KR102430605B1 - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

[화학식 2]

This invention provides the liquid crystal aligning film for which orientation control ability is provided with high efficiency, and the area|region of the optimal polarization|polarized-light ultraviolet irradiation amount is wide, and the liquid crystal aligning agent for obtaining it. According to this invention, the following (A) component and (B) component are contained, a photoreactive group is contained in either or both of the side chain of (A) component, and (B) component, (A) component and ( B) An optically active composition characterized in that the component forms a liquid crystalline supramolecules through hydrogen bonding: (A) a polymer having a side chain containing a carboxylic acid group structure, and (B) the following formulas (1) and ( 2) At least 1 sort(s) of compound chosen from the compound represented by [the definition of the symbol in a formula is as described in the specification].
[Formula 1]

[Formula 2]

Description

A liquid crystal aligning agent, a liquid crystal aligning film, and a liquid crystal display element {LIQUID CRYSTAL ALIGNMENT AGENT, LIQUID CRYSTAL ALIGNMENT FILM, AND LIQUID CRYSTAL DISPLAY ELEMENT}

TECHNICAL FIELD The present invention relates to a liquid crystal aligning agent, a liquid crystal aligning film, and a liquid crystal display element using the same, and a polymer film suitable for manufacturing an optical element in which molecular orientation such as a retardation film or a polarization diffraction element is controlled.

BACKGROUND ART Liquid crystal display elements are known as light-weight, thin, and low-power display devices, and in recent years they have been used for large-scale television applications, and have achieved remarkable development. A liquid crystal display element clamps a liquid crystal layer with a pair of transparent board|substrates provided with an electrode, and is comprised, for example. And in a liquid crystal display element, the organic film which consists of an organic material is used as a liquid crystal aligning film so that a liquid crystal may become a desired orientation state between board|substrates.

That is, a liquid crystal aligning film is provided in the surface in contact with the liquid crystal of the board|substrate which clamps a liquid crystal as a structural member of a liquid crystal display element, and is playing the role of orientating a liquid crystal in a fixed direction between the board|substrates. And in addition to the role of orientating a liquid crystal in fixed directions, such as a direction parallel to a board|substrate, the role of controlling the pretilt angle of a liquid crystal may be calculated|required by a liquid crystal aligning film, for example. The ability to control the orientation of a liquid crystal in such a liquid crystal aligning film (it is hereafter called orientation control ability.) is provided by orientation-processing with respect to the organic film which comprises a liquid crystal aligning film.

Conventionally, the rubbing method is known as an orientation processing method of the liquid crystal aligning film for providing orientation control ability. In the rubbing method, the surface of an organic film such as polyvinyl alcohol or polyamide or polyimide on a substrate is rubbed in a certain direction with a cloth such as cotton, nylon, or polyester in a certain direction (rubbing), in the rubbing direction (rubbing direction) A method of aligning liquid crystals. Since this rubbing method can implement|achieve the alignment state of a relatively stable liquid crystal easily, it has been used in the manufacturing process of the conventional liquid crystal display element. And as an organic film used for a liquid crystal aligning film, the polyimide-type organic film excellent in reliability, such as heat resistance, and an electrical property, has been mainly selected.

However, as for the rubbing method of rubbing the surface of the liquid crystal aligning film which consists of polyimide etc., generation|occurrence|production of dust generation and static electricity may become a problem. In addition, due to the recent increase in precision of liquid crystal display elements and the irregularities caused by the electrodes on the corresponding substrates and the switching active elements for driving liquid crystals, the surface of the liquid crystal aligning film cannot be uniformly rubbed with a cloth, and uniform liquid crystal alignment can be realized. There were cases where there was no

Then, as another orientation processing method of the liquid crystal aligning film which does not rub, the photo-alignment method is examined actively.

Although there are various methods in the photo-alignment method, anisotropy is formed in the organic film which comprises a liquid crystal aligning film by linearly polarized light or collimated light, and a liquid crystal is orientated according to the anisotropy. As the main orientation method, polarized ultraviolet irradiation is used to irradiate a polarized ultraviolet light using a "photodegradable type" or polyvinyl cinnamate that causes anisotropic decomposition to a molecular structure by irradiation with polarized ultraviolet light, and two side chains parallel to polarized light are used. When using a "dimerization type" that generates a dimerization reaction (crosslinking reaction) in the double bond portion of (for example, refer to Patent Document 1), a side chain type polymer having azobenzene in the side chain, polarized light "Isomerization type" which irradiates an ultraviolet-ray, causes an isomerization reaction in the azobenzene part of a side chain parallel to polarization|polarized-light, and orientates a liquid crystal in the direction orthogonal to the polarization direction (for example, refer nonpatent literature 2). ) is known.

On the other hand, the new photo-alignment method (henceforth an orientation amplification method) using the photosensitive side chain type polymer|macromolecule which can express liquid crystallinity is examined in recent years. This is to the film|membrane which has photosensitive side chain type polymer|macromolecule which can express liquid crystallinity, orientation-processed by polarized light irradiation, and after that, through the process of heating the side chain type polymer film, orientation control ability was provided to obtain a coating film. At this time, the slight anisotropy expressed by polarized light irradiation becomes a driving force, and liquid crystalline side chain type polymer|macromolecule itself is efficiently reorientated by self-organization. As a result, as a liquid crystal aligning film, highly efficient orientation processing is implement|achieved, and the liquid crystal aligning film to which high orientation control ability was provided can be obtained (for example, refer patent document 2).

In addition, the polymer film obtained by this orientation amplification method can be used as various optical elements, such as retardation film, in addition to the use of a liquid crystal aligning film, since birefringence is expressed by molecular orientation.

Patent Publication No. 3893659 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 light optimal for the introduction of highly efficient anisotropy to the liquid crystal aligning film used for the orientation amplification method corresponds to the irradiation amount of the polarized ultraviolet light which optimizes the amount with which the photosensitive group photoreacts in the coating film. As a result of irradiating the ultraviolet-ray which polarized with respect to the liquid crystal aligning film used for an orientation amplification method, when there are few photosensitive groups of the side chain which photoreacts, it will not become sufficient photoreaction amount. In that case, even if it heats after that, sufficient self-organization does not advance. On the other hand, when the photosensitive group of the photoreactive side chain becomes excess, the film|membrane obtained will become rigid, and it may become a hindrance of advancing of the self-assembly by subsequent heating.

Currently, among the liquid crystal aligning films used for the orientation amplification method, the area of the irradiation amount of the optimal polarization|polarized-light ultraviolet-ray mentioned above exists because the sensitivity of the photoreactive group in the polymer used is high. As a result, the fall of the manufacturing efficiency of a liquid crystal display element poses a problem.

In addition, when the firing temperature of the liquid crystal aligning film is low, the reliability of the liquid crystal display element may decrease due to the influence of residual solvents, etc., but the liquid crystal aligning agent obtained by the orientation amplification method has a temperature higher than the liquid crystal expression temperature of the polymer liquid crystal due to its properties. Since calcination cannot be carried out in , the calcination temperature is generally low, and residual solvents and the like are one factor that lowers reliability.

Then, an object of this invention is to provide the liquid crystal aligning film with a wide process margin in which orientation control ability is provided with high efficiency, and can adjust to an optimal polarization|polarized-light ultraviolet irradiation amount and an optimal baking temperature.

MEANS TO SOLVE THE PROBLEM The present inventors discovered the following invention, as a result of earnestly examining in order to achieve the said subject.

<1> following (A) component and (B) component are contained, a photoreactive group is contained in any one or both of the side chain of (A) component, and (B) component, (A) component and (B) An optically active composition, characterized in that the component forms a liquid crystalline supramolecules through hydrogen bonding.

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

(B) at least one compound selected from the following formula (1) or (2), an aromatic heterocyclic compound represented by pyrazine and naphthyridine:

[Formula 1]

[During the meal,

X represents a single bond or an alkylene, ether, ester, azo, thioether, disulfide, tetrazine, disubstituted alkene, alkyne, or phenylene having 1 to 12 carbon atoms;

S represents ether, ester or phenylene,

Py each independently represents a structure selected from the following group, and in the following structures, a dotted portion is a portion bonded to X in Formula (1), and a portion bonded to S in Formula (2) to be.

[Formula 2]

].

The optically active composition of <2> said <1> WHEREIN: It is good that the said (A) component contains a carboxylic acid group and a photoreactive group in one side chain structure.

<3> In the optically active composition of <1> or <2>, the content of the component (B) is preferably 0.5 wt% to 70 wt% with respect to the weight of the polymer of the component (A).

<4> In the optically active composition according to any one of <1> to <3>, the component (A) is any one carboxylic acid group selected from the group consisting of the following formulas (3) and (4) It is preferable that it is a polymer which has a side chain containing a structure.

[Formula 3]

[During the meal,

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].

<5> In the optically active composition according to any one of <1> to <4>, the component (B) is preferably at least one compound selected from the following.

[Formula 4]

[Formula 5]

[Formula 6]

[During the meal,

n represents an integer of 1 to 3,

l represents an integer of 2 to 6, and

m represents the integer of 1-4].

The liquid crystal aligning agent containing the optically active composition in any one of <6> said <1>-<5>.

The liquid crystal aligning film obtained from the liquid crystal aligning agent of <7> said <6>.

A liquid crystal display element provided with the liquid crystal aligning film of <8> said <7>.

According to the present invention, an optically active composition, which is highly efficient in orientation control ability, and has a wide region of optimal polarized ultraviolet irradiation dose, or a liquid crystal expression temperature of a polymer liquid crystal can be preferably selected, and a liquid crystal containing the composition An aligning agent, the liquid crystal aligning film obtained from this liquid crystal aligning agent, the board|substrate which has this liquid crystal aligning film, and the transverse electric field drive type liquid crystal display element which has this board|substrate can be provided. Furthermore, by using the optically active composition, it is possible to provide a polymer film having a wide process margin (polarized ultraviolet irradiation amount and firing temperature) in the production of an optical element, such as a retardation film or the like.

1 is a graph showing the dichroism obtained in Example 8 and Comparative Example 2. FIG.
Fig. 2 is a graph showing the degree of in-plane orientation S at each dose obtained in Example 10 and Comparative Example 3;

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in detail.

<Optical Active Composition>

The optically active composition of the present invention contains the following component (A) and component (B), and contains a photoreactive group in either or both of component (A) and component (B), and component (A) and ( It is characterized in that the component B) forms a liquid crystal supramolecules through hydrogen bonding.

(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 formulas (1) and (2):

[Formula 7]

[During the meal,

X represents a single bond or an alkylene, ether, ester, azo, thioether, disulfide, tetrazine, disubstituted alkene, alkyne, and phenylene having 1 to 12 carbon atoms;

S represents ether, ester or phenylene,

Py each independently represents a structure selected from the following group, and in the following structures, a dotted portion is a portion bonded to X in Formula (1), and a portion bonded to S in Formula (2) to be.

[Formula 8]

].

Although it is not certain why the composition which satisfies the said structural requirement exhibits the effect which can solve the subject of this invention, it is thought as follows generally.

It is said that the polymer which has a side chain containing the carboxylic acid group structure which is (A) component in this invention shows a supramolecular liquid crystal by the hydrogen bond between carboxylic acids. In such a supramolecular liquid crystal, the structure of the aromatic ring-carboxylic acid-carboxylic acid-aromatic ring forming a hydrogen bond has a mesogenic structure as shown below, and the temperature range showing liquid crystallinity and the absorption band of ultraviolet light It is thought that the etc. are mostly determined in this mesogen site|part.

[Formula 9]

At this time, if the aromatic heterocyclic structure as the component (B) of the present invention is present, a part of the carboxylic acid forms a mesogenic structure by hydrogen bonding (or interaction such as an ionic bond) with the heterocyclic ring, and liquid crystal to manifest sexuality. As a result, the temperature range showing liquid crystallinity, the absorption band of ultraviolet rays, and the like change. In the present invention, by freely selecting these combinations, it becomes possible to adjust the expression temperature region of the liquid crystal, the sensitivity to ultraviolet rays, and the like to an arbitrary range. In addition, they are not intended to limit the present invention as a theory.

<<(A) component>>

(A) A component is a polymer which has a side chain containing a carboxylic acid group structure. At this time, although a carboxylic acid group and a photoreactive group are contained in one side chain structure, or the other side chain containing a photoreactive group may exist in a polymer, from the point of optically active composition reaction efficiency, it is a carboxylic acid group and a photoreactive group in one side chain structure. It is preferable to contain an acid group and a photoreactive group.

When a carboxylic acid group and a photoreactive group are contained in one side chain structure, the general formula of the side chain (henceforth a specific side chain is also called) can be represented by said Formula (3) and (4).

In the formulas (3) and (4), A represents a group selected from a single bond, -O-, -COO-, -CONH-, and -NH-, and among them, -O-, -COO- is preferable.

Further, in the formulas (3) and (4), B represents a group selected from a single bond, -O-, -COO-, -CONH-, -NH-, and -CH=CH-COO-, among them, -O- and -COO- are preferable from a viewpoint of liquid crystalline expression.

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

l and m are each independently an integer of 0-12. Especially, the viewpoint of liquid crystalline expression to the integer of 2-8 is preferable.

Although the specific example of the side chain structure shown by said Formula (3) and (4) is illustrated as follows, it is not limited to these.

[Formula 10]

In formula, m represents the integer of 2-12.

<<the manufacturing method of the polymer>>

(A) The polymer of component can be obtained by the polymerization reaction of the monomer containing the specific side chain mentioned above. Moreover, it can obtain also by copolymerization of the monomer which has a side chain containing a photoreactive group, and the monomer which has a side chain containing a carboxylic acid group. Moreover, it can copolymerize with another monomer in the range which does not impair liquid crystalline expression ability.

Examples of the other monomer include an industrially available monomer capable of a radical polymerization reaction.

As a specific example of another monomer, an unsaturated carboxylic acid, an acrylic acid ester compound, a methacrylic acid ester compound, a maleimide compound, an acrylonitrile, maleic anhydride, a styrene compound, a vinyl compound, etc. are mentioned.

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, 2,2, 2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, Tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate , and 8-ethyl-8-tricyclodecyl acrylate.

As a methacrylic acid ester compound, for example, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate , Phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methacrylate Toxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-propyl -2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate, and the like. Cyclic ethers such as glycidyl (meth) acrylate, (3-methyl-3-oxetanyl) methyl (meth) acrylate, and (3-ethyl-3-oxetanyl) methyl (meth) acrylate A (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.

As a maleimide compound, maleimide, N-methyl maleimide, N-phenyl maleimide, N-cyclohexyl maleimide, etc. are mentioned, for example.

It does not specifically limit about the manufacturing method of the polymer of (A) component, The general-purpose method handled industrially can be used. Specifically, it can manufacture by cationic polymerization using the vinyl group of a specific side chain monomer, radical polymerization, or anionic polymerization. Among these, radical polymerization is particularly preferable from the viewpoint of easiness of reaction control and the like.

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

A radical thermal polymerization initiator is a compound which generate|occur|produces a radical by heating more than decomposition temperature. As such a radical thermal polymerization initiator, for example, ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), hydroperoxides ( Hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyketals (dibutyl peroxide, etc.) oxycyclohexane, etc.), alkyl peresters (peroxyneodecanoic acid-tert-butyl ester, peroxypivalic acid-tert-butyl ester, peroxy 2-ethylcyclohexanoic acid-tert-amyl ester, etc.), persulfate compounds (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), azo compounds (azobisisobutyronitrile, 2,2'-di(2-hydroxyethyl) azobisisobutyronitrile, etc.) can Such a radical thermal polymerization initiator may be used individually by 1 type, or may be used in combination of 2 or more type.

A radical photoinitiator will not be specifically limited if it is a compound which starts radical polymerization by light irradiation. Examples of such a radical photopolymerization initiator include benzophenone, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, xanthone, thioxanthone, isopropylxanthone, and 2,4-diethylthioxanthone. , 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexylphenylketone, iso Propylbenzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1-[4-( Methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,4-dimethylaminobenzoate ethyl, 4 -Dimethylaminobenzoic acid isoamyl, 4,4'-di(t-butylperoxycarbonyl)benzophenone, 3,4,4'-tri(t-butylperoxycarbonyl)benzophenone, 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, 2-(4'-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxystyryl) reyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2'-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-pentyloxystyryl)-4,6-bis(trichloromethyl) -s-triazine, 4-[p-N,N-di(ethoxycarbonylmethyl)]-2,6-di(trichloromethyl)-s-triazine, 1,3-bis(trichloromethyl)- 5-(2'-chlorophenyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(4'-methoxyphenyl)-s-triazine, 2-(p-dimethylaminostiazine Lil) benzoxazole, 2-(p-dimethylaminostyryl) benzthiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis(7-diethylaminocoumarin), 2-(o- Chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra kiss (4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1, 2'-biimidazole, 2,2'bis(2,4-dibromophenyl)-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-morpholinopropionyl)-9-n- Dodecylcarbazole, 1-hydroxycyclohexylphenyl ketone, bis(5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrole-1- yl)-phenyl) titanium, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(t-hexylperoxycarbonyl) Benzophenone, 3,3'-di(methoxycarbonyl)-4,4'-di(t-butylperoxycarbonyl)benzophenone, 3,4'-di(methoxycarbonyl)-4,3 '-di(t-butylperoxycarbonyl)benzophenone, 4,4'-di(methoxycarbonyl)-3,3'-di(t-butylperoxycarbonyl)benzophenone, 2-(3 -Methyl-3H-benzothiazol-2-ylidene)-1-naphthalen-2-yl-ethanone, or 2-(3-methyl-1,3-benzothiazol-2(3H)-ylidene) -1-(2-benzoyl)ethanone etc. are mentioned. These compounds may be used independently and may be used in mixture of 2 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 for the polymerization reaction is not particularly limited as long as the resulting polymer is dissolved. The specific example is given below.

N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, Pyridine, dimethyl sulfone, hexamethyl sulfoxide, γ-butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl Ketone, 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 monoacetate, 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, amyl acetate, butyl butyrate, butyl ether, diiso Butyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, acetic acid Methyl, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, 3-methoxy methyl propionate, 3-ethoxy methyl ethyl ethyl propionate, 3-methoxy ethyl propionate, 3-ethoxypropionic acid , 3-methoxypropionic acid, 3-methoxypropionic acid propyl, 3-methoxypropionate butyl, diglyme, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N,N-dimethylpropanamide , 3-ethoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropana Mead etc. are mentioned.

These organic solvents may be used independently or may be mixed and used. Moreover, even if it is a solvent which does not dissolve the produced|generated polymer|macromolecule, you may use it in the range in which the produced|generated polymer|macromolecule does not precipitate, mixing with the organic solvent mentioned above.

Moreover, since oxygen in the organic solvent inhibits the polymerization reaction in radical polymerization, it is preferable to use the organic solvent degassed to the extent possible.

Although the polymerization temperature at the time of radical polymerization can select the arbitrary temperature of 30 degreeC - 150 degreeC, Preferably it is the range of 50 degreeC - 100 degreeC. In addition, although the reaction can be carried out at any concentration, if the concentration is too low, it becomes difficult to obtain a polymer having a high molecular weight, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring becomes difficult. , Preferably they are 1 mass % - 50 mass %, More preferably, they are 5 mass % - 30 mass %. The reaction initial stage can be performed at high concentration, and an organic solvent can be added after that.

In the radical polymerization reaction described above, when the ratio of the radical polymerization initiator is large with respect to the monomer, the molecular weight of the obtained polymer becomes small, and when the ratio of the radical polymerization initiator is small, the molecular weight of the obtained polymer becomes large. It is preferable that it is -10 mol%. Moreover, in the case of polymerization, various monomer components, a solvent, an initiator, etc. can also be added.

[Recovery of polymer]

What is necessary is just to inject|throw-in the reaction solution to a poor solvent, and just to precipitate these polymers, when collect|recovering the produced|generated polymer|macromolecule from the reaction solution of the polymer obtained by the reaction mentioned above. Examples of the poor solvent used for precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, and water. can After the polymer which was charged into the poor solvent and precipitated was recovered by filtration, the polymer can be dried at room temperature or under reduced pressure at room temperature or by heating. Moreover, when the polymer which carried out precipitation collection|recovery is made to dissolve again in an organic solvent, and operation which carries out reprecipitation collection|recovery is repeated 2 times - 10 times, the impurity in a polymer can be decreased. Examples of the poor solvent at this time include alcohols, ketones, and hydrocarbons, and the use of three or more types of poor solvents selected from these is preferable because the efficiency of purification further increases.

The molecular weight of the polymer of component (A) of the present invention is the weight average molecular weight measured by the GPC (Gel Permeation Chromatography) method, when the strength of the obtained coating film, workability at the time of coating film formation, and the uniformity of the coating film are taken into consideration, 2000-1000000 are preferable, More preferably, it is 5000-100000.

<< component B>>

The optically active composition of the present invention contains, as component (B), at least one compound selected from compounds represented by the following formula (1) or (2).

[Formula 11]

In the formulas (1) and (2), X is a single bond or an alkylene having 1 to 12 carbon atoms, ether, ester, azo, thioether, disulfide, tetrazine, disubstituted alkene, alkyne, or phenylene, preferably ester, azo, disubstituted alkene, or alkyne. Here, "disubstituted alkene" refers to a disubstituted alkene having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, and the substituent of the disubstituted alkene is an alkyl group having 1 to 5 carbon atoms, fluorine or cyano group. indicates.

In the formulas (1) and (2), S represents ether, ester or phenylene, preferably phenylene.

In the formulas (1) and (2), Py each independently represents a structure selected from the following groups. In addition, among the following structures, the part with a dot is a part couple|bonded with X in Formula (1), and is a part couple|bonded with S in Formula (2). Preferred Py is 4-pyridyl and 4-pyridylphenyl.

[Formula 12]

Although the specific example of the compound represented by said Formula (1) and (2) is illustrated below, it is not limited to this.

[Formula 13]

[Formula 14]

[Formula 15]

[During the meal,

n represents an integer of 1 to 3,

l represents an integer of 2 to 6, and

m represents the integer of 1-4].

Moreover, from a viewpoint of liquid crystalline expression, B1-B9, B16, B18 are preferable, and B1-B5 is more preferable.

It is preferable to contain 0.5 weight% - 70 weight% with respect to the weight of the polymer of the said (A) component, and, as for the said (B) component, it is more preferable to contain 5 weight% - 50 weight%.

Moreover, even if it uses the following compound as (B) component, it is possible to acquire the same effect.

[Formula 16]

<Adjustment of the optically active composition>

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 as a solution which melt|dissolved the A component, B component, and the various additives which are mentioned later as needed in the organic solvent. In that case, 1 mass % - 20 mass % are preferable, and, as for content of the component which summed up the A component, B component, and the various additives added as needed (henceforth a resin component), More preferably, 3 mass % -15 mass %, Especially preferably, it is 3 mass % - 10 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 in which the resin component is dissolved. The specific example is given below.

N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone Don, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, γ-butyrolactone, 3-methoxy-N,N-dimethylpropanamide, 3-ethoxy-N,N-dimethylpropane Amide, 3-butoxy-N,N-dimethylpropanamide, 1,3-dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclo 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 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, etc. are mentioned. These may be used independently or may be mixed and used.

The polymer contained in the optically active composition of the present invention may be any polymer having a side chain containing the above-mentioned carboxylic acid group structure, but other polymers other than those may be used in the range that does not impair liquid crystal expression ability and photosensitive performance. They may be mixed. In that case, content of the other polymer in a resin component is 0.5 mass % - 80 mass %, Preferably they are 1 mass % - 50 mass %.

The polymer etc. which are not the photosensitive side chain type polymer|macromolecule which consist of poly (meth)acrylate, a polyamic acid, a polyimide, etc., and can express liquid crystallinity are mentioned, for example as for such another polymer.

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, solvents and compounds that improve film thickness uniformity or surface smoothness when a solution of the optically active composition is applied, and compounds that improve adhesion between a coating film and a substrate.

The following are mentioned as a specific example of the solvent (poor solvent) which improves the uniformity of a film thickness and surface smoothness.

For example, isopropyl alcohol, 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 monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoethyl ether Propylene 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, methylcyclohexene, propyl ether, dihexyl ether, 1-hexanol, n-hexane , n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, Methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 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, lactic acid methyl ester, lactic acid ethyl ester, lactic acid n-propyl ester, lactic acid n-butyl ester, lactic acid isoamyl ester, etc. The solvent etc. which have a low surface tension are mentioned.

These poor solvents may be used by one type or in mixture of multiple types. When using the solvent as described above, it is preferable that the total amount of the solvent is 5% by mass to 80% by mass, so as not to significantly reduce the solubility of the entire solvent contained in the optically active composition of the present invention. Preferably they are 20 mass % - 60 mass %.

As a compound which improves the uniformity of a film thickness and surface smoothness, a fluorochemical surfactant, silicone type surfactant, nonionic surfactant, etc. are mentioned.

More specifically, for example, FTOP (registered trademark) 301, EF303, EF352 (manufactured by Tochem Products), Megapack (registered trademark) F171, F173, R-30 (manufactured by DIC), Florard FC430, FC431 (manufactured by Sumitomo 3M), AsahiGuard (registered trademark), AG710 (manufactured by Asahi Glass, Inc.), Sufflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimi Chemical) ) and the like. To [ the usage ratio of these surfactant / 100 mass parts of resin components contained in a polymer composition ], Preferably they are 0.01 mass part - 2 mass parts, More preferably, they are 0.01 mass part - 1 mass part.

As a specific example of the compound which improves the adhesiveness of a coating film and a board|substrate, the functional silane containing compound etc. which are shown below are mentioned.

For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3 -Aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxy Carbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetri 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-phenyl-3- Aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis(oxyethylene)-3-aminopropyltrimethoxysilane, N-bis(oxyethylene)-3-aminopropyltri Ethoxysilane etc. are mentioned.

In addition to improving the adhesion between the substrate and the coating film, the present invention provides an additive of the following phenoplast type or epoxy group-containing compound for the purpose of preventing a decrease in electrical properties due to backlight when a liquid crystal display element is constituted. may be contained in the optically active composition of Although a specific phenoplast type additive is shown below, it is not limited to this structure.

[Formula 17]

Specific examples of the epoxy group-containing compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and neopentyl. 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-xylenediamine, 1,3-bis(N,N-diglycidylaminomethyl ) cyclohexane, N,N,N',N',-tetraglycidyl-4,4'-diaminodiphenylmethane, and the like.

When using the compound which improves adhesiveness with a board|substrate, it is preferable that the usage-amount is 0.1 mass part - 30 mass parts with respect to 100 mass parts of the resin component contained in an optically active composition, More preferably, 1 mass part - 20 parts by mass. When the usage-amount is less than 0.1 mass part, the effect of an adhesive improvement cannot be anticipated, and when it increases more than 30 mass parts, the orientation of a liquid crystal may worsen.

A photosensitizer can also be used as an additive. Colorless sensitizers and triplet sensitizers are preferred.

Examples of the photosensitizer include an aromatic nitro compound, coumarin (7-diethylamino-4-methylcoumarin, 7-hydroxy4-methylcoumarin), ketocoumarin, carbonylbiscoumarin, aromatic 2-hydroxyketone, and amino. substituted, aromatic 2-hydroxyketones (2-hydroxybenzophenone, mono- or di-p-(dimethylamino)-2-hydroxybenzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, Benzanthrone, thiazoline (2-benzoylmethylene-3-methyl-β-naphthothiazoline, 2-(β-naphthoylmethylene)-3-methylbenzothiazoline, 2-(α-naphthoylmethylene)-3 -Methylbenzothiazoline, 2-(4-biphenoylmethylene)-3-methylbenzothiazoline, 2-(β-naphthoylmethylene)-3-methyl-β-naphthothiazoline, 2-(4-biphenoyl Methylene)-3-methyl-β-naphthothiazoline, 2-(p-fluorobenzoylmethylene)-3-methyl-β-naphthothiazoline), oxazoline (2-benzoylmethylene-3-methyl-β-naph Tooxazoline, 2-(β-naphthoylmethylene)-3-methylbenzoxazoline, 2-(α-naphthoylmethylene)-3-methylbenzoxazoline, 2-(4-biphenoylmethylene)-3- Methylbenzoxazoline, 2-(β-naphthoylmethylene)-3-methyl-β-naphthooxazoline, 2-(4-biphenoylmethylene)-3-methyl-β-naphthooxazoline, 2-( p-fluorobenzoylmethylene)-3-methyl-β-naphthooxazoline), benzothiazole, nitroaniline (m- or p-nitroaniline, 2,4,6-trinitroaniline) or nitroacenaphthene (5- nitroacenaphthene), (2-[(m-hydroxy-p-methoxy)styryl]benzothiazole, benzoin alkyl ether, N-alkylated phthalone, acetophenone ketal (2,2-dimethoxyphenylethanone) ), naphthalene, anthracene (2-naphthalenemethanol, 2-naphthalenecarboxylic acid, 9-anthracenemethanol, and 9-anthracenecarboxylic acid), benzopyran, azoindolidine, merocumarin, and the like.

Preferred are aromatic 2-hydroxyketone (benzophenone), coumarin, ketocoumarin, carbonylbiscoumarin, acetophenone, anthraquinone, xanthone, thioxanthone, and acetophenone ketal.

In the optically active composition of the present invention, as long as the effects of the present invention are not impaired other than those described above, in order to change electrical properties such as dielectric constant and conductivity of the coating film, a dielectric material, a conductive material, and furthermore, a coating film You may add a crosslinking|crosslinked compound for the purpose of raising the hardness and density of the film|membrane when it is set as.

The coating film which apply|coated and baked the above-mentioned optically active composition to a board|substrate can be used as a liquid crystal aligning film, for example. The method of apply|coating the liquid crystal aligning agent containing the optically active composition of this invention on the board|substrate which has the electrically conductive film for lateral electric field drive is not specifically limited.

As for the coating method, industrially, the method of performing by screen printing, offset printing, flexographic printing, the inkjet method, etc. is common. As another coating method, there exist a dip method, the roll coater method, the slit coater method, the spinner method (rotary coating method), the spray method, etc., You may use these according to the objective.

<<Manufacture of liquid crystal display element>>

<Process [I]>

Manufacture of the liquid crystal display element using the liquid crystal aligning agent containing the optically active composition of this invention is shown by the following processes [I] - [IV]. First, process [I] is a process of apply|coating the liquid crystal aligning agent of this invention on the board|substrate which has an electrically conductive film. After coating, the solvent is evaporated at 50 to 200°C, preferably 50 to 150°C, using a heating means such as a hot plate, heat circulation type oven or IR (infrared) type oven to obtain a coating film. It is preferable that the drying temperature at this time is lower than the liquid crystal phase expression temperature of side chain type polymer|macromolecule.

When the thickness of the coating film is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and when it is too thin, the reliability of the liquid crystal display element may decrease. Therefore, preferably 5 nm to 300 nm, more preferably 10 nm ∼150 nm.

Moreover, it is also possible to set the process of cooling the board|substrate with a coating film to room temperature after the [I] process before the subsequent [II] process.

<Process [II]>

In process [II], the ultraviolet-ray which polarized to the coating film obtained by process [I] is irradiated. In the case of irradiating the polarized ultraviolet ray to the film surface of the coating film, the polarized ultraviolet ray is irradiated through the polarizing plate from a certain direction with respect to the substrate. As the ultraviolet rays to be used, ultraviolet rays having a wavelength of 100 nm to 400 nm can be used. Preferably, an optimal wavelength is selected through a filter etc. according to the kind of coating film to be used. And, for example, in order to selectively cause a photocrosslinking reaction, ultraviolet rays having a wavelength of 290 nm to 400 nm may be selected and used. As the ultraviolet light, for example, light emitted from a high-pressure mercury lamp can be used.

The irradiation amount of the polarized ultraviolet rays depends on the coating film to be used. The irradiation amount is the amount of polarized ultraviolet light that realizes the maximum value of ΔA (hereinafter also referred to as ΔAmax), which is the difference between the ultraviolet absorbance in a direction parallel to the polarization direction of the polarized ultraviolet light and the ultraviolet absorbance in the perpendicular direction in the coating film. It is preferable to set it within the range of 1 % - 70 %, and it is more preferable to set it as 1 % - 50 % of the range.

<Process [III]>

In process [III], the coating film to which the ultraviolet-ray polarized in process [II] was irradiated is heated. By heating, orientation control ability can be provided to a coating film.

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

It is preferable that heating temperature exists in the temperature range of the temperature (henceforth liquid-crystal expression temperature) at which side chain type polymer|macromolecule expresses liquid crystallinity. In the case of the surface of a thin film like a coating film, it is expected that the liquid crystal expression temperature of the surface of a coating film is lower than the liquid crystal expression temperature at the time of observing the photosensitive side chain type polymer|macromolecule which can express liquid crystallinity in bulk. For this reason, as for heating temperature, it is more preferable that it exists in the temperature range of the liquid-crystal expression temperature on the surface of a coating film. That is, the temperature range of the heating temperature after polarization ultraviolet irradiation is a temperature 10 ° C lower than the lower limit of the temperature range of the liquid crystal expression temperature of the side chain type polymer to be used as the lower limit, and the temperature 10 ° C lower than the upper limit of the liquid crystal temperature range. It is preferable that it is a temperature in the range made into an upper limit. When the heating temperature is lower than the above temperature range, the effect of amplifying anisotropy by heat in the coating film tends to be insufficient, and when the heating temperature is too high than the above temperature range, the state of the coating film is in an isotropic liquid state (isotropic top), and in this case, it may be difficult to reorient in one direction due to self-organization.

In addition, the liquid crystal expression temperature is above the glass transition temperature (Tg) at which the side chain polymer or coating film surface undergoes phase transition from the solid phase to the liquid crystal phase, and isotropic phase transition that causes the phase transition from the liquid crystal phase to the isotropic phase (isotropic phase) Temperature (Tiso) refers to the temperature below.

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 described in step [I].

By having the above process, in the manufacturing method of this invention, highly efficient and anisotropic introduction|transduction with respect to a coating film can be implement|achieved. And the board|substrate in which the liquid crystal aligning film was formed can be manufactured with high efficiency.

<Process [IV]>

[IV] A process opposes arrange|positions the board|substrate which has a liquid crystal aligning film obtained by [III] so that both liquid crystal aligning films may oppose through a liquid crystal, produces a liquid crystal cell by a well-known method, and produces a liquid crystal display element is a process that

If an example of preparation of a liquid crystal cell or liquid crystal display element is given, the above-mentioned two board|substrates are prepared, a spacer is spread|dispersed on the liquid crystal aligning film of one board|substrate, a liquid crystal aligning film surface is made inside, and the other board|substrate The method of bonding and sealing a liquid crystal by pressure-reducing injection and sealing, or after dripping a liquid crystal to the liquid crystal aligning film surface which disperse|distributed the spacer, the method of bonding together a board|substrate and sealing, etc. can be illustrated. In this case, it is preferable to use a substrate having an electrode having a structure similar to that of a comb for lateral electric field driving as the substrate on one side. The diameter of the spacer at this time is preferably 1 µm to 30 µm, and more preferably 2 µm to 10 µm. The spacer diameter determines the distance between the pair of substrates that sandwich the liquid crystal layer, that is, the thickness of the liquid crystal layer.

In the manufacturing method of the board|substrate with a coating film of this invention, after apply|coating a polymer composition on a board|substrate to form a coating film, polarized ultraviolet-ray is irradiated. Next, by heating, highly efficient anisotropic introduction|transduction with respect to a side chain type polymer film is implement|achieved, and the board|substrate with a liquid crystal aligning film provided with the orientation control ability of a liquid crystal is manufactured.

In the coating film used for this invention, highly efficient anisotropic introduction to a coating film is implement|achieved using the principle of molecular reorientation caused by the self-organization based on the photoreaction of a side chain and 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 polymer, a coating film is formed on the substrate using the side chain polymer, then irradiated with polarized ultraviolet rays, and then, After heating, a liquid crystal display element is manufactured.

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

As described above, the substrate for a transverse electric field driving type liquid crystal display element manufactured by the method of the present invention or a transverse electric field driving type liquid crystal display element having the substrate has excellent reliability, and is suitable for a large screen, high-definition liquid crystal television, etc. can be used readily.

Hereinafter, although this invention is demonstrated using an Example, this invention is not limited to the Example.

Example

The abbreviation used in the Example is as follows.

(methacryl monomer)

[Formula 18]

(bipyridine-based additive)

[Formula 19]

(organic solvent)

THF: tetrahydrofuran

NMP: N-methyl-2-pyrrolidone

BC: Butyl Cellosolve

(Polymerization Initiator)

AIBN: 2,2'-azobisisobutyronitrile

Polymer molecular weight measurement conditions are as follows.

Apparatus: room temperature gel permeation chromatography (GPC) apparatus (SSC-7200) manufactured by Senshu Science Co., Ltd.;

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

Column temperature: 50℃

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

Flow rate: 1.0 ml/min

Standard samples for calibration curve preparation: TSK standard polyethylene oxide (molecular weights about 9000,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation, and polyethylene glycol manufactured by Polymer Laboratories (molecular weights about 12,000, 4,000, and 1,000).

<Example 1>

After dissolving M6CA (12.41 g, 35.0 mmol) in THF (111.7 g) and deaeration with a diaphragm pump, AIBN (0.287 g, 1.8 mmol) was added and deaeration was performed again. After that, it was made to react at 60 degreeC for 30 hours, and the polymer solution of methacrylate was obtained. This polymer solution was added dropwise to diethyl ether (500 ml), and the obtained precipitate was filtered. This deposit was wash|cleaned with diethyl ether, it was made to dry under reduced pressure in 40 degreeC oven, and the methacrylate polymer powder (A) was obtained. The number average molecular weight of this polymer was 11000, and the weight average molecular weight was 26000.

NMP (29.29g) was added to the obtained methacrylate polymer powder (A) (6.0g), and it stirred at room temperature for 5 hours, and was made to melt|dissolve. NMP (14.7g) and BC (50.0g) were added to this solution, and it stirred for 5 hours, and obtained the liquid crystal aligning agent (A1).

Moreover, 0.03 g (5 mass % with respect to solid content) of bipyridine-type additive BPy is added with respect to 10.0 g of said liquid crystal aligning agent (A1), it stirs at room temperature for 3 hours, and it melt|dissolves, and a liquid crystal aligning agent (A2) is prepared did.

Moreover, 0.03g (5 mass % with respect to solid content) of bipyridine-type additive BPyStyl is added with respect to 10.0g of said liquid crystal aligning agent (A1), it stirs and melts at room temperature for 3 hours, and a liquid crystal aligning agent (A3) is prepared did.

Moreover, 0.03g (5 mass % with respect to solid content) of bipyridine-type additive BPyC2 is added with respect to 10.0g of said liquid crystal aligning agent (A1), it stirs at room temperature for 3 hours, and it melt|dissolves, and a liquid crystal aligning agent (A4) is prepared did.

Moreover, 0.03g (5 mass % with respect to solid content) of bipyridine-type additive BPyC3 is added with respect to 10.0g of said liquid crystal aligning agent (A1), it stirs at room temperature for 3 hours, and it melt|dissolves, and a liquid crystal aligning agent (A5) is prepared did.

<Example 2>

After dissolving M6BA (15.32 g, 50.0 mmol) in THF (141.6 g) and deaeration with a diaphragm pump, AIBN (0.411 g, 2.5 mmol) was added and deaeration was performed again. After that, it was made to react at 60 degreeC for 30 hours, and the polymer solution of methacrylate was obtained. This polymer solution was added dropwise to diethyl ether (1500 ml), and the obtained precipitate was filtered. This deposit was wash|cleaned with diethyl ether, it was made to dry under reduced pressure in 40 degreeC oven, and the methacrylate polymer powder (B) was obtained. The number average molecular weight of this polymer was 13000, and the weight average molecular weight was 31000.

NMP (29.29g) was added to the obtained methacrylate polymer powder (B) (6.0g), and it stirred at room temperature for 5 hours, and was made to melt|dissolve. NMP (14.7.5g) and BC (50.0g) were added to this solution, and it stirred for 5 hours, and obtained the liquid crystal aligning agent (B1).

Moreover, 0.03 g (5 mass % with respect to solid content) of bipyridine-type additive BPyStyl is added with respect to 10.0 g of said liquid crystal aligning agent (B1), it stirs at room temperature for 3 hours, and it melt|dissolves, and a liquid crystal aligning agent (B2) is prepared did.

<Example 3>

The liquid crystal cell was manufactured using the liquid crystal aligning agent (A2) obtained in Example 1, and the orientation of a low molecular liquid crystal was confirmed. The conditions of the irradiation amount of polarization|polarized-light UV in an orientation process, and the heating temperature after polarization|polarized-light UV irradiation were changed, and the conditions from which optimal orientation was obtained were confirmed.

[Production of liquid crystal cell]

The substrate was a glass substrate having a size of 30 mm × 40 mm, a thickness of 0.7 mm, and a comb-tooth-shaped pixel electrode formed by patterning an ITO film was used. The pixel electrode has a comb-tooth shape formed by arranging a plurality of "<"-shaped electrode elements in which the center part was bent. The width in the transverse direction of each electrode element is 10 µm, and the distance between the electrode elements is 20 µm. Since the pixel electrode forming each pixel is constituted by arranging a plurality of "<"-shaped electrode elements in which the central part is bent, the shape of each pixel is not a rectangular shape, but is bent in the central part like the electrode element, It has a shape resembling the letter "K" in bold. And each pixel is divided|segmented up and down with the bent part in the center as a boundary, and has the 1st area|region above and the 2nd area|region below the bending|flexion part. Comparing the 1st area|region and the 2nd area|region of each pixel, the formation direction of the electrode element of the pixel electrode which comprises them differs. That is, based on the alignment treatment direction of the liquid crystal alignment film to be described later, in the first region of the pixel, the electrode element of the pixel electrode is formed to form an angle of +15° (clockwise), and in the second region of the pixel, the pixel electrode The electrode elements are formed to form an angle of -15° (clockwise). That is, in the first region and the second region of each pixel, the directions of the rotational operation (in-plane switching) in the substrate plane of the liquid crystal caused by the voltage application between the pixel electrode and the counter electrode are opposite to each other. is structured to be The liquid crystal aligning agent (A2) obtained in Example 1 was spin-coated to the board|substrate with the prepared said electrode. Then, it dried for 90 second with a 70 degreeC hotplate, and formed the liquid crystal aligning film with a film thickness of 100 nm. Then, after irradiating 3-13 mJ/cm<2> of 313 nm ultraviolet-ray to the coating film surface through a polarizing plate, it heated with a 140-170 degreeC hotplate for 10 minutes, and obtained the board|substrate with a liquid crystal aligning film. Moreover, it orientation-processed by forming a coating film similarly also to the glass substrate which has a columnar spacer with a height of 4 micrometers in which the electrode is not formed as a counter board|substrate. The sealing compound (XN-1500T by Kyoritsu Chemical) was printed on the liquid crystal aligning film of one board|substrate. Then, the liquid crystal aligning film surface faced and the other board|substrate was adhere|attached so that an orientation direction might be set to 0 degree, and then, the sealing compound was thermosetted and the empty cell was produced. Liquid crystal MLC-2041 (made by Merck Corporation) was inject|poured into this empty cell by the reduced pressure injection method, the injection port was sealed, and the liquid crystal cell provided with the structure of IPS (In-Planes Switching) mode liquid crystal display element was obtained.

The obtained liquid crystal cell was sandwiched between the polarizing plates which used the cross nicol, and the orientation of the liquid crystal was confirmed. Moreover, the alternating voltage of 8 Vpp was applied between each electrode, and it was confirmed whether the liquid crystal of a pixel part drives. The result of the liquid-crystal orientation by the irradiation amount of polarization|polarized-light UV and the subsequent heating temperature to the following table|surface is shown. In addition, the thing by which orientation defects, such as a flow orientation, were confirmed after liquid crystal injection, and the thing by which there was no orientation defect and favorable liquid-crystal orientation was displayed by (circle).

<Example 4>

By the method similar to Example 3, the liquid crystal cell was manufactured using the liquid crystal aligning agent (A3), and the orientation of the obtained liquid crystal cell was confirmed. In Table 2 below, the result of the liquid-crystal orientation of a liquid crystal cell is shown.

<Example 6>

By the method similar to Example 3, the liquid crystal cell was manufactured using the liquid crystal aligning agent (A4), and the orientation of the obtained liquid crystal cell was confirmed. In Table 3 below, the result of the liquid-crystal orientation of a liquid crystal cell is shown.

<Example 7>

By the method similar to Example 3, the liquid crystal cell was manufactured using the liquid crystal aligning agent (A5), and the orientation of the obtained liquid crystal cell was confirmed. In Table 4 below, the result of the liquid-crystal orientation of a liquid crystal cell is shown.

<Comparative Example 1>

By the method similar to Example 3, the liquid crystal cell was manufactured using the liquid crystal aligning agent (A1), and the orientation of the obtained liquid crystal cell was confirmed. The result of the liquid-crystal orientation of a liquid crystal cell is shown in following Table 5.

From the results of Tables 1 to 5, it was confirmed that by adding a pyridine-based additive, the heating temperature at which the optimal orientation was obtained and the irradiation amount of polarized UV with respect to the comparative example changed. In particular, regarding the heating temperature, since there is concern about deterioration of the electrical properties of the liquid crystal display element due to the influence of the residual solvent, etc., it is required to perform the firing at as high a temperature as possible. Being able to arbitrarily select the heating conditions to be obtained leads to broadening the range of material selection.

It is thought that the reason for the change of the optimal irradiation amount and heating temperature is due to the change of the UV absorption band and the sensitivity and reaction rate by UV by changing the mesogenic part of a supramolecular liquid crystal.

[Evaluation as a polymer film]

<Example 7>

Next, with respect to 10.0 g of liquid crystal aligning agent (A1), 0.06 g (10 mass % with respect to solid content) of bipyridine-type additive BPy is added, it stirs at room temperature for 3 hours, and it melt|dissolves, and prepares an optically active composition (A6) did.

Moreover, 0.3 g (50 mass % with respect to solid content) of bipyridine type additive BPy was added with respect to 10.0 g of liquid crystal aligning agents (A1), it stirred at room temperature for 3 hours, and it melt|dissolved, and the liquid crystal aligning agent (A7) was prepared.

<Example 8>

The optically active composition (A6) obtained in Example 7 was applied to a 1.1 mm quartz substrate by spin coating so as to have a film thickness of 100 nm, and dried on a hot plate at 70°C.

The dichroism at the time of irradiating 313 nm polarization|polarized-light UV to this coating film from 0 J/cm<2> to 30 J/cm<2> was traced. In addition, the measurement of dichroism (triangle|delta)A measured the polarization|polarized-light UV-vis absorption spectrum, and computed it with the following formula|equation.

Dichromaticity △A = A//-A⊥

(A// is the absorbance in the parallel direction to the irradiated polarized UV, and A⊥ is the absorbance in the ⊥ direction to the irradiated polarized UV. The absorbance is a value of the absorbance at 313 nm.)

The dichroism in the case of using the optically active composition (A7) was also calculated by the same method.

In addition, UV-3100 (made by Shimadzu Corporation) was used for the measurement of the polarization|polarized-light UV-vis absorption spectrum.

<Comparative Example 2>

By the method similar to Example 8, the dichroism of a liquid crystal aligning agent (A1) was also computed. The dichroism obtained in Example 8 and Comparative Example 2 is shown in FIG.

<Example 9>

Next, with respect to 10.0 g of liquid crystal aligning agent (A1), 0.06 g (10 mass % with respect to solid content) of bipyridine-type additive BPyAz is added, it stirs at room temperature for 3 hours, and it melt|dissolves, and prepares an optically active composition (A8) did.

<Example 10>

The optically active composition (A8) obtained in Example 9 was applied to a 1.1 mm quartz substrate by spin coating so as to have a film thickness of 100 nm, and dried on a hot plate at 70°C.

In-plane order parameter after irradiating this coating film with polarized UV of 313 nm from 0 mJ/cm 2 to 150 mJ/cm 2 (in-plane orientation degree S) was tracked. In addition, the measurement of the in-plane orientation degree S measured the polarization|polarized-light UV-vis absorption spectrum, and computed it with the following formula|equation.

In-plane orientation S = (A//-A⊥)/(Al + 2As)

(Al indicates the larger absorbance in the polarized UV absorption spectrum (A// and A⊥), and As indicates the smaller absorbance in the polarized UV absorption spectrum.)

<Comparative example 3>

In-plane orientation degree S at the time of using a liquid crystal aligning agent (A1) by the same method was also computed.

The in-plane orientation degree S in each irradiation amount obtained from Example 10 and Comparative Example 3 is shown in FIG.

Evaluation of Examples 7 and 8 WHEREIN: By adding a bipyridine-type additive, it was confirmed that it is possible to change the irradiation amount of polarization|polarized-light UV which shows maximum dichroism, and the magnitude|size of dichroism.

Moreover, in the evaluation of Examples 9 and 10, it was confirmed that the optimal irradiation area|region which enlarges an in-plane orientation degree widens dramatically compared with the case where there is no bipyridine-type additive.

As described above, it was thought that the reason for the change in the optimal irradiation amount and heating temperature in Examples 1 to 10 was because the UV absorption band and the sensitivity and reaction rate by UV were changed due to the change in the mesogenic structure of the supramolecular liquid crystal.

Claims (8)

The following (A) component and (B) component are contained, a photoreactive group is contained in any one or both of the side chain of (A) component, and (B) component, (A) component and (B) component are hydrogen An optically active composition characterized in that through bonding, a liquid crystalline supramolecules are formed.
(A) the polymer which has any 1 type of photosensitive side chain chosen from the group which consists of following formula (3) and (4), and
(B) at least 1 sort(s) of compound chosen from the compound represented by following formula (1) or (2):
[Formula 1]

[During the meal,
X represents a single bond or an alkylene, ether, ester, azo, thioether, disulfide, tetrazine, disubstituted alkene, alkyne, or phenylene having 1 to 12 carbon atoms;
S represents ether, ester or phenylene,
Py each independently represents a structure selected from the following group, and in the following structures, a dotted portion is a portion bonded to X in Formula (1), and a portion bonded to S in Formula (2) to be
[Formula 2]

],
[Formula 3]

[During the meal,
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 represents a phenyl group or a naphthyl group,
l and m are each independently an integer of 1 to 12.] delete The method of claim 1,
The optically active composition, wherein the component (B) is contained in an amount of 0.5% by weight to 70% by weight with respect to the weight of the polymer of the component (A). delete The method of claim 1,
The optically active composition, wherein the component (B) is at least one compound selected from the following.
[Formula 4]

[Formula 5]

[Formula 6]

[During the meal,
n represents an integer of 1 to 3,
l represents an integer of 2 to 6, and
m represents the integer of 1-4]. The liquid crystal aligning agent containing the optically active composition in any one of Claims 1, 3, and 5. The liquid crystal aligning film obtained from the liquid crystal aligning agent of Claim 6. A liquid crystal display element provided with the liquid crystal aligning film of Claim 7.

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