with fluorine and arbitrary non-adjacent carbon atoms may be substituted by oxygen atoms,

a represents 1 or 2,

When X and Y are both a single bond and a is 1, Z represents a hydrogen atom, a fluorine atom, an iodine atom, a bromine atom, a chlorine atom, a hydroxyl group, a nitro group, An amino group which may be substituted with an alkyl chain of 1 to 36 carbon atoms, or a cyano group,

At least one of Q and X includes a disubstituted alkene or a disubstituted alkyn which may be substituted with a monovalent organic group on the carbon atom.

Although it is not clear whether the composition satisfying the above-described constituent elements exerts the effect of solving the problem of the present invention, it is generally considered as follows.

It is said that the polymer having a side chain containing a carboxylic acid group structure as component (A) in the present invention represents a supramolecular liquid crystal by hydrogen bonding between carboxylic acids. In such a supramolecular liquid crystal, the structure of the aromatic ring-carboxylic acid-carboxylic acid-aromatic ring forming the hydrogen bond has a mesogen structure as shown below, and the temperature range indicating liquid crystallinity, And the like are thought to be determined almost at this mesogenic part.

[Chemical Formula 6]

At this time, when the aromatic carboxylic acid as the component (B) of the present invention is present, a carboxylic acid-carboxylic acid hydrogen bond is formed between the heterogeneous molecule and the component (A) A different physical property is given to the composition. As a result, a temperature range showing liquid crystallinity, an absorption band of ultraviolet rays, and the like change. In the present invention, by freely selecting a combination of these, it is possible to adjust the temperature range of the liquid crystal and the sensitivity to ultraviolet rays to an arbitrary range. Further, these are theoretical and do not limit the present invention.

<< Component (A) >>

The component (A) is a polymer having a side chain containing a carboxylic acid group structure. According to one preferred embodiment of the present invention, the component (A) does not contain a photoreactive group in the structure. That is, the preferred component (A) contains a carboxylic acid group in one side chain structure and does not contain a photoreactive group in the structure.

The non-carboxylic acid component may be copolymerized with the side chain component having a carboxylic acid structure at the terminal. In order to obtain good anisotropy (uniaxial orientation), the component having a terminal carboxylic acid structure is preferably at least 50 mol% Or more.

The general formula of such a side chain in the component (A) is preferably represented by the following formula (2).

(7)

In the formula (2), A represents a group selected from a single bond, -O-, -COO-, -CONH- and -NH-, and among them, -O- and -COO- are preferable from the viewpoint of liquid crystallinity Do.

B represents a group selected from a single bond, -O-, -COO-, -CONH-, -NH-, -CH = CH-COO- and from the viewpoint of liquid crystallinity, -O- and -COO- desirable.

Ar ₁ and Ar ₂ each independently represent a phenyl group or a naphthyl group.

l and m each independently represent an integer of 0 to 12, preferably an integer of 2 to 12; Among them, an integer of 2 to 8 is preferable from the viewpoint of liquid crystal display.

Specific examples of the side chain structure represented by the above formula (2) are illustrated below, but are not limited thereto.

[Chemical Formula 8]

In the above formula, p represents an integer of 0 to 12.

<< Preparation of Polymer >>

The polymer of the component (A) can be obtained by a polymerization reaction of a monomer containing the above-described specific side chain. It can also be obtained by copolymerization of a monomer having a side chain containing a photoreactive group and a monomer having a side chain containing a carboxylic acid group. Further, it can be copolymerized with other monomers within a range that does not inhibit the liquid crystalline property.

Other monomers include, for example, industrially available monomers capable of radical polymerization.

Specific examples of other monomers include unsaturated carboxylic acids, acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds and vinyl compounds.

Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid.

Examples of the acrylic acid ester compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, Acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxy triethylene glycol acrylate, 2-ethoxy ethyl acrylate, 2-ethoxyethyl acrylate, Methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate , And 8-ethyl-8-tricyclodecyl acrylate.

Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthrylmethyl methacrylate , Phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, Methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-propyl methacrylate, 2-ethylhexyl methacrylate, Adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate. Cyclic ethers such as glycidyl (meth) acrylate, (3-methyl-3-oxetanyl) methyl (meth) acrylate and (3-ethyl-3-oxetanyl) methyl (Meth) acrylate compound having a group can also be used.

Examples of the vinyl compound include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.

Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, and bromostyrene.

Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

The method for producing the polymer of the component (A) is not particularly limited, and a general-purpose method that is dealt with industrially can be used. Specifically, it can be produced by cation polymerization, radical polymerization or anionic polymerization using a vinyl group of a specific side chain monomer. Of these, radical polymerization is particularly preferable from the viewpoints of ease of reaction control and the like.

As the polymerization initiator for the radical polymerization, known compounds such as a radical polymerization initiator and a reversible addition-cleavage type chain transfer (RAFT) polymerization reagent can be used.

The radical thermal polymerization initiator is a compound which generates a radical by heating at a decomposition temperature or higher. Examples of such a radical thermal polymerization initiator include ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide, diacyl peroxides such as acetyl peroxide and benzoyl peroxide, hydroperoxides such as (Di-tert-butyl peroxide, dicumyl peroxide, di-lauroyl peroxide, etc.), peroxyketal (dibutyl peroxide, (Peroxyneodecanoic acid-tert-butyl ester, peroxypivalic acid-tert-butyl ester, peroxy 2-ethylcyclohexanoic acid-tert-amyl ester, etc.), persulfate Azo compounds such as azobisisobutylonitrile and 2,2'-di (2-hydroxyethyl) azobisisobutyronitrile, and the like can be used in combination with an organic peroxide such as potassium persulfate, potassium persulfate, sodium persulfate, ammonium persulfate, . These radical thermal polymerization initiators may be used singly or in combination of two or more.

The radical photopolymerization initiator is not particularly limited as long as it is a compound that initiates radical polymerization by light irradiation. Examples of such a radical photo polymerization initiator include benzophenone, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2-methyl-4-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, 1-hydroxycyclohexyl phenyl ketone, Benzoquinone, benzanthrone, 2-methyl-1- [4- (4-methylpiperazin-1-yl) (Methylthio) phenyl] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) Di (t-butylperoxycarbonyl) benzophenone, 3,4,4'-tri (t-butylperoxycarbonyl) benzophenone, 2,4 , 6-trimethylbenzoyldiphenylphosphine oxide, 2- (4'-methoxystyryl Bis (trichloromethyl) -s-triazine, 2- (3 ', 4'-dimethoxystyryl) -4,6-bis Bis (trichloromethyl) -s-triazine, 2- (2'-methoxystyryl) -4,6-bis (trichloro Methyl) -s-triazine, 2- (4'-pentyloxystyryl) -4,6-bis (trichloromethyl) -s- triazine, 4- [pN, N-di (ethoxycarbonylmethyl ) - 2,6-di (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2'-chlorophenyl) (Trichloromethyl) -5- (4'-methoxyphenyl) -s-triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p- dimethylaminostyryl) benzothiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis (7-diethylaminocoumarin), 2- (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl- '-Bimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetrakis (4-ethoxycarbonylphenyl) 2,2'-bis (2,4-dichlo Phenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2' bis (2,4-dibromophenyl) -4,4 ' -Tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl- Imidazole, 3- (2-methyl-2-dimethylaminopropionyl) carbazole, 3,6-bis Bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, 3,3 ', 4,4'-tetra (t-hexylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, Di (methoxycarbonyl) -4,4'-di (t-butylperoxycarbonyl) benzophenone, 3,4'-di (methoxycarbonyl) -4,3'-di Peroxycarbonyl) benzophenone, 4,4'-di (methoxycarbonyl) -3,3'-di (t-butylperoxycarbonyl) benzophenone, 2- (3-methyl- 2-ylidene) -1-naphthalen-2-yl-ethanone, or 2- (3- Yl-1,3-benzothiazol-2 (3H) -ylidene) -1- (2-benzoyl) ethanone. These compounds may be used alone or in combination of two or more.

The radical polymerization method is not particularly limited, and an emulsion polymerization method, a suspension polymerization method, a dispersion polymerization method, a precipitation polymerization method, a bulk polymerization method, a solution polymerization method and the like can be used.

The organic solvent used in the polymerization reaction is not particularly limited as long as the resulting polymer dissolves. Specific examples thereof are given below.

N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, But are not limited to, pyridine, dimethyl sulfone, hexamethyl sulfoxide,? -Butyrolactone, isopropyl alcohol, methoxymethyl pentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, Ketones, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol mono Butyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol mono Diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene Glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, But are not limited to, ethyl acetate, butyl butylate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, Propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, acetic acid Methoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid, 3-ethoxypropionic acid, 3- Methoxy-N, N-dimethylpropanamide, 3-ethoxy-N, N-dimethylaminopropylamine, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, Dimethyl propanamide, 3-butoxy-N, N-dimethylpropanamide, and the like.

These organic solvents may be used alone or in combination. Further, a solvent which does not dissolve the produced polymer may be mixed with the above-mentioned organic solvent within the range in which the produced polymer is not precipitated.

Further, in the radical polymerization, oxygen in the organic solvent causes the polymerization reaction to be inhibited. Therefore, it is preferable to use an organic solvent which has been degassed to the extent possible.

The polymerization temperature in the radical polymerization can be selected from any of 30 ° C to 150 ° C, preferably 50 ° C to 100 ° C. If the concentration is excessively low, it becomes difficult to obtain a polymer having a high molecular weight. If the concentration is too high, the viscosity of the reaction liquid becomes excessively high and it becomes difficult to carry out uniform stirring. , Preferably 1% by mass to 50% by mass, and more preferably 5% by mass to 30% by mass. In the initial stage of the reaction, it is carried out at a high concentration, and then an organic solvent can be added.

In the above-mentioned radical polymerization reaction, when the ratio of the radical polymerization initiator to the monomer is small, the molecular weight of the obtained polymer is small, and if it is small, the molecular weight of the obtained polymer is large. To 10 mol%. In the polymerization, various monomer components, solvents, initiators, etc. may be added.

[Recovery of Polymer]

When the produced polymer is recovered from the reaction solution of the polymer obtained by the above-described reaction, the reaction solution may be put into a poor solvent to precipitate the polymer. Examples of the poor solvent used in the precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, . The polymer precipitated by charging into a poor solvent can be recovered by filtration and then dried at room temperature or under reduced pressure or under normal pressure. In addition, by repeating the operation of redissolving the polymer recovered and recovered in an organic solvent and re-precipitating and recovering the polymer twice to 10 times, impurities in the polymer can be reduced. As the poor solvent at this time, for example, alcohols, ketones, hydrocarbons and the like can be mentioned, and when three or more poor solvents selected from these are used, the purification efficiency is further increased, which is preferable.

The molecular weight of the polymer of the component (A) of the present invention is preferably in the range of from 2000 (weight average molecular weight) measured by GPC (Gel Permeation Chromatography) to 2000 To 1,000,000, and more preferably from 5,000 to 100,000.

<< Ingredients of B >>

The optically active composition of the present invention contains a compound represented by the following formula (1) as a component (B).

[Chemical Formula 9]

In the above formula (1), Q represents a single bond, alkylene having 1 to 12 carbon atoms, disubstituted alkene which may be substituted with a monovalent organic group on the carbon atom, or disubstituted alkyne.

The alkylene having 1 to 12 carbon atoms is preferably an alkylene having 2 to 6 carbon atoms, more preferably an alkylene having 2 to 4 carbon atoms, such as ethylene, propylene, butylene And the like.

The above-mentioned "disubstituted alkene in which the hydrogen atom on the carbon may be substituted with a monovalent organic group" in Q means that the hydrogen atom on the carbon of the disubstituted alkene is substituted by a constant monovalent organic group, and such monovalent organic group Specific examples thereof include alkyl groups such as a methyl group and an ethyl group, fluorine atoms, cyano groups and the like, preferably a methyl group or a cyano group, and more preferably a cyano group. The term "disubstituted alkene" refers to a disubstituted alkene having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms. Specific examples thereof include an ethynyl group, a propenyl group, and a butenyl group.

The "disubstituted alkyne" in Q means a disubstituted alkene having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, and specific examples thereof include an ethynyl group, a propynyl group, and a butynyl group.

In the above formula (1), T may be an arbitrary carbon atom other than the bond to Q or X, which may be substituted with an oxygen atom, a nitrogen atom or a sulfur atom, Refers to an aromatic ring having 5 or 6 carbon rings or heterocyclic rings, or two to four of these rings bonded or condensed, which may be substituted with a monovalent organic group.

Here, the "carbon ring or heterocyclic ring of 5 or 6 atoms" means a carbon ring of 5 or 6 atoms, and a heterocyclic ring of 5 or 6 atoms. The term &quot; structure in which two or four of the rings are bonded or condensed &quot; means any two to four rings which can be selected from a 5- or 6-membered carbon ring, a 5- or 6-membered heterocycle, , A structure bonded to a bonding site of a substituent, or a structure in which the above-mentioned 2 to 4 rings form a 2- to 4-ring group structure by condensing a ring.

Such a carbon ring or heterocyclic ring of 5 or 6 atoms, in which any carbon atom other than Q or X may be substituted by an oxygen atom, a nitrogen atom or a sulfur atom, or two to four of these rings may be bonded or axially bonded Examples of the aromatic ring having a ring structure include benzene, biphenyl, terphenyl, naphthalene, anthracene, pyrene, pyridine, furan, pyrrole, thiophene, pyrazine and pyrimidine. Here, when any carbon atom other than Q or X is substituted by an oxygen atom, a nitrogen atom or a sulfur atom, the substitution is preferably one or two or more, preferably 1 or 2, more preferably 1 carbon atom .

According to another preferred embodiment of the present invention, the compound of formula (1) excludes compounds containing at least one pyrazine structure, naphthyridine structure, or phenazine structure. According to one more preferred embodiment of the present invention, the compound of the formula (1) excludes a compound containing at least two pyridine structures, a pyrazine structure, a naphthyridine structure, and a compound containing at least one phenazine structure.

According to one preferred embodiment of the present invention, the compound of formula (1) excludes compounds containing two or more pyridine structures. Examples of the compound having two or more pyridine structures as referred to herein include compounds having two or more pyridine structures (bipyridine) or two or more compounds. Typically, the pyridine structure has both ends of the compound (in the formula Coming to both ends in the). In the formula (1), for example, at least a is 2 and T is pyridine.

According to a preferred embodiment of the present invention, T represents a group selected from the group consisting of benzene, biphenyl, terphenyl, naphthalene, anthracene, pyrene, pyridine, and the like, in which hydrogen atoms on any carbon atom other than Q or X may be substituted with a monovalent organic group , Furan, pyrrole, or thiophene. More preferably, T is a group having any structure of benzene, biphenyl, terphenyl, naphthalene, anthracene, or pyrene, which may be substituted with a monovalent organic group on a hydrogen atom on any carbon atom other than X, Represents an aromatic ring.

The "monovalent organic group" in T which may be substituted with a hydrogen atom on any carbon atom other than Q or X is preferably an alkyl group such as a methyl group or an ethyl group, an alkoxy group such as a methoxy group or an ethoxy group More preferably a methyl group, a methoxy group, a fluorine, a cyano group, a nitro group, or a dimethylamino group, more preferably a methyl group, a methoxy group, a nitro group, Or a cyano group.

In the above formula (1), X represents a single bond, alkylene having 1 to 12 carbon atoms, disubstituted alkene which may be substituted with a monovalent organic group on the carbon atom, or disubstituted alkyne.

Here, the alkylene having 1 to 12 carbon atoms is preferably alkylene having 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms, such as ethylene, propylene, and butylene. Specific examples include:

The above-mentioned "disubstituted alkene wherein the hydrogen atom on the carbon may be substituted with a monovalent organic group" in X means that the hydrogen atom on the carbon of the disubstituted alkene is substituted by a constant monovalent organic group, and such monovalent organic group Specific examples thereof include alkyl groups such as a methyl group and an ethyl group, fluorine atoms, cyano groups and the like, preferably a methyl group or a cyano group, and more preferably a cyano group. The term "disubstituted alkene" refers to a disubstituted alkene having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms. Specific examples thereof include an ethynyl group, a propenyl group, and a butenyl group.

The "disubstituted alkyne" in X means a disubstituted alkene having 2 to 6, preferably 2 to 4 carbon atoms, and specific examples thereof include an ethynyl group, a propynyl group, and a butynyl group.

In the formula (1), Y represents a single bond, an ether, an azo, a thioether, or an ester, preferably a single bond (Q is a divalent alkene in which a hydrogen atom on a carbon atom may be substituted with a monovalent organic group , Or a disubstituted alkyne), or azo (when Q does not contain a photoreactive group alkene or alkyne).

In the above formula (1), Z represents an alkylene group having 1 to 36 carbon atoms, in which arbitrary hydrogen atoms may be substituted with fluorine, and arbitrary non-adjacent carbon atoms may be substituted with oxygen atoms, Represents an alkylene group having 1 to 10 carbon atoms.

a represents 1 or 2;

Z is a hydrogen atom, a fluorine atom, an iodine atom, a bromine atom, a chlorine atom, a hydroxyl group, a nitro group, or a nitrogen atom is optionally 1 (1) Or an amino group which may be substituted with an alkyl chain having 2 to 2 carbon atoms or a cyano group, and preferably Z may be substituted by fluorine, hydroxyl group or cyano group.

In the formula (1), at least one of Q and X necessarily includes a disubstituted alkene or a disubstituted alkyne which may be substituted with a monovalent organic group on the carbon atom.

According to one preferred embodiment of the present invention, in the formula (1)

- when a is 1, Q is a disubstituted alkene or a disubstituted alkyne in which the hydrogen atom on the carbon atom may be substituted with a monovalent organic group, or Y is azo,

- when a is 2, Q is a disubstituted alkene or a disubstituted alkyne in which the hydrogen atom on the carbon atom may be substituted with a monovalent organic group.

Specific examples of the compound represented by the formula (1) are illustrated below, but are not limited thereto.

[Chemical formula 10]

(11)

In the formula, R represents an alkyl group having 1 to 36 carbon atoms, in which any non-adjacent carbon atom may be substituted with an oxygen atom, and preferably represents an alkyl group having 1 to 10 carbon atoms.

n represents an integer of 2 to 5;

R 'represents a nitrogen atom which may be substituted with an oxygen atom, a sulfur atom, or a hydrogen atom on the nitrogen atom, and preferably represents an oxygen atom or a nitrogen atom. The "monovalent organic group" in R 'represents an alkyl group having 1 to 10 carbon atoms or a phenyl group, in which any carbon atom may be substituted with an oxygen atom, if it is not adjacent, and preferred examples thereof include a methyl group, Ethoxyethyl group, phenyl group, and the like.

The component (B) is contained preferably in an amount of 0.5% by weight to 70% by weight, more preferably 5% by weight to 30% by weight, based on the weight of the polymer of the component (A).

&Lt; Preparation of optically active composition &gt;

The optically active composition used in the present invention is preferably prepared as a coating liquid so as to be suitable for forming a coating film. That is, it is preferable to prepare a solution prepared by dissolving the component (A), the component (B), and various additives to be added as required, which will be described later, in an organic solvent. The content of the component (hereinafter also referred to as resin component) of the total of the component (A), the component (B) and various additives to be added as required is preferably 1% by mass to 20% by mass, 3% by mass to 15% by mass, and particularly preferably 3% by mass to 10% by mass.

<Organic solvent>

The organic solvent used in the optically active composition of the present invention is not particularly limited as long as it is an organic solvent for dissolving the resin component. Specific examples thereof are given below.

N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N- Dimethyl sulfoxide, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide,? -Butyrolactone, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy- Amide, 3-butoxy-N, N-dimethylpropanamide, 1,3-dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isobutyl ketone, methyl isopropyl ketone, Hexanone, ethylene carbonate, propylene carbonate, diglyme, 4-hydroxy-4-methyl-2-pentanone, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl Ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether Dipropylene glycol monoacetate monopropyl ether, dipropylene glycol monoacetate monopropyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, Methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, and the like. These may be used alone or in combination.

The polymer contained in the optically active composition of the present invention may be any polymer having a side chain containing the carboxylic acid group structure described above. However, other polymers other than the polymer may be used within the range that does not impair the liquid crystal- Or may be mixed. At this time, the content of the other polymer in the resin component is 0.5% by mass to 80% by mass, preferably 1% by mass to 50% by mass.

Such another polymer includes, for example, a polymer which is composed of poly (meth) acrylate, polyamic acid, polyimide or the like and is not a photosensitive side chain type polymer capable of exhibiting liquid crystallinity.

The optically active composition of the present invention may contain components other than the components (A) and (B). Examples thereof include, but are not limited to, a solvent or a compound that improves film thickness uniformity or surface smoothness when applying a solution of an optically active composition, a compound that improves adhesion between a coating film and a substrate, and the like.

Specific examples of the solvent (poor solvent) for improving the uniformity of the film thickness and the surface smoothness include the following.

Examples of the solvent include isopropyl alcohol, methoxymethyl pentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl Carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol- Butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, di Propylene glycol monoacetate monoethyl ether Propylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, Hexane, n-pentane, n-pentane, n-butane, n-butane, n-butane, Propyleneglycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, methyl ethyl ketone, ethyl lactate, ethyl lactate, ethyl lactate, methyl lactate, ethyl acetate, , 3-methoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy- 2-propanol, 1-butoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol- Lactic acid methyl ester, lactic acid ethyl ester, lactic acid n-propyl ester, lactic acid n-butyl ester, lactic acid isoamyl ester, lactic acid ethyl ester-2-acetate, dipropylene glycol, 2- (2- ethoxypropoxy) propanol, And a solvent having a low surface tension such as an ester.

These poor solvents may be used either singly or in combination. When the above-mentioned solvent is used, it is preferably 5% by mass to 80% by mass of the entire solvent so that the solubility of the entire solvent contained in the optically active composition of the present invention is not remarkably lowered, And preferably 20% by mass to 60% by mass.

Examples of the compound that improves film thickness uniformity and surface smoothness include a fluorine-based surfactant, a silicon-based surfactant, and a nonionic surface-active agent.

More specifically, for example, F-TOP (registered trademark) 301, EF303, EF352 (manufactured by Tohchem Products), Megapack (registered trademark) F171, F173, R-30 SC101, SC102, SC103, SC104, SC105, and SC106 (manufactured by AGC Seiyaku Chemical Co., Ltd.) (trade name, manufactured by Sumitomo 3M Limited), Asahi Guard (registered trademark) AG710 (manufactured by Asahi Glass Co., Ltd.), Surflon (registered trademark) And the like. The use ratio of these surfactants is preferably 0.01 parts by mass to 2 parts by mass, more preferably 0.01 parts by mass to 1 part by mass based on 100 parts by mass of the resin component contained in the polymer composition.

Specific examples of the compound that improves the adhesion between the coating film and the substrate include the following functional silane-containing compounds and the like.

For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3 3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxy (2-aminoethyl) Aminopropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, Amine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl Acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N- Bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N- Aminopropyltriethoxysilane, and the like.

In addition to the improvement of the adhesion between the substrate and the coating film, in order to prevent the deterioration of the electric characteristics due to the backlight when the liquid crystal display element is constituted, additives such as the following phenoplast series or epoxy group- In the optically active composition of the present invention. Specific phenoplast additives are shown below, but the structure is not limited thereto.

[Chemical Formula 12]

Specific 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, neo Pentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6 Tetraglycidyl-2,4-hexanediol, N, N, N ', N', -tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylamino Methyl) cyclohexane, N, N, N ', N', -tetraglycidyl-4, 4'-diaminodiphenylmethane and the like.

When a compound improving the adhesion with the substrate is used, the amount of the compound to be used is preferably 0.1 part by mass to 30 parts by mass, more preferably 1 part by mass to 100 parts by mass with respect to 100 parts by mass of the resin component contained in the optically active composition, 20 parts by mass. If the amount is less than 0.1 part by mass, the effect of improving the adhesion can not be expected. If the amount is more than 30 parts by mass, the alignment property of the liquid crystal may be deteriorated.

As an additive, a photosensitizer may be used. Colorless sensitizer and triplet sensitizer are preferable.

Examples of the photosensitizer include an aromatic nitro compound, coumarin (7-diethylamino-4-methylcoumarin, 7-hydroxy4-methylcoumarin), ketocoumarin, carbonylbiscumarin, aromatic 2- (2-hydroxybenzophenone, mono- or di-p- (dimethylamino) -2-hydroxybenzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, (2-benzoylmethylene-3-methyl- beta -naphthothiazoline, 2- (beta -naphthoylmethylene) -3-methylbenzothiazoline, 2- (alpha -naphthoylmethylene) -3 -Methyl-β-naphthothiazoline, 2- (4-biphenoylmethylene) -3-methylbenzothiazoline, 2- Methyl-β-naphthothiazoline, 2- (p-fluorobenzoylmethylene) -3-methyl-β-naphthothiazoline), oxazoline (2-benzoylmethylene- Oxazoline, 2- (p-naphthoylmethylene) - 3-methylbenzooxazoline, 2- (? -Naphthoylmethylene) -3-methylbenzooxazoline, 2- (4-biphenoylmethylene) Methyl-beta-naphthooxazoline, 2- (4-biphenoylmethylene) -3-methyl- beta -naphthoxazoline, 2- (p- fluorobenzoylmethylene) Nitroaniline, 2,4,6-trinitroaniline) or nitroascenaphthene (5-nitroasnamphthylene), (2 - [(m-hydroxy- (2-naphthalene), 2-naphthalene, 2-naphthalene, 2-naphthalene, 2-naphthalene, Carboxylic acid, 9-anthracene methanol, and 9-anthracenecarboxylic acid), benzopyran, azoindolizine, merocoumarin, and the like.

Preferred are aromatic 2-hydroxy ketone (benzophenone), coumarin, ketocoumarin, carbonylbiscumarin, acetophenone, anthraquinone, xanthone, thioxanthone, and acetophenone ketal.

The optically active composition of the present invention may contain a dielectric material, a conductive material and, moreover, a coating film for the purpose of changing electrical properties such as dielectric constant and electrical conductivity of the coating film as long as the effects of the present invention are not impaired , A crosslinking compound may be added for the purpose of increasing the hardness and density of the film.

The coating film formed by applying and baking the above-mentioned optically active composition onto a substrate can be used, for example, as a liquid crystal alignment film. The method of applying the liquid crystal aligning agent containing the optically active composition of the present invention onto a substrate having a conductive film for transverse electric field driving is not particularly limited.

The coating method is generally carried out by a screen printing method, an offset printing method, a flexo printing method, an ink jet method, or the like. Examples of other coating methods include a dipping method, a roll coater method, a slit coater method, a spinner method (spin coating method), a spraying method, and the like, depending on the purpose.

<< Production of Liquid Crystal Display Device >>

The production of the liquid crystal display element using the liquid crystal aligning agent containing the optically active composition of the present invention is represented by the following steps [I] to [IV].

That is, a substrate having a liquid crystal alignment film can be produced by a method including the following [I] to [III].

[I] a step of applying a liquid crystal aligning agent containing the optically active composition of the present invention onto a substrate having a conductive film to form a coated film;

[II] a step of irradiating the coating film obtained in [I] with polarized ultraviolet light; And

[III] a step of heating the coating film obtained in [II];

Subsequently, a liquid crystal display element can be manufactured by a method including the obtained step [IV] for a substrate having a liquid crystal alignment film.

[IV] A step of obtaining a liquid crystal display element by arranging a substrate having a liquid crystal alignment film obtained in [III] so that both liquid crystal alignment films are opposed to each other with a liquid crystal interposed therebetween.

&Lt; Process [I] &gt;

Process [I] is a process of applying the liquid crystal aligning agent of the present invention onto a substrate having a conductive film. After application, the coating film can be obtained by evaporating the solvent at 50 to 200 DEG C, preferably 50 to 150 DEG C by a heating means such as a hot plate, a heat circulation type oven or an IR (infrared) type oven. The drying temperature at this time is preferably lower than the liquid crystal phase expression temperature of the side chain type polymer.

The thickness of the coating film is disadvantageous from the viewpoint of power consumption of the liquid crystal display element if it is excessively large and from 5 to 300 nm, To 150 nm.

Further, after the step [I], a step of cooling the substrate having the coating film formed thereon to the room temperature before the subsequent step [II] may be formed.

&Lt; Process [II] &gt;

In the step [II], the coated film obtained in the step [I] is irradiated with polarized ultraviolet rays. When polarized ultraviolet rays are irradiated to the film surface of the coating film, polarized ultraviolet rays are irradiated to the substrate from a certain direction through the polarizer. As the ultraviolet ray to be used, ultraviolet rays having a wavelength in the range of 100 nm to 400 nm can be used. Preferably, the optimum wavelength is selected through a filter or the like depending on the type of the coating film to be used. For example, ultraviolet rays having a wavelength of 290 nm to 400 nm may be selectively used so as to cause a photo-crosslinking reaction. As ultraviolet rays, for example, light emitted from a high-pressure mercury lamp can be used.

The irradiation amount of the polarized ultraviolet ray depends on the coating film to be used. The irradiation dose is the amount of the polarized ultraviolet ray to realize the maximum value of DELTA A (hereinafter also referred to as DELTA Amax), which is the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of the polarized ultraviolet ray and the ultraviolet absorbance in the perpendicular direction Is preferably within a range of 1% to 70%, and more preferably within a range of 1% to 50%.

&Lt; Process [III] &gt;

In the step [III], the coated film irradiated with polarized ultraviolet rays in the step [II] is heated. By heating, orientation control ability can be imparted to the coating film.

As the heating, a heating means such as a hot plate, a heat circulation type oven, or an IR (infrared) type oven may be used. The heating temperature can be determined in consideration of the temperature at which the liquid crystal property of the coating film to be used is expressed.

The heating temperature is preferably within the temperature range of the temperature at which the side chain type polymer exhibits liquid crystallinity (hereinafter referred to as liquid crystal forming temperature). In the case of a thin film surface such as a coating film, it is expected that the liquid crystal development temperature at the surface of the coating film is lower than the liquid crystal development temperature when the photosensitive side chain type polymer capable of exhibiting liquid crystallinity is observed in bulk. For this reason, it is more preferable that the heating temperature is within the temperature range of the liquid crystal forming temperature on the surface of the coating film. That is, the temperature range of the heating temperature after irradiation with polarized ultraviolet light is set to a temperature lower by 10 占 폚 than the lower limit of the temperature range of the liquid crystal display temperature of the side chain type polymer used and a temperature 10 占 폚 lower than the upper limit of the liquid crystal temperature range It is preferable that the temperature is in the range of the upper limit. If the heating temperature is lower than the above temperature range, the effect of amplifying the anisotropy due to heat in the coating film tends to become insufficient. If the heating temperature is higher than the above temperature range, the coating film is in an isotropic liquid state (isotropic phase) , And in this case, it may become difficult to reorient in one direction by self-organization.

In addition, the liquid crystal display temperature is higher than the glass transition temperature (Tg) at which phase transition occurs from the solid phase to the liquid crystal phase, or the isotropic phase transition temperature (isotropic phase transition temperature) from the liquid crystal phase to the isotropic phase (Tiso). &Lt; / RTI &gt;

The thickness of the coating film formed after heating is preferably 5 nm to 300 nm, more preferably 50 nm to 150 nm, for the same reason as described in the step [I].

With the above process, introduction of anisotropy into the coating film with high efficiency can be realized in the manufacturing method of the present invention. A substrate on which a liquid crystal alignment film is formed with high efficiency can be produced.

&Lt; Process [IV] &gt;

In the step of [IV], a substrate having a liquid crystal alignment film obtained in [III] is disposed opposite to both liquid crystal alignment films through a liquid crystal, and a liquid crystal cell is manufactured by a known method, .

Two examples of the production of the liquid crystal cell or the liquid crystal display device are described below. The two substrates are prepared, the spacer is dispersed on the liquid crystal alignment film of the substrate of the single wafer, and the liquid crystal alignment film surface is inward, A method in which a liquid crystal is injected under reduced pressure, or a method in which a liquid crystal is dropped on a surface of a liquid crystal alignment film on which a spacer is dispersed, and then the substrate is bonded and sealed. At this time, it is preferable to use a substrate having electrodes having the same structure as a comb-like driving electrode for lateral electric field driving on one side of the substrate. The diameter of the spacer at this time is preferably from 1 탆 to 30 탆, more preferably from 2 탆 to 10 탆. This spacer diameter determines the distance between a pair of substrates sandwiching the liquid crystal layer, that is, the thickness of the liquid crystal layer.

In the method for producing a substrate on which a coating film is formed according to the present invention, a polarizing ultraviolet ray is irradiated after coating a polymer composition on a substrate to form a coating film. Subsequently, by heating, introduction of high-efficiency anisotropy into the side-chain type polymer film is realized, and a substrate on which a liquid crystal alignment film having a liquid crystal alignment control ability is formed is produced.

In the coating film used in the present invention, introduction of high efficiency anisotropy into the coating film is realized by utilizing the principle of molecular reorientation induced by the light reaction of the side chains and the self-organization based on liquid crystallinity. In the production method of the present invention, in the case of a structure having a photocrosslinkable group as a photoreactive group in the side chain type polymer, a coating film is formed on the substrate by using the side chain type polymer, then irradiated with polarized ultraviolet rays, And then a liquid crystal display element is manufactured.

By doing so, the liquid crystal display element provided by the present invention exhibits high reliability against external stress such as light or heat.

As described above, the transverse electric field driving type liquid crystal display element substrate manufactured by the method of the present invention or the transverse electric field driving type liquid crystal display element having the substrate is excellent in reliability and can be used for a liquid crystal television Can be preferably used.

Hereinafter, the present invention will be described using examples, but the present invention is not limited to the examples.

Example

The abbreviations used in the examples are as follows.

(Methacryl monomer)

M6BA: 4 '- ((6- (methacryloyloxy) hexyl) oxy) - [1,1'-biphenyl] -4-

[Chemical Formula 13]

(Shinnam acid addition agent)

[Chemical Formula 14]

(Organic solvent)

THF: tetrahydrofuran

NMP: N-methyl-2-pyrrolidone

BC: butyl cellosolve

(Polymerization initiator)

AIBN: 2,2'-azobisisobutyronitrile

The conditions for measuring the molecular weight of the polymer are as follows.

Apparatus: Room temperature gel permeation chromatography (GPC) apparatus (SSC-7200) manufactured by Senshu Scientific Corporation,

Column: Column (KD-803, KD-805) manufactured by Shodex Co.,

Column temperature: 50 ° C

Eluent: 30 mmol / l of lithium bromide-hydrate (LiBr 占 O 2O) as additive, 30 mmol / l of phosphoric anhydride crystal (o-phosphoric acid), 30 ml of tetrahydrofuran (THF ) &Lt; / RTI &gt; 10 ml / l)

Flow rate: 1.0 ml / min

Standard sample for preparing a calibration curve: TSK standard polyethylene oxide (molecular weight: about 9,000,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation; and polyethylene glycol (molecular weight about 12,000, 4,000, 1,000) manufactured by Polymer Laboratories.

&Lt; Example 1 &gt;

M6BA (15.32 g, 50.0 mmol) was dissolved in THF (141.6 g) and deaerated by a diaphragm pump. Then, AIBN (0.411 g, 2.5 mmol) was added and degassed again. Thereafter, reaction was carried out at 60 DEG C for 30 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to diethyl ether (1500 ml), and the resulting precipitate was filtered. The precipitate was washed with diethyl ether and dried under reduced pressure in an oven at 40 ° C to obtain a methacrylate polymer powder (B). This polymer had a number average molecular weight of 13,000 and a weight average molecular weight of 31,000.

NMP (29.29 g) was added to the resulting methacrylate polymer powder (B) (6.0 g) and dissolved by stirring at room temperature for 5 hours. NMP (14.75 g) and BC (50.0 g) were added to this solution and stirred for 5 hours to obtain liquid crystal aligning agent (B1).

To the 10.0 g of the liquid crystal aligning agent (B1), 0.03 g (5% by mass based on the solid content) of 4MCA as a synnamic acid additive was added and dissolved by stirring at room temperature for 3 hours to prepare a liquid crystal aligning agent (B2-5) Respectively.

In the same manner, the liquid crystal aligning agents B2-10 to B6-50, in which the kind and amount of the cinnamic acid additive were changed as shown in the following table, were adjusted.

&Lt; Example 2 &gt;

A liquid crystal cell was prepared using the liquid crystal aligning agent (B2-5) obtained in Example 1, and the orientation properties of the low molecular weight liquid crystal were confirmed. The irradiation amount of the polarized UV in the alignment treatment and the heating temperature after the polarized UV irradiation were changed to confirm the conditions under which the optimum orientation was obtained.

[Production of liquid crystal cell]

The substrate used was a glass substrate having a size of 30 mm x 40 mm and a thickness of 0.7 mm and provided with a comb-shaped pixel electrode formed by patterning an ITO film. The pixel electrode has a comb-like shape formed by arranging a plurality of elongated electrode elements bent at a central portion. The width of each electrode element in the short direction is 10 占 퐉, and the interval between the electrode elements is 20 占 퐉. Since the pixel electrode forming each pixel is constituted by arranging a plurality of elongated electrode elements bent at the center portion, the shape of each pixel is not a rectangular shape, and the shape of the bold Shaped shape. Each pixel has a first region that is on the upper side of the bent portion and a second region that is the lower side, which are vertically divided with the center bent portion as a boundary. When the first region and the second region of each pixel are compared with each other, the electrode elements of the pixel electrodes constituting the first region and the second region are different from each other. That is, in the first region of the pixel, the electrode element of the pixel electrode is formed so as to form an angle of + 15 degrees (clockwise direction) in the alignment direction of the liquid crystal alignment film, Is formed at an angle (clockwise direction) of -15 degrees. That is, in the first region and the second region of each pixel, the direction of rotation (in-plane switching) of the liquid crystal caused by the application of the voltage between the pixel electrode and the counter electrode is reversed . The liquid crystal aligning agent (A2) obtained in Example 1 was spin-coated on the prepared substrate on which the electrode was formed. Subsequently, the substrate was dried with a hot plate at 70 DEG C for 90 seconds to form a liquid crystal alignment film having a thickness of 100 nm. Subsequently, ultraviolet rays of 313 nm were irradiated onto the coated film surface through a polarizing plate at 3 to 13 mJ / cm 2, and then heated on a hot plate at 140 to 170 ° C for 10 minutes to obtain a substrate having a liquid crystal alignment film formed thereon. A coating film was similarly formed on a glass substrate having a columnar spacer having a height of 4 占 퐉 in which no electrode was formed as a counter substrate, and alignment treatment was carried out. A sealant (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) was printed on the liquid crystal alignment film of one of the substrates. Subsequently, the other substrate was bonded so that the liquid crystal alignment film surface faced the alignment direction at 0 °, and then the sealant was thermally cured to prepare empty cells. Liquid crystal MLC-2041 (manufactured by Merck Co., Ltd.) was injected into this empty cell by a low pressure injection method and the injection port was sealed to obtain a liquid crystal cell having a configuration of an IPS (In-Planes Switching) mode liquid crystal display device.

The obtained liquid crystal cell was placed between polarizing plates made of cross-nicol, and the alignment property of the liquid crystal was confirmed. An AC voltage of 8 Vpp was applied between the electrodes to confirm whether or not the liquid crystal of the pixel portion was driven.

The following table shows the results of the amount of polarized UV irradiation and the result of liquid crystal aligning property by heating temperature thereafter.

&Quot; x &quot; indicates that orientation defects such as a flow orientation are confirmed after liquid crystal injection, and &quot; o &quot; indicates alignment defects and good alignment properties.

&Lt; Example 3 &gt;

A liquid crystal cell was prepared by using the liquid crystal aligning agent (B2-10) in the same manner as in Example 2, and the orientation properties of the obtained liquid crystal cell were confirmed.

Table 3 below shows the results of liquid crystal alignment of the liquid crystal cell.

<Example 4>

A liquid crystal cell was prepared using the liquid crystal aligning agent (B2-30) in the same manner as in Example 2, and the orientation properties of the obtained liquid crystal cell were confirmed.

Table 4 below shows the results of the liquid crystal orientation of the liquid crystal cell.

&Lt; Example 5 &gt;

A liquid crystal cell was fabricated using the liquid crystal aligning agent (B2-50) in the same manner as in Example 2, and the orientation properties of the obtained liquid crystal cell were confirmed.

Table 5 below shows the results of the liquid crystal alignability of the liquid crystal cell.

&Lt; Example 6 &gt;

A liquid crystal cell was fabricated using the liquid crystal aligning agent (B3-10) in the same manner as in Example 2, and the alignment property of the obtained liquid crystal cell was confirmed.

Table 6 below shows the results of the liquid crystal alignability of the liquid crystal cell.

&Lt; Example 7 &gt;

A liquid crystal cell was prepared by using the liquid crystal aligning agent (B4-10) in the same manner as in Example 2, and the alignment property of the obtained liquid crystal cell was confirmed.

Table 7 below shows the result of the liquid crystal alignment property of the liquid crystal cell.

&Lt; Example 8 &gt;

A liquid crystal cell was produced by using the liquid crystal aligning agent (B5-10) in the same manner as in Example 3, and the orientation properties of the obtained liquid crystal cell were confirmed.

Table 8 below shows the results of the liquid crystal orientation of the liquid crystal cell.

&Lt; Example 9 &gt;

A liquid crystal cell was prepared by using the liquid crystal aligning agent (B6-5) in the same manner as in Example 2, and the orientation properties of the obtained liquid crystal cell were confirmed.

Table 9 below shows the results of liquid crystal orientation of the liquid crystal cell.

&Lt; Comparative Example 1 &

A liquid crystal cell was produced using the liquid crystal aligning agent (B1) in the same manner as in Example 2, and the orientation properties of the obtained liquid crystal cell were confirmed.

Table 10 below shows the results of the liquid crystal alignability of the liquid crystal cell.

From the results shown in Tables 1 to 10, it was confirmed that the heating temperature and the irradiation amount of the polarized UV to which optimum orientation property was obtained for Comparative Example 1 were changed by adding the additive of Shinnam acid system.

As shown in Comparative Example 2, the liquid crystal can not be aligned because the polymer having only B1 can not exhibit anisotropy. From the results of Tables 3 to 9, it is understood from the results of Tables 3 to 9 that by adding an additive It was confirmed that the liquid crystal could be oriented and the irradiation temperature of the polarizing UV and the heating temperature at which the optimum orientation was obtained could be changed by changing the type and amount of the additive.

In particular, with regard to the heating temperature, since the electric characteristics of the liquid crystal display element may be deteriorated due to the influence of residual solvent or the like, it is required to perform firing at a temperature as high as possible. The reason why the heating conditions to be obtained can be arbitrarily selected leads to a wider selection of materials.

The reason why the optimal irradiation amount or heating temperature is changed is considered to be the change in the sensitivity or response rate due to the absorption band of UV or UV due to the change of the mesogen portion of the liquid crystal of supramolecules.

[Evaluation as polymer film]

&Lt; Example 10 &gt;

The optically active composition (B2-10) prepared in Example 1 was coated on a quartz substrate of 1.1 mm by a spin coat method so as to have a film thickness of 100 nm and dried with a hot plate at 70 占 폚.

This coating film was irradiated with a polarized UV of 313 nm from 0 J / cm 2 to 30 J / cm 2, and then subjected to a heat treatment (so-called orientation amplification treatment by self-organization of polymer liquid crystals) for 10 minutes on a hot plate at 170 ° C . (Fig. 1) and dichroism (Fig. 2) at 262 nm before and after heating at 170 캜 were traced for the polarized UV irradiation substrate. Further, the change in absorbance and the measurement of dichroism [Delta] A were measured by measuring the polarized UV-vis absorption spectrum and calculated by the following formula.

Dichroism A = A ||-A⊥

(Where A is the absorbance in the parallel direction with respect to the irradiated polarized UV and A? Represents the absorbance in the? Direction with respect to the irradiated polarized UV). The absorbance is the value of the absorbance at 262 nm.

In the figures, "LPUV" shows the results for a polarized UV irradiated substrate before heating at 170 ° C. and "anneal" (annealed) shows results for a polarized UV irradiated substrate after heating at 170 ° C. The &quot; Exposure energy &quot; of the horizontal axis in the drawing indicates the exposure amount.

The absorbance change at 262 nm (FIG. 3) and the dichroism (FIG. 4) in the case of using the optically active composition (B4-10) were also calculated in the same manner.

UV-3100 (manufactured by Shimadzu Corporation) was used for measurement of the polarized UV-vis absorption spectrum.

1 and 3, almost no change is observed after the polarized UV irradiation, but since the vertical component increases and the parallel component decreases after the heating (annealing), the absorption component in the parallel direction is rearranged, In the in-plane vertical direction.

In Fig. 2 and Fig. 4, the dichroism (DELTA A) is a negative value, which means that anisotropy exists in a direction perpendicular to the irradiation axis (in-plane).

&Lt; Comparative Example 2 &

The dichroism of the liquid crystal aligning agent (B1) was also calculated in the same manner as in Example 10, but no remarkable dichroism was observed in any irradiation region.

&Lt; Example 11 &gt;

The in-plane order parameter (in-plane orientation S) of each of the thin films was measured in the same manner as in Example 10, except that B-2-10 was used for the optically active compositions (B2-5, B2-30, B2-50) Respectively. Also, the measurement of the in-plane orientation degree S was performed by measuring the polarized UV-vis absorption spectrum and calculating the following equation.

Plane orientation S = (A? - A ||) / (A⊥ + 2A ||)

(Where A? Represents the absorbance of the perpendicular component with respect to the polarized UV irradiation axis in the measurement of the absorbance of the thin film after the heat treatment, and A | represents the absorbance of the parallel component).

Also, A? And A || Absorbance values at 314 nm were all used.

&Lt; Comparative Example 3 &

The in-plane orientation S in the case of using the liquid crystal aligning agent (B1) was also calculated in the same manner.

The in-plane orientation S at each irradiation dose obtained from Example 11 and Comparative Example 3 is shown in Fig.

It can be seen from FIG. 5 that all of them are oriented in the direction perpendicular to the light irradiation axis because they take a positive value. Also, in the drawings, the larger the numerical value, the higher the degree of orientation.

From the evaluations of Example 10 and Comparative Example 2, it was confirmed that the addition of the additive of the cinnamic acid system results in a change in absorbance and dichroism which is not expressed only by the liquid crystal aligning agent (B1), and a change in the amount of irradiated polarized UV and the size of the dichroism It was confirmed that it was possible.

From the evaluations of Example 11 and Comparative Example 3, it was found that the addition of the additive of the cinnamic acid system makes it possible to produce an in-plane orientation degree which is not expressed only by the liquid crystal aligning agent (B1) It is apparent that the optimum irradiation area is increased.

As described above, the reason why the irradiation amount and the heating temperature were optimum in Examples 1 to 11 was considered to be that the mesogenic structure of the supramolecular liquid crystal was changed and the sensitivity or reaction rate due to UV absorption band or UV was changed.

The present invention and its excellent effects are as described above. However, in order to further confirm the above, an experiment was conducted on the light stability of the coating film as described below.

&Lt; Example 12 &gt;

(B2-5, B-2-10, B2-30, B2-50) after measurement of the In-plane order parameter (S in plane orientation) used in Example 11 was measured for a ratio of 313 nm Polarized UV light was irradiated at a rate of 1 J / cm 2, and the stability test of the coating film against the UV absorption spectrum before and after irradiation of the unpolarized UV light at 313 nm was carried out.

&Lt; Comparative Example 4 &

The structural formula of the used M6CA ((E) -3- (4 - ((6- (methacryloyloxy) hexyl) oxy) phenyl) acrylic acid) is shown below.

[Chemical Formula 15]

The optically active composition (B7) having the same solid concentration was obtained by using the same polymer (number average molecular weight: 11000, weight average molecular weight: 26000) in which M6CA of Example 1 was replaced with M6CA.

Using this optically active composition (B-7), a coating film was prepared in the same manner as in Example 10, irradiated with 6 mJ / cm 2 of 313 nm polarized UV, and then heated with a hot plate at 170 캜 for 10 minutes Substrate. In this substrate, similarly to Example 12, a 313 nm non-polarized UV light was irradiated at 1 J / cm 2, and a confirmation experiment was performed on the stability of the coating film against the UV absorption spectrum before and after irradiation of 313 nm of unpolarized UV light Respectively.

The in-plane orientation S before and after non-polarized UV irradiation obtained from Example 12 and Comparative Example 4 is shown in Fig.

In the figures, "after annealed" shows the results for the polarized UV irradiated substrate after the heating treatment at 170 ° C., and "after exposed" shows the results for the polarized UV irradiated substrate after the unpolarized UV irradiation at 313 nm.

From the evaluation of Example 12 and Comparative Example 4, it was found that even when the coating film (B-2-30: Fig. 6A) prepared by the method of the present invention was subjected to the non-polarized UV light irradiation at 313 nm Did not cause a spectral change.

On the other hand, in the coating film (B7: Fig. 6B) made of pM6CA prepared in Comparative Example 4, since the anisotropy was lost after the irradiation with the unpolarized UV light of 313 nm, it became clear that the coating film was sensitive to light and low in light resistance.

It was also confirmed that even in the case of other coating films (B2-5, B-2-10, B2-50) in which the addition amount of 4MCA was different, even if unpolarized UV light irradiation of 313 nm was performed, no spectral change occurred before and after the irradiation .

Claims (10)

(A) and a component (B), wherein the component (B) contains a photoreactive group, and the component (A) and the component (B) &Lt; / RTI &gt;
(A) a polymer having a side chain containing a carboxylic acid group structure, and
(B) at least one compound selected from compounds represented by the following formula (1).
[Chemical Formula 1]

[Wherein,
Q represents a single bond, an alkylene having 1 to 12 carbon atoms, a disubstituted alkene or a disubstituted alkyne in which the hydrogen atom on the carbon atom may be substituted with a monovalent organic group,
T may be an arbitrary carbon atom other than Q or X and may be substituted with an oxygen atom, a nitrogen atom or a sulfur atom, and a hydrogen atom on any carbon atom other than Q or X may be substituted with a monovalent organic group An aromatic ring having 5 or 6 carbon atoms or heterocyclic rings or a structure in which 2 to 4 of these rings are bonded or condensed,
X represents a single bond, alkylene of 1 to 12 carbon atoms, disubstituted alkene which may be substituted with a monovalent organic group on the carbon atom, or disubstituted alkyne,
Y represents a single bond, an ether, an azo, a thioether, or an ester,
Z represents an alkylene group of 1 to 36 carbon atoms in which arbitrary hydrogen atoms may be substituted with fluorine and arbitrary non-adjacent carbon atoms may be substituted by oxygen atoms,
a represents 1 or 2,
When X and Y are both a single bond and a is 1, Z represents a hydrogen atom, a fluorine atom, an iodine atom, a bromine atom, a chlorine atom, a hydroxyl group, a nitro group, An amino group which may be substituted with an alkyl group of 1 to 36 carbon atoms, or a cyano group,
At least one of Q and X includes a disubstituted alkene or a disubstituted alkyn which may be substituted with a monovalent organic group on the carbon atom. The method according to claim 1,
T in the formula (1) is a group selected from the group consisting of benzene, biphenyl, terphenyl, naphthalene, anthracene, pyrene, pyridine, furan, and the like, which may be substituted with a monovalent organic group on any carbon atom other than Q or X, Pyrrole, thiophene, or thiophene. 3. The method according to claim 1 or 2,
In the formula (1), T represents any structure of benzene, biphenyl, terphenyl, naphthalene, anthracene, or pyrene, which may have a hydrogen atom on any carbon atom other than Q or X bonded thereto, &Lt; / RTI &gt; 4. The method according to any one of claims 1 to 3,
Wherein the component (A) does not contain a photoreactive group in the structure. 5. The method according to any one of claims 1 to 4,
Wherein the component (B) is contained in an amount of 0.5% by weight to 70% by weight based on the weight of the polymer of the component (A). 6. The method according to any one of claims 1 to 5,
Wherein the component (A) is a polymer having a side chain containing a carboxylic acid group structure represented by the following formula (2).
(2)

[In the formula (2)
A represents a group selected from a single bond, -O-, -COO-, -CONH-, and -NH-,
B represents a group selected from a single bond, -O-, -COO-, -CONH-, -NH-, and -CH = CH-COO-,
Ar ₁ and Ar ₂ each independently represent a phenyl group or a naphthyl group,
and l and m are each independently an integer of 0 to 12. 7. The method according to any one of claims 1 to 6,
Wherein the component (B) is at least one compound selected from the following.
(3)

[Chemical Formula 4]

[Wherein,
R represents an alkyl group having 1 to 36 carbon atoms in which any non-adjacent carbon atom may be substituted with an oxygen atom,
n represents an integer of 2 to 5,
R 'represents a nitrogen atom which may be substituted with a monovalent organic group by an oxygen atom, a sulfur atom, or a hydrogen atom on the nitrogen atom, and the monovalent organic group in R' may be an oxygen atom, An alkyl group having 1 to 10 carbon atoms, or a phenyl group. A liquid crystal aligning agent comprising the optically active composition according to any one of claims 1 to 7. A liquid crystal alignment film obtained from the liquid crystal alignment agent according to claim 8. A liquid crystal display element comprising the liquid crystal alignment film according to claim 9.

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