TW201625744A - Liquid crystal alignment agent and liquid crystal alignment film using photoreactive hydrogen bonding polymer liquid crystal - Google Patents

Abstract

To provide a liquid crystal alignment film with high efficiency alignment controllability and a wider area of optimum irradiation amount of polarized ultraviolet light. An optically active composition, characterized in that the optically active composition contains the following component (A) and component (B). Component (A) contains photoreactive groups, component (A) and component (B) form liquid crystal-based supra-molecular through hydrogen bonding, wherein component (A) has a polymer containing a side chain of carboxylic acid group structure, and component (B) is at least one compound selected from aromatic compounds represented by the following formula (1) [wherein definition of symbols is defined as in the specification].

Description

Liquid-reactive liquid crystal alignment agent and liquid crystal alignment film using photoreactive hydrogen bonding polymer liquid crystal

The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element using the same, or a polymer film suitable for producing an optical element in which a control molecule such as a retardation film or a polarizing diffraction element is aligned.

Liquid crystal display elements are known as lightweight, thin, and low power consumption display devices, and have been in recent years for use in large-scale television applications and the like. The liquid crystal display element is configured by, for example, arranging a liquid crystal layer on a transparent substrate by one of the electrodes. Further, in the liquid crystal display device, an organic film made of an organic material is used as the liquid crystal alignment film so that the liquid crystal becomes a desired alignment state between the substrates.

In other words, the constituent members of the liquid crystal alignment film-type liquid crystal display device are formed on the surface of the substrate sandwiching the liquid crystal adjacent to the liquid crystal, and serve to make the liquid crystal alignment between the substrates in a certain direction. Further, the liquid crystal alignment film is required to have a role of controlling the pretilt angle of the liquid crystal in addition to the role of aligning the liquid crystal in a certain direction such as a direction parallel to the substrate. The ability of the liquid crystal alignment film to control the liquid crystal alignment (hereinafter referred to as the alignment control energy) is performed by the organic film constituting the liquid crystal alignment film. It is given by the line alignment process.

A method of aligning a liquid crystal alignment film for imparting alignment control energy has been known in the past. The rubbing method is a method of rubbing (friction) the surface of the polyvinyl alcohol or the polyimide film or the polyimide film on the substrate with a cotton, nylon, polyester or the like in a certain direction to make the liquid crystal in the wiping direction (friction) Direction) The method of alignment. Since this rubbing method can easily realize the alignment state of the comparatively stable liquid crystal, it has been used in the manufacturing process of the conventional liquid crystal display element. In addition, the organic film used for the liquid crystal alignment film is mainly selected from a polyimide-based organic film having excellent reliability such as heat resistance and electrical properties.

However, the rubbing method of wiping the surface of the liquid crystal alignment film formed of polyimide or the like has a problem of generating dust or static electricity. Further, in recent years, the surface of the liquid crystal alignment film cannot be uniformly wiped by the cloth due to the high definition of the liquid crystal display element or the unevenness caused by the switching of the active element by the electrode on the substrate or the liquid crystal driving. Sometimes it is impossible to achieve uniform liquid crystal alignment.

Therefore, other alignment treatment methods for liquid crystal alignment films that do not rub have been actively reviewed for the optical alignment method.

There are various methods for the photo-alignment method, but anisotropic property is formed in the organic film constituting the liquid crystal alignment film by linear polarized light or collimate light, and the liquid crystal is aligned according to the anisotropy. The main alignment method is known as a "photodecomposition type" which generates an anisotropic decomposition of a molecular structure by irradiation of a polarized ultraviolet ray, or a polarized ultraviolet ray by using a polyvinyl laurate, which is in a side chain parallel to the polarized light. Dimerization reaction in the double bond The "dimerization type" (refer to, for example, Patent Document 1) of the (crosslinking reaction) is used when a side chain type polymer having an azobenzene in a side chain is used, and a polarized ultraviolet ray is irradiated, and the side chain is parallel to the polarized light. The isomerization reaction is carried out in the nitrogen benzene portion, and the liquid crystal is "isomerized" in the direction orthogonal to the polarization direction (see, for example, Non-Patent Document 2).

On the other hand, in recent years, a novel photoalignment method (hereinafter also referred to as an alignment amplification method) using a photosensitive side chain type polymer which exhibits liquid crystallinity has been reviewed. This is a method of aligning a film having a photosensitive side chain type polymer exhibiting liquid crystallinity by polarized light irradiation, and then, by subjecting the side chain type polymer film to heating, a coating agent imparting alignment control energy is obtained. Membrane. At this time, only a slight anisotropy exhibited by the polarized light irradiation becomes a driving force, and the liquid crystalline side chain type polymer itself is realigned efficiently by self-organization. As a result, it is possible to obtain a liquid crystal alignment film to which high alignment control energy is imparted (see, for example, Patent Document 2).

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

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 3893659

[Patent Document 2] International Publication No. WO2014/054785

[Non-patent literature]

[Non-Patent Document 1] M. Shadt et al., Jpn. J. Appl. Phys. 31, 2155 (1992)

[Non-Patent Document 2] K. Ichimura et al., Chem. Rev. 100, 1847 (2000)

The irradiation amount of the polarized ultraviolet light which is most suitable for the highly efficient anisotropic introduction of the liquid crystal alignment film used in the alignment amplification method corresponds to the irradiation amount of the polarized ultraviolet light which is optimal for the amount of the photosensitive base light reaction in the coating film. As a result of irradiating the polarized light after the polarizing of the liquid crystal alignment film used in the alignment amplification method, if the photosensitive group of the side chain of the photoreaction is small, a sufficient amount of photoreaction cannot be obtained. In this case, sufficient self-organization is not performed even after subsequent heating. On the other hand, when the photosensitive group of the side chain of the photoreaction is excessive, the obtained film becomes rigid, and there is a case where the self-organization due to subsequent heating is hindered.

At present, in the liquid crystal alignment film used in the alignment amplification method, since the sensitivity of the photoreactive group in the polymer used is high, the region in which the above-mentioned optimum polarized ultraviolet ray is irradiated is narrow. As a result, the manufacturing efficiency of the liquid crystal display element is lowered.

Further, when the firing temperature of the liquid crystal alignment film is low, there is a possibility that the reliability of the liquid crystal display element is lowered due to the influence of residual solvent or the like, but The liquid crystal alignment agent obtained by the alignment amplification method cannot be fired at a temperature higher than the liquid crystal display temperature of the polymer liquid crystal. Therefore, in general, when the baking temperature is low, the residual solvent or the like causes a decrease in reliability.

Accordingly, it is an object of the present invention to provide a liquid crystal alignment film which imparts an alignment control energy with high efficiency and which can be adjusted to an optimum polarized ultraviolet irradiation amount or an optimum firing temperature.

The inventors of the present invention conducted a positive review to achieve the above problems, and found the following invention.

<1> An optically active composition comprising the following components (A) and (B), wherein (A) contains a photoreactive group, and (A) and (B) are hydrogen-bonded. The liquid crystalline supramolecules are formed: (A) a polymer having a side chain having a carboxylic acid group structure, and (B) at least one compound selected from the compounds represented by the following formula (1).

Wherein Q represents a single bond, or an alkylene group having 1 to 12 carbon atoms, and T represents an oxygen source capable of passing any carbon atom other than the Q or X bond Substituting a nitrogen atom or a sulfur atom, and a hydrogen atom on any carbon atom other than the Q or X bond may be substituted with a monovalent organic group of a 5 or 6 membered carbocyclic or heterocyclic ring, or such a ring An aromatic ring of 2 to 4 bonds or condensed rings, X represents a single bond or an alkyl group having 1 to 12 carbon atoms, and Y represents a single bond, an ether, an azo, a thioether, or an ester, and Z represents Any hydrogen atom may be substituted with fluorine, and any non-adjacent carbon atom may be substituted with an alkyl group having 1 to 36 carbon atoms of the oxygen atom, and a represents 1 or 2, but X and Y are both single bonds. And when a is 1, Z is an alkyl group having 1 to 36 carbon atoms which may be optionally subjected to hydrogen atoms on hydrogen, fluorine, iodine, bromine, chlorine, hydroxyl, nitro or nitrogen atoms through 1 or 2 carbon atoms. Substituted amine group, or cyano group substituted].

<2> In the optically active composition of the above <1>, T in the formula (1) may represent a benzene having a hydrogen atom at any carbon atom other than the Q or X bond, which may be substituted with a monovalent organic group. An aromatic ring of any of benzene, terphenyl, naphthalene, anthracene, anthracene, pyridine, furan, pyrrole or thiophene.

<3> In the optically active composition of the above <1> or <2>, T in the formula (1) may represent that a hydrogen atom having any carbon atom other than the Q or X bond may be substituted with a monovalent organic group. An aromatic ring of any of benzene, biphenyl, terphenyl, naphthalene, anthracene or anthracene.

(4) The optically active composition according to any one of <1> to <3> wherein the component (A) may have a carboxyl group in one side chain structure. Acid group and photoreactive group.

(5) The optically active composition according to any one of the above items (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). .

The optically active composition according to any one of the above-mentioned items (1) to (5), wherein the component (A) may be selected from the group consisting of the following formulas (2) and (3). a polymer of a side chain of a carboxylic acid group structure,

Wherein A represents a group selected from a single bond, -O-, -COO-, -CONH-, -NH-, and -CH=CH-COO-, and B represents a single bond, -O-, -COO -, -CONH-, -NH-, and -CH=CH-COO- selected groups, except in formula (2), at least one of A and B is -CH=CH-COO-, Ar ₁ and Ar ₂ each independently represents a phenyl or naphthyl group, and l and m are each independently an integer of 0 to 12].

The optically active composition according to any one of <1> to <6> wherein the component (B) is at least one selected from the group consisting of

Wherein R represents any unsubstituted carbon atom which may be substituted with an alkyl group having 1 to 36 carbon atoms, and R' represents an oxygen atom, a sulfur atom, or a hydrogen atom on the nitrogen may be substituted with a monovalent value. The nitrogen atom of the organic group, and any hydrogen atom of the one-valent organic group in the above R' may be substituted with a fluorine atom, and it is indicated that any carbon atom may be substituted with an oxygen atom as long as it is not adjacent to 1 to 10 Alkyl, or phenyl].

<8> A liquid crystal alignment agent containing the optically active composition according to any one of <1> to <7> above.

<9> A liquid crystal alignment film obtained by the liquid crystal alignment agent described in <8>.

<10> A liquid crystal display element comprising the liquid described in <9> Crystalline alignment film.

According to the present invention, it is possible to provide an optically active composition which imparts an alignment control energy with high efficiency and which has a wide range of optimum polarized ultraviolet irradiation amount, or which can appropriately select a liquid crystal display temperature of a polymer liquid crystal, and contains the composition. A liquid crystal alignment agent, a liquid crystal alignment film obtained from the liquid crystal alignment agent, a substrate having the liquid crystal alignment film, and a lateral electric field drive type liquid crystal display element having the substrate. Further, by using the optically active composition, it is possible to provide a polymer film having a wide process margin (polarizing ultraviolet irradiation amount or firing temperature) in a manufacturing optical element such as a retardation film.

Fig. 1 is a graph showing changes in absorbance at an exposure amount of 314 nm when the optically active composition (A2-10) produced in Example 1 was used.

Fig. 2 is a graph showing the change in dichroism of the exposure amount at 314 nm when the optically active composition (A2-10) produced in Example 1 was used.

Fig. 3 is a graph showing the change in absorbance for an exposure amount of 314 nm when the optically active composition (A3-10) was used.

Fig. 4 is a graph showing the change in dichroism of the exposure amount at 314 nm when the optically active composition (A3-10) was used.

Fig. 5 is a graph showing the in-plane ordering degree S (in-plane order parameter) of each irradiation amount (exposure amount) obtained in Example 5 and Comparative Example 3. A diagram of the ordering parameters in the plane.

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

<Optical active composition>

The optically active composition of the present invention is characterized in that it contains the following components (A) and (B), and the component (A) contains a photoreactive group, and the components (A) and (B) are permeated. Hydrogen bonds form liquid crystalline supramolecules.

(A) a polymer having a side chain having a carboxylic acid group structure, and (B) at least one compound selected from the aromatic compound represented by the following formula (1).

Wherein Q represents a single bond or an alkylene group having 1 to 12 carbon atoms, and T represents any carbon atom other than a Q or X bond which may be substituted by an oxygen atom, a nitrogen atom or a sulfur atom, and Q Or a carbon atom or a heterocyclic ring of 5 or 6 members in which a hydrogen atom on any carbon atom other than the X bond is substituted by a monovalent organic group, or a structure in which 2 to 4 bonds or condensed rings of the ring are bonded. Aromatic Ring, X represents a single bond or an alkyl group having 1 to 12 carbon atoms, Y represents a single bond, an ether, an azo, a thioether, or an ester, and Z represents an arbitrary hydrogen atom which may be substituted with fluorine, and optionally not adjacent The carbon atom may be substituted with an alkyl group having 1 to 36 carbon atoms of the oxygen atom, and a represents 1 or 2. However, X and Y are both single bonds, and when a is 1, Z is hydrogen and fluorine. The hydrogen atom on the iodine, bromine, chlorine, hydroxyl group, nitro group or nitrogen atom may be optionally substituted with one or two amine groups substituted with an alkyl group having 1 to 36 carbon atoms or a cyano group.

It is not clear whether the composition satisfying the above-described constituent elements exhibits an effect of solving the problem of the present invention, but it is considered as follows.

The polymer having a side chain having a carboxylic acid group structure of the component (A) in the present invention can be said to exhibit a supramolecular liquid crystal due to hydrogen bonding between the carboxylic acids. This supramolecular liquid crystal system is considered to have a structure in which a hydrogen bond-forming aromatic ring-carboxylic acid-carboxylic acid-aromatic ring is a mesogen structure as described below, and exhibits a liquid crystal temperature range or an ultraviolet absorption band. Both are determined by the mesogenic site.

In this case, when the aromatic carboxylic acid of the component (B) of the present invention is present, a carboxylic acid-carboxylic acid hydrogen bond between the heterogeneous molecules is formed with the component (A), and the component is formed only by the component (A). Composition of different physical properties. As a result, the temperature range in which liquid crystallinity is exhibited or the absorption band of ultraviolet rays or the like is changed. The present invention can adjust the display temperature region of the liquid crystal or the sensitivity to ultraviolet rays or the like to an arbitrary range by freely selecting the combination of the above. Again, these are theories and do not limit the invention.

<(A) component>

The component (A) is a polymer having a side chain containing a carboxylic acid structure. In the present invention, the component (A) contains a photoreactive group. In this case, a carboxylic acid group and a photoreactive group may be contained in one side chain structure, and other side chains containing a photoreactive group may be present in the polymer, but from the viewpoint of the reaction efficiency of the optically active composition Preferably, one side chain structure contains a carboxyl group and a photoreactive group.

Further, the side chain component having a carboxylic acid structure at the terminal may be copolymerized with the non-carboxylic acid component, but in order to obtain an anisotropy (uniaxial alignment), it is preferred that the component having a terminal carboxylic acid structure contains at least 50 m. %the above.

When a carboxylic acid group and a photoreactive group are contained in one side chain structure, the general formula of the side chain (hereinafter, also referred to as a specific side chain) can be preferably represented by the following formulas (2) and (3).

In the above formulae (2) and (3), A represents a group selected from the group consisting of a single bond, -O-, -COO-, -CONH-, -NH-, and -CH=CH-COO-, wherein From the viewpoint of exhibiting liquid crystallinity, it is preferably -O- or -COO-.

B represents a group selected from the group consisting of a single bond, -O-, -COO-, -CONH-, -NH-, and -CH=CH-COO-, and it is preferred from the viewpoint of exhibiting liquid crystallinity. -O-, -COO-.

However, in the formula (2), at least one of A and B is -CH=CH-COO-.

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

l and m are each an integer of 0 to 12, preferably an integer of 2 to 12. Among them, from the viewpoint of exhibiting liquid crystallinity, it is preferably an integer of 2 to 8.

Specific examples of the side chain structure represented by the above formulas (2) and (3) are exemplified below, but are not limited thereto.

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

<Production of Polymers>

The polymer of the component (A) can be obtained by a polymerization reaction of a monomer having the above specific side chain. Further, it can also be obtained by copolymerization of a monomer having a side chain containing a photoreactive group with a monomer having a side chain containing a carboxylic acid group. In addition, it can be copolymerized with other monomers within a range that does not impair the ability to exhibit liquid crystallinity.

Other monomers are listed, for example, as monomers which are commercially available for free radical polymerization.

Specific examples of the other monomer include an unsaturated carboxylic acid, an acrylate compound, a methacrylate compound, a maleimide compound, acrylonitrile, maleic anhydride, a styrene compound, and a vinyl compound.

Specific examples of the unsaturated carboxylic acid are exemplified by acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and the like.

The acrylate compound is exemplified by, for example, methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, and propylene. Ethyl phthalate, decyl methacrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxy acrylate Ester, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, acrylic acid 2 -propyl-2-adamantyl ester, 8-methyl-8-tricyclodecyl acrylate, and 8-ethyl-8-tricyclodecyl acrylate.

The methacrylate compound is exemplified by, for example, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, decyl methacrylate, decyl methacrylate. Methyl ester, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, methacrylate 2- Methoxyethyl ester, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, methyl 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl methacrylate 8-tricyclic decyl ester and the like.

Glycidyl (meth)acrylate, (3-methyl-3-oxetanyl)methyl (meth)acrylate, and (meth)acrylic acid (3-ethyl-3-oxa) A (meth) acrylate compound having a cyclic ether group such as cyclobutyl)methyl ester.

The vinyl compound is exemplified by vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.

The styrene compound is exemplified by, for example, styrene, methylstyrene, chlorostyrene, bromostyrene or the like

The maleidinide compound is exemplified by, for example, maleic imine, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

The method for producing the polymer of the component (A) is not particularly limited, and a widely used method employed in the industry can be used. Specifically, it can be produced by cationic polymerization, radical polymerization or anionic polymerization using a vinyl group of a specific side chain monomer. Among these, radical polymerization is optimal from the viewpoint of easiness of reaction control and the like.

As the polymerization initiator for radical polymerization, a conventional compound such as a radical polymerization initiator, a reversible addition-broken chain transfer (RAFT) polymerization reagent, or the like can be used.

The radical thermal polymerization initiator is a compound which generates a radical by heating to a temperature higher than a decomposition temperature. The radical thermal polymerization initiator is exemplified by, for example, a ketone peroxide (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), a dimercapto peroxide (ethyl sulfonyl peroxide, Benzoyl peroxide, etc.), hydrogen peroxide (hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl hydrogen peroxide (di-tertiary butyl) Peroxide, dicumyl peroxide, dilauroyl peroxide, etc., peroxyketals (dibutylperoxycyclohexane, etc.), alkyl peresters (peroxy Tert-butyl neodecanoate, tert-butyl peroxypivalate, triamyl peroxy 2-ethylcyclohexanoate, etc.) Persulfate (potassium persulfate, sodium persulfate, over Ammonium sulfate, etc., azo compounds (azo Bis-isobutyl phthalate, and 2,2'-bis(2-hydroxyethyl)azobisisobutyrine, etc.). These radical thermal polymerization initiators may be used alone or in combination of two or more.

The radical photopolymerization initiator is not particularly limited as long as it is a compound which initiates radical polymerization by light irradiation. The radical photopolymerization initiator may be exemplified by benzophenone, michlae's ketone, 4,4'-bis(diethylamino)benzophenone, xanthone, thioxanthone, and isopropylidene. Ketoxanone, 2,4-diethylthioxanthone, 2-ethylhydrazine, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4'- Isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy Benzo-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one , 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid Amyl ester, 4,4'-bis(t-butylperoxycarbonyl)benzophenone, 3,4,4'-tris(t-butylperoxycarbonyl)benzophenone, 2,4 ,6-trimethylbenzimidyldiphenylphosphine oxide, 2-(4'-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-( 3',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2',4'-dimethoxystyryl)- 4,6-double ( Trichloromethyl)-s-triazine, 2-(2'-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-pentyloxy Styryl)-4,6-bis(trichloromethyl)-s-triazine, 4-[p-N,N-bis(ethoxycarbonylmethyl)]-2,6-di(trichloro) Methyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(2'-chlorophenyl)-s-triazine, 1,3-bis(trichloromethyl)-5 -(4'-A Oxyphenyl)-s-triazine, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-mercaptobenzene Thiazole, 3,3'-carbonyl bis(7-diethylaminocoumarin), 2-(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2' -biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-indole (4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2 '-Bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dibromobenzene -4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5 , 5'-tetraphenyl-1,2'-biimidazole, 3-(2-methyl-2-dimethylaminopropionyl)carbazole, 3,6-bis(2-methyl-2- Morpholinylpropionyl)-9-n-dodecylcarbazole, 1-hydroxycyclohexyl phenyl ketone, bis(5-2,4-cyclopentadien-1-yl)-bis (2,6 -difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, 3,3',4,4'-tetrakis(t-butylperoxycarbonyl)benzophenone, 3,3 ',4,4'-tetra(trihexylperoxycarbonyl)benzophenone, 3,3'-bis(methoxycarbonyl)-4,4'-di(t-butylperoxycarbonyl) Benzophenone, 3,4'-bis(methoxycarbonyl)-4,3'- (t-butylperoxycarbonyl)benzophenone, 4,4'-bis(methoxycarbonyl)-3,3'-bis(t-butylperoxycarbonyl)benzophenone, 2- (3-methyl-3H-benzothiazol-2-ylidene)-1-naphthalen-2-yl-ethanone, or 2-(3-methyl-1,3-benzothiazole-2 (3H) - subunit)-1-(2-benzylidene) ethyl ketone and the like. These compounds may be used singly 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, or the like can be used.

The organic solvent used in the polymerization reaction can be produced as long as it There is no particular limitation on the dissolution of the polymer. Specific examples thereof are listed below.

N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylene Indamine, dimethyl hydrazine, tetramethyl urea, pyridine, dimethyl hydrazine, hexamethylarylene, γ-butyrolactone, isopropanol, methoxymethylpentanol, dipentene, B Kefenyl ketone, methyl decyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellulolytic, ethyl cellulolytic, methyl cellosolve acetate Ester, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl Ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol diethylene glycol Ethyl 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 single B Acid ester monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene Alcohol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl Ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethyl carbonate, propyl carbonate , methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, 3 -ethyl ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, 3-methyl Butyl oxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentyl Ketone, 3-methoxy-N,N-dimethylpropanamide, 3-ethoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropane Amidoxime and the like.

These organic solvents may be used singly or in combination. Further, even a solvent which does not dissolve the produced polymer may be used in the organic solvent in a range in which the formed polymer is not precipitated.

Further, since the oxygen in the organic solvent in the radical polymerization is a cause of hindering the polymerization reaction, the organic solvent is preferably degassed to the extent possible.

The polymerization temperature in the radical polymerization may be any temperature from 30 ° C to 150 ° C, but preferably in the range of from 50 ° C to 100 ° C. Further, the reaction can be carried out at any concentration, but when the concentration is too low, it is difficult to obtain a polymer having a high molecular weight. When the concentration is too high, the viscosity of the reaction liquid becomes too high and it is difficult to uniformly stir, so the monomer concentration is preferably 1% by mass. ~50% by mass, more preferably 5% by mass to 30% by mass. The initial stage of the reaction 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 is larger than that of the monomer, the molecular weight of the obtained polymer becomes small, and when the amount of the polymer is small, the molecular weight of the polymer becomes large, so the radical initiator The ratio is preferably from 0.1 mol% to 10 mol% relative to the monomer to be polymerized. Further, various monomer components, solvents, initiators, and the like may be added during the polymerization.

[Recovery of Polymers]

Recycling from the reaction solution of the polymer obtained by the above reaction In the case of a polymer, the reaction solution may be poured into a weak solvent to precipitate the polymer. The weak solvent used for precipitation may be exemplified by methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, A. Ethyl ethyl ether, water, and the like. The polymer precipitated in the weak solvent is recovered by filtration, and then dried at normal temperature or under reduced pressure under normal pressure or reduced pressure. Further, when the operation of re-dissolving the polymer recovered by precipitation in an organic solvent and reprecipitation recovery is repeated 2 to 10 times, impurities in the polymer can be reduced. The weak solvent at this time is, for example, an alcohol, a ketone, a hydrocarbon or the like. When three or more kinds of weak solvents selected from the above are used, it is preferable because the purification efficiency can be further improved.

The molecular weight of the polymer of the component (A) of the present invention, in consideration of the strength of the obtained coating film, the workability at the time of formation of the coating film, and the uniformity of the coating film, the weight average molecular weight measured by GPC (gel permeation chromatography) method It is preferably from 2,000 to 1,000,000, more preferably from 5,000 to 100,000.

<B component>

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

In the above formula (1), Q represents a single bond or an alkylene group having 1 to 12 carbon atoms, and preferably represents a single bond or an alkylene group having 1 to 6 carbon atoms. More The alkylene group is preferably an alkylene group having 2 to 4 carbon atoms, and specific examples thereof include an ethyl group, a propyl group, and a butyl group.

In the above formula (1), T represents that any carbon atom other than the Q or X bond may be substituted by an oxygen atom, a nitrogen atom or a sulfur atom, and a hydrogen atom may be substituted on any carbon atom other than the Q or X bond. A carbocyclic or heterocyclic ring of 5 or 6 members substituted with a monovalent organic group, or an aromatic ring having a structure in which 2 to 4 of these rings are bonded or condensed.

Here, the "carbon ring or heterocyclic ring of 5 or 6 members" means a heterocyclic ring containing a carbon ring, 5 members or 6 members of 5 or 6 members. Further, the term "the structure of 2 to 4 bonds or condensed rings of the rings" means any 2 to 4 rings which can be selected from a carbon ring of 5 or 6 members, a heterocyclic ring of 5 or 6 members, The structure has a structure in which a bond portion directly bonded to a substituent is bonded to each other, or a structure in which two to four rings condense the ring to form a ring of a 2-4 ring type.

Thus, as a 5- or 6-membered carbocyclic or heterocyclic ring having any carbon atom other than the Q or X bond, which may be substituted by an oxygen atom, a nitrogen atom or a sulfur atom, or 2 to 4 bonds of the ring The aromatic ring of the structure of the condensed ring is exemplified by, for example, benzene, biphenyl, terphenyl, naphthalene, anthracene, anthracene, pyridine, furan, pyrrole or thiophene, pyrazine, pyrimidine or the like. Here, when any carbon atom other than the Q or X bond is substituted with an oxygen atom, a nitrogen atom or a sulfur atom, the substitution may be 1 or 2 or more, preferably 1 or 2, more preferably 1 carbon. Atomic substitution.

According to a preferred embodiment of the invention, the compound of formula (1) excludes compounds comprising more than two pyridine structures. Here, the term "two or more pyridine structures" means two pyridine structures (bipyridine). Or more than two or more, typically the pyridine structure is located at both ends of the compound (in the formula (1), which may be located next to the carboxyl group). In the formula (1), for example, at least a is 2 and T is pyridine.

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

According to a preferred embodiment of the present invention, T represents a benzene, a biphenyl, a terphenyl, a naphthalene, an anthracene, an anthracene having a hydrogen atom on any carbon atom other than the Q or X bond, and may also be substituted with a monovalent organic group. An aromatic ring of any of pyridine, furan, pyrrole or thiophene. More preferably, T represents a fragrance having any structure of benzene, biphenyl, terphenyl, naphthalene, anthracene or anthracene having a hydrogen atom on any carbon atom other than Q or X or a bond which may also be substituted with a monovalent organic group. Family ring.

Further, in T, a so-called "monovalent organic group" which may be substituted with a hydrogen atom on any carbon atom other than the Q or X bond is preferably an alkyl group such as a methyl group or an ethyl group, or an alkyl group such as a methoxy group or an ethoxy group. a halogen atom such as an oxy group, a nitro group, a cyano group, a dimethylamino group or a fluorine atom, more preferably a methyl group, a methoxy group, a fluorine group, a cyano group, a nitro group or a dimethylamino group, and more preferably a methyl group. , methoxy or cyano.

In the above formula (1), X represents a single bond or an alkylene group having 1 to 12 carbon atoms, and preferably represents an alkylene group having 1 to 6 carbon atoms. More preferably, the alkylene group is an alkylene group having 2 to 4 carbon atoms, and specific examples thereof include an ethyl group, a propyl group, and a butyl group.

In the above formula (1), Y represents a single bond, an ether, a thioether or an ester, and preferably represents a single bond or an ether.

In the above formula (1), Z represents an arbitrary hydrogen atom which may be substituted with fluorine, and any non-adjacent carbon atom may be substituted with an alkyl group having 1 to 36 carbon atoms, preferably an arbitrary hydrogen atom. It can be substituted into fluorine, and any non-adjacent carbon atom can be substituted with an alkylene group having 1 to 10 carbon atoms.

a represents 1 or 2.

Further, in the above formula (1), both X and Y are each a single bond, and when a is 1, Z is a hydrogen atom which can be hydrogen, fluorine, iodine, bromine, chlorine, a hydroxyl group, a nitro group or a nitrogen atom. Optionally, it may be substituted with one or two amine groups substituted with an alkyl chain having 1 to 36 carbon atoms or a cyano group. Preferably, Z may be substituted by fluorine, a hydroxyl group or a cyano group.

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

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

Further, in the above formula, R' represents an oxygen atom or a sulfur atom, or a hydrogen atom on the nitrogen which may be substituted with a nitrogen atom of a monovalent organic group, and preferably represents an oxygen atom or a nitrogen atom. In the above R', the "monovalent organic group" means an alkyl group having 1 to 10 carbon atoms or a phenyl group which may be substituted with an oxygen atom as long as it is not adjacent, and a specific example is a methyl group. Ethyl, methoxyethyl, phenyl, and the like.

The weight of the component (B) relative to the polymer of the component (A) is preferably from 0.5% by weight to 70% by weight, more preferably from 5% by weight to 30% by weight.

<Modulation of Optically Active Composition>

The optically active composition used in the present invention is preferably prepared into a coating liquid in a form suitable for forming a coating film. In other words, it is preferred to dissolve the (A) component, the component (B), and various additives which are added as needed, as needed, in an organic solvent to prepare a solution. In this case, the content of the components (hereinafter also referred to as resin components) in which the components (A) and (B) are added as needed is preferably from 1% by mass to 20% by mass, more preferably 3% by mass. ~15% by mass, preferably 3% by mass to 10% by mass.

<Organic solvents>

The organic solvent used in the optically active composition of the present invention is not particularly limited as long as it can dissolve the resin component. Specific examples thereof are listed below.

N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N- Ethyl pyrrolidone, N-vinylpyrrolidone, dimethyl hydrazine, tetramethyl urea, pyridine, dimethyl hydrazine, hexamethylarylene, γ-butyrolactone, 3-methoxy- N,N-dimethylpropanamide, 3-ethoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, 1,3-two Methyl-imidazolidinone, ethyl amyl ketone, methyl decyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethyl carbonate, carbonic acid Propyl ester, 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 monoacetic acid Ester 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, and the like. These may be used singly or in combination.

The polymer contained in the optically active composition of the present invention may all be a polymer having a side chain having the above carboxylic acid group structure, but may be mixed in a range which does not impair the liquid crystal display performance and photosensitivity. Other polymers. In this case, the content of the other polymer in the resin component is from 0.5% by mass to 80% by mass, preferably from 1% by mass to 50% by mass.

Such a polymer is exemplified by a polymer which is not a side chain type polymer which exhibits liquid crystallinity, and which is formed of poly(meth)acrylate, polyglycolic acid or polyimine.

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

Specific examples of the solvent (weak solvent) for improving film thickness uniformity or surface smoothness are as follows.

For example, isopropanol, methoxymethylpentanol, 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 tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetic acid Ester 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, Amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methyl cyclohexene, propyl ether, dihexyl ether, 1-hexanol, n-hexane, n-pentane, n-octane, two Ethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, 3-methoxypropionic acid Ester, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, Butyl 3-methoxypropionate, 1-methoxy-2-propanol Alcohol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1 -monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, methyl lactate, lactic acid An organic solvent having a low surface tension such as ethyl ester, n-propyl lactate, n-butyl lactate or isoamyl lactate.

These weak solvents may be used alone or in combination of plural kinds. When the solvent is used as described above, it is preferably 5% by mass to 80% by mass, more preferably 20% by mass, based on the total solubility of the solvent contained in the optically active composition of the present invention. %~60% by mass.

The compound which improves film thickness uniformity or surface smoothness is exemplified by a fluorine-based surfactant, a polyfluorene-based surfactant, a nonionic surfactant, and the like.

More specifically, for example, EF TOP (registered trademark) EF301, EF303, EF352 (manufactured by TOKEMU PRODUCTS), MEGAFAC (registered trademark) F171, F173, R-30 (manufactured by DIC Corporation), FLORARD FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.) ASAHI GUARD (registered trademark) AG710 (manufactured by Asahi Glass Co., Ltd.), SURFLON (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimi Chemical Co., Ltd.). The use ratio of the surfactant is preferably 0.01 parts by mass to 2 parts by mass, more preferably 0.01 parts by mass to 1 part by mass, per 100 parts by mass of the resin component contained in the polymer composition.

Specific examples of the compound which improves the adhesion between the coating film and the substrate are the following compounds containing a functional decane.

Listed as, for example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2-aminopropyltriethoxydecane, N -(2-Aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-ureido Propyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-aminopropyltriethyl Oxydecane, N-triethoxydecylpropyltriethylamine, N-trimethoxydecylpropyltriethylamine, 10-trimethoxydecyl-1,4,7 -triazanonane, 10-triethoxydecyl-1,4,7- Triazadecane, 9-trimethoxydecyl-3,6-diazadecyl acetate, 9-triethoxydecyl-3,6-diazadecyl acetate, N-benzyl 3-aminopropyltrimethoxydecane, N-benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl 3-aminopropyltriethoxydecane, N-bis(oxyethylene)-3-aminopropyltrimethoxydecane, N-bis(oxyethylene)-3-aminopropyltriethoxy Decane and so on.

Further, in addition to improving the adhesion between the substrate and the coating film, in order to prevent deterioration of electrical characteristics due to the backlight when the liquid crystal display element is formed, the optically active composition of the present invention may contain the following phenoplast (phenoplast). An additive to a compound containing an epoxy group. Specific phenolic plastic additives are shown below, but are not limited to this configuration.

Specific examples of the epoxy group-containing compound are ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and neopentyl Alcohol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromo neopentyl glycol diglycidyl ether, 1,3,5,6-four Glycidyl-2,4-hexanediol, N,N,N',N'-tetraglycidyl-inter- Xylene diamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diamine Diphenylmethane and the like.

When the compound which improves the adhesion to the substrate is used, the amount thereof is preferably from 0.1 part by mass to 30 parts by mass, more preferably from 1 part by mass to 20 parts by mass, per 100 parts by mass of the resin component contained in the optically active composition. Share. When the amount used is less than 0.1 part by mass, the effect of improving the adhesion cannot be expected, and when it is more than 30 parts by mass, the alignment of the liquid crystal may be deteriorated.

A photosensitizer can also be used as an additive. Preferred are colorless sensitizers and triplet sensitizers.

Photosensitizers include aromatic nitro compounds, coumarin (7-diethylamino-4-methylcoumarin, 7-hydroxy-4-methylcoumarin), ketocoumarin, carbonyl Dicoumarin, aromatic 2-hydroxyketone, and amine-substituted aromatic 2-hydroxyketone (2-hydroxybenzophenone, mono or di-p-(dimethylamino)-2-hydroxydi Benzophenone), acetophenone, anthracene, xanthone, thioxanthone, benzoxanone, thiazoline (2-benzylidenemethylidene-3-methyl-β-naphthylthiazoline, 2-(β-naphthylmethylidene methylene)-3-methylbenzothiazoline, 2-(α-naphthylmethylidene methylene)-3-methylbenzothiazoline, 2-(4 -biphenolylmethylene)-3-methylbenzothiazoline, 2-(β-naphthylmethylidenemethyl)-3-methyl-β-naphthylthiazoline, 2-(4-linked Phenolic methylene)-3-methyl-β-naphthylthiazoline, 2-(p-fluorobenzhydrylmethylene)-3-methyl-β-naphthylthiazoline), oxazoline (2-Benzylmercaptomethyl-3-methyl-β-naphthyloxazoline, 2-(β-naphthylmethylidenemethylene)-3-methylbenzoxazoline, 2- (α-naphthylmethylidene methylene)-3-methylbenzoxazoline, 2-(4-biphenolol methylene)-3-methylbenzoxazoline, 2-(β- Naphthoquinone Kea methyl) -3-methyl-β-naphthyloxazoline, 2-(4-bisphenol benzylidene)-3-methyl-β-naphthyloxazoline, 2-(p-fluorobenzhydryl) Methylene)-3-methyl-β-naphthyloxazoline), benzothiazole, nitroaniline (m- or p-nitroaniline, 2,4,6-trinitroaniline) or nitro Bismuth (5-nitroguanidine), (2-[(m-hydroxy-p-methoxy)styryl]benzothiazole, benzoin alkyl ether, N-alkyl phthalone, Acetophenone ketal (2,2-dimethoxyphenylethanone), naphthalene, anthracene (2-naphthalenemethanol, 2-naphthalenecarboxylic acid, 9-fluorene methanol and 9-anthracenecarboxylic acid), benzopyridinium Anthracene, azo acridine, furan coumarin and the like.

Preferred are aromatic 2-hydroxyketone (benzophenone), coumarin, ketocoumarin, carbonyl dicoumarin, acetophenone, anthracene, xanthone, thioxanthone and acetophenone. Ketal.

In addition to the above, the optically active composition of the present invention may be added with a dielectric or a conductive material to change the dielectric properties of the coating film or electrical conductivity, and further, as long as the effect of the present invention is not impaired. A crosslinkable compound may be added to increase the film hardness or density at the time of film formation.

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

The coating method is generally carried out in the industry by screen printing, lithography, flexographic printing or ink jet printing. Other coating methods include a dipping method, a roll coating method, a slit coating method, a spin coating method (spin coating method), a spray coating method, and the like, and these may be used depending on the purpose.

<Manufacture of Liquid Crystal Display Element>

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

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

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

[II] a step of irradiating a polarized ultraviolet ray to the coating film obtained in [I]; and

[III] a step of heating the coating film obtained in [II]; and subsequently, the obtained substrate having a liquid crystal alignment film can be produced by a method comprising the following step [IV].

[IV] The step of obtaining a liquid crystal display element by disposing a liquid crystal in such a manner that the liquid crystal alignment film obtained by [III] is disposed opposite to the liquid crystal alignment film of the two.

<Step [I]>

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

When the thickness of the coating film is too thick, the power consumption of the liquid crystal display element is disadvantageous. When the film thickness is too thin, the reliability of the liquid crystal display element may be lowered. Therefore, it is preferably from 5 nm to 300 nm, more preferably from 10 nm to 150 nm.

Further, after the step [I], the step of cooling the substrate on which the coating film is formed to room temperature may be provided before the step [II].

<Step (II)>

In the step [II], the coating film obtained in the step [I] is irradiated with polarized ultraviolet rays. When the film surface of the coating film is irradiated with polarized ultraviolet rays, the substrate is irradiated with polarized ultraviolet rays through the polarizing plate from a certain direction. The ultraviolet rays used can use ultraviolet rays having a wavelength in the range of 100 nm to 400 nm. Preferably, the optimum wavelength is selected by a filter or the like depending on the type of the coating film to be used. Further, for example, in the form of selectively inducing a photocrosslinking reaction, ultraviolet rays having a wavelength in the range of 290 nm to 400 nm can be selected. Ultraviolet light, for example, can be emitted from a high pressure mercury lamp.

The amount of ultraviolet light that is polarized is related to the coating film used. The amount of irradiation is preferably a polarized ultraviolet ray having a maximum difference of ΔA (hereinafter also referred to as ΔAmax) which is a difference between the ultraviolet absorbance in the direction parallel to the polarized direction of the polarized ultraviolet light and the ultraviolet absorbance in the vertical direction. Within the range of 1% to 70%, it is better to be in the range of 1% to 50%.

<Step [III]>

The step [III] is a film which is heated by the polarized ultraviolet irradiation in the step [II]. By heating, an alignment control energy can be imparted to the coating film.

Heating means a heating means such as a hot plate, a heat cycle type oven or an IR (infrared) type oven. The heating temperature can be determined by considering the temperature at which the coating film to be used exhibits liquid crystallinity.

The heating temperature is preferably within a temperature range in which the side chain type polymer exhibits liquid crystallinity (hereinafter referred to as liquid crystal display temperature). In the case of the film surface of the coating film, the liquid crystal display temperature of the surface of the coating film is estimated to be lower than the liquid crystal display temperature when the photosensitive side chain type polymer which exhibits liquid crystallinity is observed as a whole. Therefore, the heating temperature is better in the temperature range in which the liquid crystal on the surface of the coating film exhibits temperature. That is, the temperature range of the heating temperature after the polarized ultraviolet irradiation is preferably such that the temperature lower than the lower limit of the temperature range of the liquid crystal display temperature of the side chain type polymer used is set to the lower limit, and is lower than the upper limit of the liquid crystal temperature range. The temperature at 10 ° C is set to the temperature in the range of the upper limit. When the heating temperature is lower than the above temperature range, there is a tendency that the anisotropic amplification effect by heat in the coating film is insufficient, and when the heating temperature is excessively higher than the above temperature range, the state of the coating film is close to the isotropic property. The tendency of the liquid state (isotropic phase), in this case, it is difficult to re-align in one direction by self-organization.

Further, the liquid crystal display temperature means that the surface of the side chain type polymer or the coating film is transferred from the solid phase to the glass transition temperature (Tg) which occurs in the liquid phase, and causes the phase transition from the liquid crystal phase to the isotropic phase ( The isotropic phase transfers the temperature below the in-phase temperature (Tiso).

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

By having the above steps, the production method of the present invention can efficiently achieve the introduction of anisotropic properties to the coating film. Moreover, the substrate with the liquid crystal alignment film can be efficiently manufactured.

<Step [IV]>

[IV] The step of disposing the liquid crystal alignment film on the substrate having the liquid crystal alignment film obtained in [III] so that the liquid crystal alignment films of the two are opposed to each other, and forming the liquid crystal cell by a conventional method to produce a liquid crystal display element. step.

When one example of the production of a liquid crystal cell or a liquid crystal display device is used, two substrates are prepared, and the spacer is spread on the liquid crystal alignment film of one substrate so that the liquid crystal alignment film surface is inside, and the other substrate is bonded. A method of injecting a liquid crystal and sealing it under reduced pressure, or a method in which a liquid crystal is dropped on a liquid crystal alignment film surface on which a separator is dispersed, and a substrate is bonded and sealed. In this case, it is preferable to use a substrate having an electrode such as a comb-tooth structure for driving a lateral electric field. The separator at this time preferably has a diameter of from 1 μm to 30 μm, more preferably from 2 μm to 10 μm. The spacer diameter will determine the distance between one of the liquid crystal layers and the substrate, that is, the thickness of the liquid crystal layer.

In the method for producing a coated film substrate of the present invention, a polymer composition is applied onto a substrate to form a coating film, and then the polarized ultraviolet rays are irradiated. Then, the substrate is introduced into the liquid crystal alignment film having the alignment control energy of the liquid crystal by efficiently introducing the anisotropic property to the side chain type polymer film by heating.

The coating film used in the present invention utilizes the molecular reorientation principle caused by the photoreaction of the side chain and the self-organization of the liquid crystal, thereby efficiently introducing the anisotropy into the coating film. In the method of the present invention, when the side chain type polymer has a photocrosslinkable group as a photoreactive group, the side chain type polymer is used to form a coating film on the substrate, and then the polarized ultraviolet ray is irradiated, followed by the irradiation. After heating, a liquid crystal display element was produced.

As described above, 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 substrate for a lateral electric field drive type liquid crystal display device manufactured by the method of the present invention or the lateral electric field drive type liquid crystal display device having the substrate is excellent in reliability, and can be preferably used for a large-screen and high-definition liquid crystal. TV, etc.

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

[Examples]

The abbreviations used in the examples are as follows.

(methacrylic monomer)

M6CA: (E)-3-(4-((6-(methacryloxy)hexyl)oxy)phenyl)acrylic acid

(carboxylic acid additive)

(Organic solvents)

THF: tetrahydrofuran

NMP: N-methyl-2-pyrrolidone

BC: butyl cellomycin

(polymerization initiator)

AIBN: 2,2'-azobisisobutyronitrile

The molecular weight measurement conditions of the polymer are as follows.

Device: room temperature gel permeation chromatography (GPC) device manufactured by SENSHU Scientific Co., Ltd. (SSC-7200)

Column: Shodex pipe column (KD-803, KD-805)

Column temperature: 50 ° C

Dissolution: N,N'-dimethylformamide (lithium bromide-hydrate (LiBr‧H ₂ O) as an additive is 30 mmol/L, phosphoric acid ‧ anhydrous crystal (o-phosphoric acid) is 30 mmol/L, tetrahydrofuran ( THF) is 10ml/L)

Flow rate: 1.0ml/min

Standard sample for calibration line preparation: TSK standard polyethylene oxide (molecular weight approximately 9,000, 150,000, 100,000, 30,000) manufactured by TOSOH Co., Ltd., and polyethylene glycol manufactured by Polymer Laboratories Inc. (molecular weight approximately 12,000, 4,000) , 1,000)

<Example 1>

M6CA (12.41 g, 35.0 mmol) was dissolved in THF (111.7 g), and degassed with a septum pump, and then AIBN (0.287 g, 1.8 mmol) was added and degassed. Subsequently, the reaction was carried out at 60 ° C for 30 hours to obtain a methacrylate polymer solution. The polymer solution was added dropwise to diethyl ether (500 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 (A). The polymer had a number average molecular weight of 11,000 and a weight average molecular weight of 26,000.

NMP (29.29 g) was added to the obtained methacrylate polymer powder (A) (6.0 g), and the mixture was stirred at room temperature for 5 hours to be dissolved. NMP (14.7 g) and BC (50.0 g) were added to the solution, and the mixture was stirred for 5 hours to obtain a liquid crystal alignment agent (A1).

In addition, 0.03 g (5% by mass based on the solid content) of the cinnamic acid-based additive 6MN2C was added to 10.0 g of the liquid crystal alignment agent (A1), and the mixture was stirred at room temperature for 3 hours to dissolve the liquid crystal alignment agent (A2-). 5).

Similarly, the liquid crystal alignment agents A2-10 to A7-50 were prepared by changing the kind and amount of the cinnamic acid additive shown in the following table.

<Example 2>

The liquid crystal cell was produced using the liquid crystal alignment agent (A2-5) obtained in Example 1, and the alignment of the low molecular liquid crystal was confirmed. The conditions of the irradiation amount of the polarized light UV in the liquid crystal alignment treatment and the heating temperature after the polarized UV irradiation were changed, and the conditions for obtaining the most suitable orientation were confirmed.

[Production of liquid crystal cell]

A glass substrate having a substrate size of 30 mm × 40 mm and a thickness of 0.7 mm was used, and a comb-shaped pixel electrode formed by patterning an ITO film was disposed. The pixel electrode has a comb-like shape in which a plurality of electrode elements having a U-shape in which the central portion is curved are arranged in plural. The width of each electrode element in the short-side direction was 10 μm, and the interval between the electrode elements was 20 μm. Since the pixel electrode forming each pixel is formed by arranging a plurality of electrode elements having a U-shaped central portion, the shape of each pixel is not a rectangular shape, and the image curved in the central portion in the same manner as the electrode element is a bold body. The shape of the word. Further, each of the pixels is divided into upper and lower sides by a curved portion at the center thereof, and has a first region on the upper side of the curved portion and a second region on the lower side. When the first region and the second region of each pixel are compared, the direction in which the electrode elements constituting the pixel electrodes are formed is different. In other words, when the alignment processing direction of the liquid crystal alignment film described later is a reference, the first region of the pixel is formed such that the electrode element of the pixel electrode is at an angle of +15° (clockwise), and the second region of the pixel is The electrode element of the pixel electrode is formed at an angle of -15° (clockwise). In other words, in the first region and the second region of each pixel, the direction of the rotation of the liquid crystal in the substrate plane (in-plane switching) caused by the voltage application between the pixel electrode and the counter electrode is mutually It is constructed in the opposite direction. The liquid crystal alignment agent (A2) obtained in Example 1 was spin-coated on the substrate to which the above electrode was prepared. Subsequently, the film was dried on a hot plate at 70 ° C for 90 seconds to form a liquid crystal alignment film having a film thickness of 100 nm. Next, the coating film surface was irradiated with ultraviolet rays of 313 nm of 3 to 13 mJ/cm ² through a polarizing plate, and then heated at 140 to 170 ° C for 10 minutes to obtain a substrate with a liquid crystal alignment film. Further, a coating film was formed on the glass substrate having a columnar spacer having a height of 4 μm as an electrode on the opposite substrate, and an alignment treatment was performed. A sealant (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) was printed on a liquid crystal film of a substrate. Next, the other substrate is bonded so that the liquid crystal alignment film faces and the alignment direction becomes 0°, and then the sealing agent is thermally cured to form a cell. Liquid crystal MLC-2041 (manufactured by Merck Co., Ltd.) was injected into the cells by a pressure reduction 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 element.

The obtained liquid crystal cell was placed between polarizing plates set to be crossed with Nichol, and the alignment 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 results of the liquid crystal alignment according to the irradiation amount of UV and the subsequent heating temperature are shown in the following table.

In addition, it is confirmed that the alignment of the liquid crystal after the liquid crystal injection is indicated When it is "X", it is indicated as "○" when there is no misalignment and it is confirmed that the liquid crystal alignment is good.

<Example 3>

In the same manner as in Example 2, a liquid crystal cell was produced using a liquid crystal alignment agent (A2-10), and the alignment of the obtained liquid crystal cell was confirmed.

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

<Comparative Example 1>

In the same manner as in Example 2, a liquid crystal cell was produced using a liquid crystal alignment agent (A1), and the alignment of the obtained liquid crystal cell was confirmed.

Table 4 below lists the results of liquid crystal alignment of liquid crystal cells.

From the results of Tables 1 to 3, it was confirmed that the addition of the aromatic carboxylic acid-based additive resulted in a change in the irradiation temperature at which the optimum alignment property or the irradiation amount of the polarized light UV was obtained in Comparative Example 1.

In particular, regarding the heating temperature, there is a concern that the electrical characteristics of the crystal display element are deteriorated due to the influence of the residual solvent or the like. Therefore, it is required to perform firing at a relatively high temperature as much as possible, and the additive can be arbitrarily selected to obtain an optimum temperature. The directional heating conditions result in a wide range of material selection.

The reason for changing the optimum irradiation amount or heating temperature is considered to be Due to changes in the mesogenic portion of the supramolecular liquid crystal, the absorption band of UV or the change in sensitivity or reaction rate due to UV is caused.

[As evaluation of polymer film] <Example 4>

The optically active composition (A2-10) produced in the above Example 1 was applied onto a 1.1 mm quartz substrate by a spin coating method so as to have a film thickness of 100 nm, and dried on a hot plate at 70 °C.

The coating film was irradiated with a polarizing UV of 313 nm of 0 J/cm ² to 30 J/cm ² , and then heat-treated with a hot plate of 170 ° C for 10 minutes (so-called alignment amplification treatment by self-organization of polymer liquid crystal).

The polarized UV-irradiated substrate was subjected to the change in absorbance at 314 nm before and after heating at 170 ° C (Fig. 1) and dichroism (Fig. 2). Further, the measurement of the change in absorbance and the measurement of dichroism ΔA was carried out by measuring the polarized UV-vis absorption spectrum and calculating it by the following formula.

Dichroism △A=A||-A⊥

(A|| represents the absorbance in the parallel direction with respect to the polarized light UV of the irradiation, and A⊥ represents the absorbance in the x direction with respect to the polarized light UV of the irradiation. The absorbance is the value of the absorbance at 314 nm).

In the figure, "LPUV" indicates the result of irradiating the substrate with polarized UV light before heating at 170 ° C, and "anneal" indicates the result of irradiating the substrate with polarized UV light after heating at 170 ° C, and the exposure of the horizontal axis of the graph Energy means the amount of exposure.

The change in absorbance at 314 nm (Fig. 3) and dichroism (Fig. 4) when the optically active composition (A3-10) was used was also calculated in the same manner.

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

It can be seen from Fig. 1 and Fig. 3 that almost no change is observed after polarized UV irradiation. However, after heating (annealing), the vertical component increases and the parallel component decreases, so that the absorption components in the parallel direction are realigned and the surface is irradiated with respect to the light. Rearranged in the vertical direction.

In FIGS. 2 and 4, the negative dichromaticity (ΔA) means that there is anisotropy in the vertical direction (in-plane) with respect to the irradiation axis.

<Comparative Example 2>

The dichroism of the liquid crystal alignment agent (A1) was also calculated in the same manner as in Example 4, but no significant dichroism was observed in any of the irradiation regions.

<Example 5>

The optically active compositions (A2-5, A2-30, and A2-50) were also treated in the same manner as in Example 4, and the in-plane ordering parameters (in-plane orientation S) of each film were traced in cooperation with A2-10.

The measurement of the in-plane internal orientation S was carried out by measuring the polarized UV-vis absorption spectrum and calculating it by the following formula.

Orientation degree S=(A⊥-A||)/(A⊥+2A||)

(Here, A ⊥ indicates the absorbance of the vertical component with respect to the polarization UV irradiation axis in the measurement of the absorbance of the film after heat treatment, and A | | indicates the absorbance of the parallel component).

Further, both A⊥ and A|| use the absorbance at 314 nm.

<Comparative Example 3>

The in-plane orientation S when the liquid crystal alignment agent (A1) was used was also calculated in the same manner.

The in-plane alignment degree S of each irradiation amount obtained in Example 5 and Comparative Example 3 is shown in Fig. 5 .

In Fig. 5, since both have positive values, it can be seen that they are aligned in the vertical direction with respect to the light irradiation axis. The larger the value in the figure, the higher the alignment.

From the evaluation of Example 4 and Comparative Example 2, it was confirmed that by adding an additive of cinnamic acid type, an absorbance change or a dichroism change which cannot be exhibited only by the liquid crystal alignment agent (A1) is produced, and the amount of polarized UV irradiation can be further obtained. Or the size of the dichroism changes.

According to the evaluation of Example 5 and Comparative Example 3, it was found that by adding the cinnamic acid-based additive, the in-plane orientation which cannot be exhibited by the liquid crystal alignment agent (A1) can be produced, and the amount of the cinnamic acid-based addition can be increased. The optimum irradiation area in which the in-plane orientation is increased changes.

In the first to fifth embodiments, the reason why the optimum irradiation amount and the heating temperature are changed is considered to be that the absorption band of UV or the sensitivity or reaction rate due to UV is changed by changing the mesogenic structure of the supramolecular liquid crystal. Caused by.

Claims (10)

An optically active composition comprising the following components (A) and (B), wherein the component (A) contains a photoreactive group, and the component (A) and the component (B) are hydrogen-bonded to form a liquid crystal. a supramolecule: (A) a polymer having a side chain having a carboxylic acid group structure, and (B) at least one compound selected from a compound represented by the following formula (1), Wherein Q represents a single bond or an alkylene group having 1 to 12 carbon atoms, and T represents any carbon atom other than a Q or X bond which may be substituted by an oxygen atom, a nitrogen atom or a sulfur atom, and Q Or a carbon atom or a heterocyclic ring of 5 or 6 members in which a hydrogen atom on any carbon atom other than the X bond is substituted by a monovalent organic group, or a structure in which 2 to 4 bonds or condensed rings of the ring are bonded. An aromatic ring, X represents a single bond or an alkylene group having 1 to 12 carbon atoms, Y represents a single bond, an ether, an azo, a thioether, or an ester, and Z represents an arbitrary hydrogen atom which may be substituted with fluorine, and any The adjacent carbon atom may be substituted with an alkyl group having 1 to 36 carbon atoms of the oxygen atom, and a represents 1 or 2, but X and Y are both single bonds, and when a is 1, Z is hydrogen. The hydrogen atom on the fluorine, iodine, bromine, chlorine, hydroxyl, nitro, or nitrogen atom may be optionally substituted with one or two amine groups substituted with an alkyl group having 1 to 36 carbon atoms or a cyano group. The optically active composition of claim 1, wherein T in the formula (1) represents a benzene, a biphenyl, a terphenyl which has a hydrogen atom at any carbon atom other than the Q or X bond, which may be substituted with a monovalent organic group. An aromatic ring of any of naphthalene, anthracene, pyrene, pyridine, furan, pyrrole or thiophene. The optically active composition of claim 1 or 2, wherein T in the formula (1) represents a benzene, a biphenyl having a hydrogen atom on any carbon atom other than the Q or X bond, which may be substituted with a monovalent organic group. An aromatic ring of any structure of terphenyl, naphthalene, anthracene or anthracene. The optically active composition according to any one of claims 1 to 3, wherein the component (A) contains a carboxylic acid group and a photoreactive group in one side chain structure. The optically active composition 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). The optically active composition according to any one of claims 1 to 5, wherein the component (A) has a side containing a carboxylic acid group structure selected from the group consisting of the following formulas (2) and (3) Chain polymer, Wherein A represents a group selected from a single bond, -O-, -COO-, -CONH-, -NH-, and -CH=CH-COO-, and B represents a single bond, -O-, -COO -, -CONH-, -NH-, and -CH=CH-COO- selected groups, except in formula (2), at least one of A and B is -CH=CH-COO-, Ar ₁ and Ar ₂ each independently represents a phenyl or naphthyl group, and l and m are each independently an integer of 0 to 12]. The optically active composition according to any one of claims 1 to 6, wherein the component (B) is at least one selected from the group consisting of Wherein R represents any unsubstituted carbon atom which may be substituted with an alkyl group having 1 to 36 carbon atoms, and R' represents an oxygen atom, a sulfur atom, or a hydrogen atom on the nitrogen may be substituted with a monovalent value. The nitrogen atom of the organic group, and the one-valent organic group in the above R' represents an alkyl group having 1 to 10 carbon atoms or a phenyl group which may be substituted with an oxygen atom as long as it is not adjacent. A liquid crystal alignment agent containing the optically active composition according to any one of claims 1 to 7. A liquid crystal alignment film obtained by the liquid crystal alignment agent of claim 8. A liquid crystal display element comprising the liquid crystal alignment film of claim 9.