KR102336487B1 - Liquid-crystal display element and method for manufacturing liquid-crystal display element - Google Patents

Abstract

A liquid crystal display element comprising a pair of substrates facing each other, a liquid crystal layer sandwiched between the substrates, and a liquid crystal aligning film obtained from a liquid crystal aligning agent containing a polymer on at least one liquid crystal layer side of the substrate, the liquid crystal layer comprising: Formed from a liquid crystal composition containing a polymerizable compound and a liquid crystal, the polymerizable compound has a polymerizable unsaturated bond group, a hydrogen-bonding functional group, and at least one aromatic ring in the vicinity of the functional group, wherein the functional group is hydrogen between molecules By forming bonds, a mesogenic structure is formed.

Description

A liquid crystal display element and a manufacturing method of a liquid crystal display element

The present invention relates to a liquid crystal display element provided with a liquid crystal material containing a polymerizable compound and a method for manufacturing the liquid crystal display element.

As a liquid crystal display element used for a liquid crystal television, a liquid crystal display, etc., the MVA (Multi-domain Vertical Alignment) system excellent in the viewing angle characteristic is known (for example, refer patent document 1). In the MVA system, the liquid crystal having negative dielectric anisotropy is vertically aligned by forming a projection or a slit for controlling the direction in which the liquid crystal falls on the substrate or the display electrode. According to this MVA method, the alignment of the liquid crystal at the time of voltage application can be controlled in a plurality of different directions even when the liquid crystal aligning film is not subjected to a rubbing treatment. As a result, there is a problem that the response speed decreases.

As a technique for improving this response speed, a PSA system (Polymer sustained Alignment) is known. In the PSA system, a polymerizable compound that polymerizes with light or heat is added to a liquid crystal, and after production of a liquid crystal cell, an ultraviolet ray is irradiated in a state in which the liquid crystal is inclined while applying an electric field. Thereby, a polymeric compound is superposed|polymerized or bridge|crosslinked, and a liquid crystal is orientated in an oblique direction (for example, refer patent document 2). In this PSA system, since the liquid crystals incline all at once, the response speed becomes faster than that of the MVA system. Moreover, in PSA system, since a rubbing process is unnecessary, problems, such as a flaw of the surface of the liquid crystal aligning film which generate|occur|produce in a rubbing process, dust generation, and the influence by mechanical force or static electricity, do not arise.

On the other hand, the photo-alignment method is known as a technique which is quick in response and does not perform a rubbing process (for example, refer patent document 3). The photo-alignment method makes the polymer contained in a liquid crystal aligning film generate|occur|produce photoreactions, such as a photolysis reaction and a photodimerization reaction, by irradiation of the polarized ultraviolet-ray, and fixes the orientation direction of a liquid crystal. Such a photo-alignment method is a transverse electric field driving method, such as an IPS method (In-Plane Switching) or an FFS method (Fringe Field Switching), while the demand for higher resolution and higher quality of liquid crystal display elements is increasing. Application to a liquid crystal display element is performed (for example, refer patent document 3). Moreover, about an IPS system, in order to further improve an orientation ability, the method combining with a PSA system has been developed in recent years.

However, in the PSA system, the solubility of the polymerizable compound added to the liquid crystal material is low, and there is a problem in that an unreacted polymerizable compound remains as an impurity in the liquid crystal material. When an unreacted polymeric compound remain|survives, the desired light sensitivity cannot be acquired and the problem that the orientation ability of a liquid crystal is not fully exhibited will arise. Moreover, when the desired light sensitivity is not obtained, the problem that an afterimage generate|occur|produces also arises. In order to make the light sensitivity higher, when the absorption of ultraviolet rays is made to the long wavelength side, it is necessary to lengthen the conjugation of the polymerizable compound. It causes a problem that the solubility to the liquid crystal material is further lowered.

Japanese Patent Laid-Open No. 2010-097226 Japanese Patent Laid-Open No. 2004-302061 Japanese Patent Laid-Open No. 2013-080193

An object of this invention is to provide the manufacturing method of the liquid crystal display element and liquid crystal display element by which generation|occurrence|production of the afterimage was suppressed in view of such a situation, it has highly sensitive orientation fixation ability.

As a result of earnest research, the present inventors found that a polymerizable compound that forms a mesogenic structure between molecules via a functional group has high solubility in liquid crystals, and completed the present invention. Therefore, this invention makes the following summary.

(1) A liquid crystal display element provided with a liquid crystal aligning film obtained from a liquid crystal aligning agent containing a polymer on the at least one liquid crystal layer side of a pair of mutually opposing board|substrate, the liquid crystal layer clamped between the said board|substrate, , The liquid crystal layer is formed of a liquid crystal composition containing a polymerizable compound and a liquid crystal, and the polymerizable compound includes a polymerizable unsaturated bond group, a hydrogen-bonding functional group, and at least one aromatic ring in the vicinity of the functional group. and the functional group forms a hydrogen bond between molecules to form a mesogenic structure.

(2) The said functional group is a carboxyl group, The liquid crystal display element as described in said (1) characterized by the above-mentioned.

(3) Said polymeric compound is at least 1 sort(s) chosen from following formula [1-1] - [1-4], The liquid crystal display element as described in said (1) or (2) characterized by the above-mentioned.

[Formula 1]

(T is an ether, ester or amide bond, S is an alkylene group having 2 to 11 carbon atoms, R is a hydrogen atom or a methyl group, n = 1 or 2)

(4) Said polymeric compound is at least 1 sort(s) chosen from following formula [2-1] - [2-3] The liquid crystal display element in any one of (1)-(3) characterized by the above-mentioned.

[Formula 2]

(5) Said polymer has group which orientates a liquid crystal perpendicularly|vertically in a side chain, The liquid crystal display element in any one of said (1)-(4) characterized by the above-mentioned.

(6) Said polymer further has photopolymerizable group in a side chain, The liquid crystal display element as described in said (5) characterized by the above-mentioned.

(7) Said photopolymerizable group is at least 1 sort(s) chosen from following formula [3-1] - [3-7] The liquid crystal display element as described in said (6) characterized by the above-mentioned.

[Formula 3]

(8) The said polymer has a photoreactive group, The liquid crystal display element in any one of said (1)-(4) characterized by the above-mentioned.

(9) The said photoreactive group is at least 1 sort(s) chosen from following formula [4-1] - [4-5] The liquid crystal display element as described in said (8) characterized by the above-mentioned.

[Formula 4]

(10) The polymer contains at least one selected from a polyimide precursor and a polyimide obtained by imidizing it, polysiloxane or poly(meth)acrylate, Any one of (1) to (9) above The liquid crystal display element as described in one.

(11) The liquid crystal display element according to any one of (5) to (7), characterized by comprising a liquid crystal cell manufactured by irradiating ultraviolet rays while applying a voltage to the liquid crystal layer.

(12) The liquid crystal display device according to (8) or (9), characterized by comprising a liquid crystal cell manufactured by irradiating the liquid crystal layer with polarized ultraviolet rays.

(13) A liquid crystal aligning film is formed in at least one of a pair of board|substrates from the liquid crystal aligning agent containing a polymer, the said pair of board|substrates are opposingly arrange|positioned so that the said liquid crystal aligning film may become inside, Between the said board|substrates, polymeric A liquid crystal layer is formed by sandwiching a liquid crystal composition containing an unsaturated bond group, a functional group forming a mesogenic structure by forming hydrogen bonds between molecules, a polymerizable compound having at least one aromatic ring in the vicinity of the functional group, and a liquid crystal and irradiating the liquid crystal layer with ultraviolet light to polymerize the polymerizable compound.

ADVANTAGE OF THE INVENTION According to this invention, it has highly sensitive orientation fixing ability, and the manufacturing method of the liquid crystal display element and liquid crystal display element by which generation|occurrence|production of an afterimage was suppressed is implement|achieved.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The present invention relates to a liquid crystal display device driven by a PSA system having a liquid crystal layer obtained from a liquid crystal composition containing a liquid crystal and a polymerizable compound.

<Polymerizable compound>

The liquid crystal composition for manufacturing a liquid crystal layer contains a liquid crystal and a polymeric compound. The polymerizable compound has a polymerizable unsaturated bond group, a hydrogen-bonded functional group, and at least one or more aromatic rings in the vicinity of the functional group, and the functional group forms a hydrogen bond between molecules to form a mesogenic structure.

A polymerizable unsaturated bond group means the ethylenic unsaturated double bond group which contributes to photopolymerization or a photocrosslinking reaction by stimulation, such as a heat|fever or an ultraviolet-ray. Specific examples thereof include a vinyl group, a (meth)acryloyl group, an isopropenyl group, an allyl group, a styryl group, and a radical polymerizable group such as α-methylene-γ-butyllactone group.

Moreover, from the deflection of the electron which generate|occur|produces with the hydrogen atom which concerns on this invention by the difference of the electronegativity of the hydrogen atom in a functional group, and the atom with high electronegativity adjacent to this hydrogen atom, in the solvent of a liquid crystal aligning agent Alternatively, a hydrogen atom in the liquid crystal alignment layer causes an attractive interaction with another atom having a high electronegativity, and refers to a bond formed between molecules through a hydrogen atom. The functional group to hydrogen-bond means group which forms a hydrogen bond between molecules in the solvent of a liquid crystal aligning film or a liquid crystal aligning agent. Such a hydrogen-bonded functional group mainly forms a dimer between molecules in a liquid crystal aligning film or in the solvent of a liquid crystal aligning agent. Since such a polymeric compound has a highly polar group, such as a carboxyl group and a hydroxyl group, solubility is very high compared with a normal polymeric compound etc. For this reason, the solubility with respect to the solvent of a polymeric compound improves, and precipitation of a polymeric compound, etc. do not generate|occur|produce easily also at the time of preservation|save of a liquid crystal aligning agent (for example, cryopreservation etc.).

Moreover, the functional group which hydrogen-bonds forms a mesogenic structure by forming a hydrogen bond between molecules. The mesogenic structure means a rigid structure for expressing liquid crystallinity. The formation of the mesogenic structure via such a hydrogen bond, that is, the formation of a rigid structure, increases the sensitivity to light of the liquid crystal layer and improves the alignment and fixability.

Moreover, it does not specifically limit as a functional group to hydrogen bond, A carboxyl group, a hydroxyl group, a urea group, an amide group, an imide group, etc. are mentioned. Among these, a carboxyl group is preferable in view of the easiness of formation of a dimer.

Further, since at least one aromatic ring of the polymerizable compound is rigid, it forms a mesogenic structure together with the functional group by being positioned in the vicinity of a functional group to be hydrogen-bonded. Since these mesogenic structures have pseudo-large mesogenic structures, the conjugation is diffused and has absorption up to the ultraviolet region on the long-wavelength side (up to 365 nm, for example). For this reason, sensitivity also becomes high also to long-wavelength ultraviolet irradiation, and orientation fixation becomes possible also in the ultraviolet irradiation of weak energy. As an aromatic ring, hydrocarbon aromatic rings, such as a benzene ring, a naphthalene ring, and an anthracene ring, and heteroaromatic rings, such as a pyridine ring, a pyrazine ring, and a pyrrole ring, are mentioned. The number of aromatic rings is not specifically limited, It is preferable that it is 1-4. Moreover, these aromatic rings may have a substituent.

As an example of the polymeric compound demonstrated above, the polymeric compound shown by said Formula [1-1] - [1-4] which has a carboxyl group, and said Formula [2-1] - [2-3] is mentioned . Since the difference in electronegativity between the hydrogen atom of a carboxyl group and the oxygen atom adjacent to this hydrogen atom is large, using these polymeric compounds WHEREIN: A dimer is formed through a stronger hydrogen bond between molecules. Since the molecule|numerator of such a polymeric compound is very small, each molecule of a dimer also becomes a very small thing. Thereby, the solubility with respect to the solvent of a polymeric compound improves further, and the sensitivity with respect to the light of a liquid crystal aligning film becomes still higher. Moreover, the polymeric compound shown by said Formula [1-1] - [1-4] or said Formula [2-1] - [2-3] forms a mesogenic structure with the carboxyl group in the vicinity of a carboxyl group has two or more aromatic rings. Thereby, the sensitivity with respect to the light of a liquid crystal aligning film becomes still higher, and orientation fixability improves more.

In addition, what is necessary is just to make the addition ratio of the polymeric compound added to a liquid crystal so that a polymeric compound may be 0.05-1.0 mass % with respect to a liquid crystal, for example. Moreover, a polymeric compound may be added to a liquid crystal aligning agent, and it is preferable that the addition ratio is 0.1-30 (mass) % with respect to a liquid crystal aligning agent.

<LCD>

A liquid crystal layer is obtained from a liquid crystal composition containing a liquid crystal and the said polymeric compound. As a liquid crystal, various liquid crystals, such as a well-known nematic liquid crystal and a smectic liquid crystal, can be used. Some nematic liquid crystals have negative or positive dielectric anisotropy. As a nematic liquid crystal having negative dielectric anisotropy, for example, a dicyanobenzene-based liquid crystal, a pyridazine-based liquid crystal, a Schiff-based liquid crystal, an azoxy-based liquid crystal, a naphthalene-based liquid crystal, a biphenyl-based liquid crystal, and a phenylcyclohexane-based liquid crystal can be heard Examples of the nematic liquid crystal having positive dielectric anisotropy include a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, an ester liquid crystal, a terphenyl liquid crystal, a biphenylcyclohexane liquid crystal, a pyrimidine liquid crystal, and a dioxane liquid crystal. , a bicyclooctane-based liquid crystal, a cuban-based liquid crystal, and the like. Examples of the smectic liquid crystal include a ferroelectric liquid crystal and an antiferroelectric liquid crystal.

<Liquid crystal aligning agent>

The liquid crystal layer is prepared on the liquid crystal alignment film. The liquid crystal aligning agent for manufacturing a liquid crystal aligning film contains a polymer and the solvent in which a polymer is dissolved. The liquid crystal aligning agent is a liquid crystal display device manufactured by 1) applying a voltage to a liquid crystal cell by irradiating ultraviolet rays, that is, a vertical-field driving type liquid crystal display device, or 2) irradiating polarized ultraviolet rays (polarized ultraviolet rays). After that, a liquid crystal cell is manufactured and the liquid crystal cell is irradiated with ultraviolet rays to form a horizontal alignment method such as an IPS method (In-Plane Switching) or an FFS method (Fringe Field Switching), that is, to a liquid crystal display device of a transverse electric field driving method. used

The liquid crystal aligning agent at the time of being used for the liquid crystal display element of a vertical alignment system contains the polymer which has group which orientates a liquid crystal perpendicularly|vertically as a polymer in a side chain. Moreover, these polymers may have a photoreactive group or an optical radical generating group in a side chain. When the polymer which has these photoreactive group or an optical radical generating group in a side chain is used, the photopolymerization or photocrosslinking reaction by irradiation of an ultraviolet-ray occurs more easily, and orientation fixation ability improves.

The liquid crystal aligning agent in the case of being used for the liquid crystal display element of a horizontal alignment system may have a photoreactive group as a polymer. By having a photoreactive group, photoreactions, such as a photoisomerization reaction by irradiation of a polarization|polarized-light ultraviolet-ray, arise, even if it does not involve a rubbing process, horizontal alignment ability is provided to a liquid crystal aligning film (so-called photoalignment). Below, the group which vertically orientates a liquid crystal, a photopolymerizable group, and a photoreactive group are demonstrated.

<A group that aligns the liquid crystal vertically>

When a liquid crystal display element is a vertical alignment system, the polymer which a liquid crystal aligning agent contains has group which orientates a liquid crystal vertically in a side chain. The group that orients the liquid crystal vertically is a group having the ability to orient the liquid crystal molecules perpendicularly to the substrate, and the structure thereof is not particularly limited as long as it has this ability. Examples of the group for vertically aligning the liquid crystal include a linear alkyl group, a linear fluoroalkyl group, a cyclic group having an alkyl group or a fluoroalkyl group at the terminal, and a steroid group. As a specific example, group represented by following formula [5] is mentioned.

[Formula 5]

R ¹ is an alkylene group having 2 to 6 carbon atoms, preferably an alkylene group having 2 to 4 carbon atoms, -O-, -COO-, -OCO-, -NHCO-, -CONH-, or an alkylene-ether group having 1 to 3 carbon atoms ( -CCO-). Among these, -O-, -COO-, -CONH-, or a C1-C3 alkylene-ether group from a viewpoint of synthetic|combination easiness is preferable. R ² , R ³ , and R ⁴ each independently represent a phenylene group or a cycloalkylene group. ^{Combinations of a, b, c, R 2} , R ³ and R ⁴ shown in Table 1 are preferable from the viewpoints of the easiness of synthesis and the ability to vertically orient the liquid crystal.

R ⁵ represents a hydrogen atom, an alkyl group having 2 to 24, preferably 5 to 8 carbon atoms, or a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, or a large cyclic group comprising these. When at least one of a, b and c is 1, ^{the structure of R 5} is preferably a hydrogen atom, an alkyl group having 2 to 14 carbon atoms, or a fluorine-containing alkyl group having 2 to 14 carbon atoms, more preferably a hydrogen atom; A C2-C12, Preferably a 2-10 alkyl group or a fluorine-containing alkyl group is shown.

Further, when a, b and c are all 0, ^{the structure of R 5} is preferably an alkyl group having 12 to 22 carbon atoms, preferably 12 to 20 carbon atoms, or a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, or It is a large cyclic group which consists of these, More preferably, it is a C12-20, Preferably it is a C12-18 alkyl group or a fluorine-containing alkyl group.

In addition, the side chain of group which orientates a liquid crystal perpendicularly|vertically may be directly couple|bonded with the principal chain of a polymer, and may be couple|bonded through a suitable coupling group. Thus, the introduction method with respect to the side chain of group which orientates a liquid crystal perpendicularly is not specifically limited.

In addition, the amount of the group for vertically aligning the liquid crystal is preferably within a range capable of fixing the alignment, and in order to further improve the sensitivity to light and the ability to fix the alignment, within a range that does not affect other properties, It is preferable to have as many as possible.

<Photopolymerizable group>

The polymer which a liquid crystal aligning agent contains may have a photopolymerizable group in a side chain further. The photopolymerizable group is a group that causes a polymerization reaction by light such as ultraviolet rays, for example, a group that polymerizes by light such as ultraviolet rays (hereinafter also referred to as a photopolymerizable group) or a group that photocrosslinks (hereinafter, photocrosslinked group). Although it will not specifically limit if it is said group, At least 1 sort(s) chosen from the photopolymerizable group shown by said Formula [3-1] - [3-7] is used preferably.

A photopolymerizable group contains in the liquid crystal aligning film obtained using the liquid crystal aligning agent containing such a polymer. When light, such as an ultraviolet-ray is irradiated to the liquid crystal display element containing a photopolymerizable group in a liquid crystal aligning film, the photopolymerizable group located in the surface where a liquid crystal aligning film and a liquid crystal contact, and the polymerizable unsaturated bond group of the above-mentioned polymeric compound photopolymerize. Or a photocrosslinking reaction is raise|generated and the orientation of the liquid crystal located in the surface of a liquid crystal aligning film is fixed more efficiently.

The photopolymerizable group (hereinafter also referred to as a photopolymerizable side chain) introduced into the side chain of the polymer is a methacryl group, an acryl group, a vinyl group, an allyl group, a styryl group, and an α-methylene-γ-butyrolactone group. The side chain containing at least 1 sort(s) chosen is preferable.

Such a photopolymerizable side chain may be directly couple|bonded with the principal chain of a polymer, and may be couple|bonded through a suitable coupling group. Thus, the introduction method of a photopolymerizable side chain is not specifically limited. As a photopolymerizable side chain, what is shown by following formula [6] is mentioned, for example.

[Formula 6]

In formula [6], R ⁶ is a single bond or -CH ₂ -, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N( CH ₃ )-, -CON(CH ₃ )-, or -N(CH ₃ )CO- is represented, and R ⁷ is a single bond or an unsubstituted or fluorine atom-substituted C1-C20 alkylene. represents a group, and -CH ₂ - of the _{alkylene group may be optionally substituted with -CF 2} - or -CH=CH-, and when any of the groups exemplified below are not adjacent to each other, they may be substituted with these groups. -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, divalent carbocyclic ring, divalent heterocyclic ring. R ⁸ represents a methacryl group, an acryl group, a vinyl group, an allyl group, a styryl group and an α-methylene-γ-butyrolactone group.

^{In addition, although R 6} in the above formula [6] can be formed by a conventional organic synthetic method, -CH ₂ -, -O-, -COO-, -NHCO-, -NH- , -CH ₂ O- is preferred.

In addition, as a divalent carbocyclic ring or divalent heterocyclic carbocyclic ring or heterocyclic ring which substitutes arbitrary -CH ₂ ^{- of R<7>} , although the following structures are mentioned specifically, it is not limited to this .

[Formula 7]

It is preferable that R<^8> is a methacryl group, an acryl group, a vinyl group, or alpha-methylene-gamma-butyrolactone group from a photopolymerizable viewpoint.

The amount of the photopolymerizable side chain is preferably in a range that can fix the orientation by reacting with irradiation of light such as ultraviolet rays to form a covalent bond. In order to further improve the sensitivity to light and the orientation fixability, As long as it does not affect other characteristics, it is preferable to have as many as possible.

<Photoreactive group>

In the case of a horizontal alignment system such as an IPS system or FFS system, which is manufactured by irradiating a liquid crystal display element with polarized ultraviolet light, the polymer contained in the liquid crystal aligning agent contains a photoreactive group that expresses liquid crystal alignment ability by use of polarized ultraviolet light. it is preferable

By irradiating a polarized ultraviolet light to a liquid crystal aligning film obtained from a liquid crystal aligning agent containing a polymer into which a photoreactive group is introduced, a photoreaction proceeds, anisotropy is imparted in the same direction as the polarization direction or in a direction perpendicular to the polarization direction, and the liquid crystal is aligned do. The photoreaction includes photodimerization and photoisomerization. The photoreactive group preferably has an unsaturated bond, particularly a double bond, and an acryl group, a vinyl group, a methacryl group, an anthracenyl group, a carconyl group, a coumarin group, a stilbene group, a maleimide group and a cinnamoyl group. can be heard

If a specific example is given, as a structure in which photodimerization reaction advances, the structure shown by said Formula [4-1] - [4-3] will be mentioned. Moreover, as a structure in which photoisomerization reaction advances, the structure shown by said Formula [4-4] and [4-5] is mentioned. The photoreactive group having a structure selected from the formulas [4-1] to [4-5] is a group in which any number of H is separated from the structures of the formulas [4-1] to [4-5]; In the formula [4-1], O is a bond or a group in which these structures are bonded to other structures (eg, an alkylene group).

In addition, such a photoreactive group may be introduce|transduced into the principal chain of a polymer, and may be introduce|transduced into a side chain. As described above, the method for introducing the photoreactive group is not particularly limited. Moreover, the polymer may have group which orientates the said liquid crystal perpendicularly|vertically together with a photoreactive group.

In addition, the amount of the photoreactive group is preferably in a range that can cause a photoreaction and fix the orientation, and in order to further improve the sensitivity to light and the orientation fixability, in a range that does not affect other properties. , preferably as many as possible.

<Polymer>

As for the polymer which a liquid crystal aligning agent contains, polysiloxane and poly(meth)acrylate other than a polyimide obtained by imidating a polyimide precursor and it are used preferably. Here, a polyimide precursor refers to a polyamic acid (it is also mentioned polyamic acid) and polyamic acid ester. Moreover, these different polymers may be contained simultaneously in a liquid crystal aligning agent, and those content rates are variously selected according to the characteristic of a liquid crystal display element. It is preferable that the total amount of the polymer which a liquid crystal aligning agent contains is 0.1-20 (mass) %. Moreover, polymers, such as the polyimide precursor which a liquid crystal aligning agent contains, a polyimide, polysiloxane, and poly(meth)acrylate, need to be meltable in the solvent contained in a liquid crystal aligning agent. Each polymer is described below.

<Polyimide precursor and polyimide obtained by imidizing it>

When the polymer which a liquid crystal aligning agent contains contains a polyimide precursor, a polyimide precursor has a repeating unit (structural unit) shown, for example by following formula [7].

[Formula 8]

In formula [7], R<_1> is a hydrogen atom or a C1-C4 alkyl group. From the viewpoint of easiness of imidation by heating, a hydrogen atom or a methyl group is particularly preferable. X ₂ is a tetravalent organic group, and the structure thereof is not particularly limited. If a specific example is given, the following formula [X-1] - [X-43] will be mentioned. From a viewpoint of liquid-crystal orientation, as for X<_2> , [X-1] - [X-10], [X-26] - [X-28], [X-31] - [X-37] are preferable.

[Formula 9]

In formula [X-1], R ₂ , R ₃ , R ₄ and R ₅ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkenyl group, or a phenyl group. . From the viewpoint of liquid crystal orientation, R ₂ , R ₃ , R ₄ and R ₅ are preferably a hydrogen atom, a halogen atom, a methyl group or an ethyl group, more preferably a hydrogen atom or a methyl group, still more preferably a formula [X1- 1] - at least 1 sort(s) selected from the group which consists of structures shown by [X1-2].

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

When the liquid crystal aligning agent is used in a liquid crystal display element is produced by irradiating polarized ultraviolet rays, a preferred structure of X ₂ is, [X1-1], [X1-2] , [X-2], [X-3], [X-5], [X-6], [X-7], [X-8], [X-9], [X-10], [X1-1], [X1-2 ] and [X-6] are particularly preferred.

Is of the formula [7], Y ₂ is a divalent organic group, the structure is not particularly limited. And if there are any specific example of Y _2, there may be mentioned the following formula [Y-1] ~ [Y -73].

[Formula 14]

[Formula 15]

[Formula 16]

[Formula 17]

[Formula 18]

[Formula 19]

[Formula 20]

[Formula 21]

[Y-8], [Y-20], [Y-21], [Y-22], [Y-28] since the improvement of solubility with respect to organic solvents, such as a polyimide precursor and polyimide, can be expected. It is preferable to have a structural unit having a structure of , [Y-29] or [Y-30].

The polyimide precursor contained in a liquid crystal aligning agent contains a diamine component (For example, the diamine which has a side chain which orientates the liquid crystal mentioned later perpendicularly, the diamine which has a photopolymerizable side chain, and the diamine which has a photoreactive group) and tetracar It is obtained by reaction of an acid dianhydride component (For example, tetracarboxylic dianhydride mentioned later, tetracarboxylic-acid diester dichloride, tetracarboxylic-acid diester, etc.). As a polyimide precursor, a polyamic acid and polyamic acid ester are mentioned, for example. Specifically, a polyamic acid is obtained by reaction of a diamine component and tetracarboxylic dianhydride. Polyamic acid ester is obtained by making a diamine component and tetracarboxylic-acid diester dichloride react in base presence, or by making a diamine component and tetracarboxylic-acid diester react in presence of a suitable condensing agent and base. Moreover, a polyimide is obtained by making this polyamic acid ring-close by dehydration, or by heat-closing polyamic acid ester. All of these polyamic acids, polyamic acid esters, and polyimides are useful as polymers for obtaining a liquid crystal aligning film.

<Diamine having a side chain that vertically orients a liquid crystal>

When a liquid crystal aligning agent is used for the liquid crystal display element of a vertical alignment system, the side chain which orientates a liquid crystal perpendicularly|vertically needs to be introduce|transduced into the diamine component used as the raw material of the polyimide precursor which a liquid crystal aligning agent contains.

As diamines having a side chain that aligns liquid crystals vertically, a long-chain alkyl group, a group having a ring structure or a branched structure in the middle of a long-chain alkyl group, a hydrocarbon group such as a steroid group, or a part or all of the hydrogen atoms of these groups The diamine which has the diamine which has the group substituted by the fluorine atom as a side chain, for example, the diamine which has a side chain shown by the said Formula [5] is mentioned. More specifically, for example, diamine having a hydrocarbon group having 8 to 30 carbon atoms or the like in which a hydrogen atom may be substituted with fluorine, and diamines represented by the following formulas [8] to [11] are mentioned, it is not going to be

[Formula 22]

(The definitions of a, b, c, and R ¹ to R ⁵ in the formula [8] are the same as in the formula [5].

[Formula 23]

[Formula 24]

(In formulas [9] and [10], A ₁₀ represents -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO-, or -NH- , A ₁₁ represents a single bond or a phenylene group, a ₁₀ represents the same structure as the side chain that vertically orients the liquid crystal represented by the formula [5], and a ₁₀ ' represents the liquid crystal represented by the formula [5] vertically represents a divalent group, which is a structure in which an element such as hydrogen is separated by one from the same structure as the side chain oriented to

[Formula 25]

(In formula [11], A ₁₄ is an alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, A ₁₅ is a 1,4-cyclohexylene group or a 1,4-phenylene group, A ₁₆ is an oxygen atom , or -COO-* (provided that the hand to which "*" is attached is bonded to A ₁₅ ), and A ₁₇ is an oxygen atom, or -COO-* (provided that the hand to which "*" is attached is (CH ₂ ) _{is combined with a 2} ) In addition, a ₁ is an integer of 0 or 1, a ₂ is an integer of 2 to 10, and a ₃ is an integer of 0 or 1.)

Coupled position of the two amino groups (-NH ₂₎ of the formula [8] is not limited. Specifically, with respect to the bonding group of the side chain, the position of 2, 3, the position of 2, 4, the position of 2, 5, the position of 2, 6, the position of 3, 4, the position of 3 and 5 on the benzene ring can be heard Especially, the reactive viewpoint at the time of synthesize|combining a polyamic acid to the position of 2 and 4, the position of 2, 5, or the position of 3 and 5 is preferable. When the easiness at the time of synthesize|combining diamine is also taken into consideration, the position of 2 and 4 or the position of 3 and 5 is more preferable.

Although the diamine shown by a following formula [A-1] - a formula [A-24] can be illustrated as a specific structure of Formula [8], it is not limited to this.

[Formula 26]

(In formula [A-1] - formula [A-5], A ₁ is a C2-C24 alkyl group or a fluorine-containing alkyl group)

[Formula 27]

(In formulas [A-6] and [A-7], A ₂ represents -O-, -OCH ₂ -, -CH ₂ O-, -COOCH ₂ -, or -CH ₂ OCO-, and A ₃ is a C1-C22 alkyl group, an alkoxy group, a fluorine-containing alkyl group, or a fluorine-containing alkoxy group)

[Formula 28]

(In formulas [A-8] to [A-10], A ₄ is -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O represents -, -OCH ₂ -, or -CH ₂ -, and A ₅ is an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group)

[Formula 29]

(In formulas [A-11] and [A-12], A ₆ is -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O -, -OCH ₂ -, -CH ₂ -, -O-, or -NH- represents, A ₇ is a fluorine group, a cyano group, a trifluoromethane group, a nitro group, an azo group, a formyl group, an acetyl group, an ace is a hydroxy group or a hydroxyl group)

[Formula 30]

(In formulas [A-13] and [A-14], A ₈ is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is the trans isomer, respectively)

[Formula 31]

(In formulas [A-15] and [A-16], A ₉ is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is the trans isomer, respectively)

[Formula 32]

Although the diamine shown by a following formula [A-25] - a formula [A-30] is mentioned as a specific example of the diamine shown by Formula [9], It is not limited to this.

[Formula 33]

(In formulas [A-25] to [A-30], A ₁₂ is -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO-, or - represents NH-, and A ₁₃ represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group)

Although the diamine shown by a following formula [A-31] - a formula [A-32] is mentioned as a specific example of the diamine shown by Formula [10], It is not limited to this.

[Formula 34]

Among them, [A-1], [A-2], [A-3], [A-4], [A-5], [ The diamines of A-25], [A-26], [A-27], [A-28], [A-29], [A-30] are preferable.

According to characteristics, such as liquid-crystal orientation at the time of setting it as a liquid crystal aligning film, a pretilt angle, a voltage holding characteristic, and an accumulation|storage electric charge, said diamine can also be used 1 type or in mixture of 2 or more types.

<Diamine which has a photopolymerizable side chain>

When a liquid crystal aligning agent is used for the liquid crystal display element of a vertical alignment system, it is preferable that the photopolymerizable side chain is introduce|transduced into the diamine component used as the raw material of the polyimide precursor which a liquid crystal aligning agent contains. As diamine which has a photopolymerizable side chain, it contains at least 1 sort(s) chosen from a methacryl group, an acryl group, a vinyl group, an allyl group, a styryl group, and (alpha)-methylene-gamma-butyrolactone group, for example, and diamine which has a side chain represented by said Formula [6]. Although the diamine shown by the following general formula [12] is mentioned more specifically, for example, it is not limited to this.

[Formula 35]

(The definitions of R ⁶ , R ⁷ and R ⁸ in Formula [12] are the same as those of Formula [6] above)

Coupled position of the two amino groups (-NH ₂₎ of the formula [12] is not limited. Specifically, with respect to the bonding group of the side chain, the position of 2, 3, the position of 2, 4, the position of 2, 5, the position of 2, 6, the position of 3, 4, the position of 3 and 5 on the benzene ring can be heard Especially, the reactive viewpoint at the time of synthesize|combining a polyamic acid to the position of 2 and 4, the position of 2, 5, or the position of 3 and 5 is preferable. When the easiness at the time of synthesize|combining diamine is also taken into consideration, the position of 2 and 4 or the position of 3 and 5 is more preferable.

As a diamine which has a photopolymerizable side chain containing at least 1 sort(s) chosen from a methacryl group, an acryl group, a vinyl group, an allyl group, a styryl group, and (alpha)-methylene-gamma-butyrolactone group, specifically, compounds such as, but not limited to.

[Formula 36]

(Wherein, R _{6 represents a group selected from -CH 2} -, -O-, -CONH-, -NHCO-, -COO-, -OCO-, -NH-, -CO-. R ₇ represents carbon number It is an alkylene group, divalent carbocyclic or heterocyclic ring formed of 1 to 30 carbon atoms, and one or more hydrogen atoms of the alkylene group, divalent carbocyclic or heterocyclic ring may be substituted with a fluorine atom or an organic group. , R ₇ , in the case where any of the following groups are not adjacent to each other, -CH ₂ - may be substituted with these groups; -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH-, -CO- R ₈ is -CH ₂ -, -O-, -CONH-, -NHCO-, -COO-, -OCO-, -NH-, -CO-, single bond _{R 9} represents a cinnamoyl group R ₁₀ represents a single bond or an alkylene group having 1 to 30 carbon atoms, a divalent carbocyclic ring or a heterocyclic ring, and this alkylene group, a divalent carbocyclic ring, or One or a plurality of hydrogen atoms in the heterocyclic ring may be substituted with a fluorine atom or an organic group, and, in R ₁₀ , when any of the following groups are not adjacent to each other, -CH ₂ - is substituted with these groups -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH-, -CO- R ₁₁ is a light selected from any of an acryl group and a methacryl group Represents a polymerizable group.)

[Formula 37]

(X is a single bond or a bonding group selected from -O-, -COO-, -NHCO-, -NH-, Y is a single bond, or an unsubstituted or fluorine atom-substituted C1-C20 alkylene represents a flag)

The diamine having a photopolymerizable side chain containing at least one selected from a methacryl group, an acrylic group, a vinyl group, an allyl group, a styryl group, and an α-methylene-γ-butyrolactone group is a liquid crystal aligning film Depending on the liquid crystal alignment property, sensitivity to light, pretilt angle, voltage retention characteristics, characteristics such as accumulated charge, and the response speed of liquid crystal when used as a liquid crystal display element, one type or a mixture of two or more types may be used. .

Moreover, the diamine which has a photopolymerizable side chain containing at least 1 sort(s) chosen from such a methacryl group, an acryl group, a vinyl group, an allyl group, a styryl group, and (alpha)-methylene-gamma-butyrolactone group is polya It is preferable to use the quantity used as 10-70 mol% of the total amount of the diamine component used for the synthesis|combination of a mixed acid, More preferably, it is 20-60 mol%, Especially preferably, it is 30-50 mol%.

<Diamine having a photoreactive group>

When a liquid crystal aligning agent is used for the liquid crystal display element of the horizontal alignment system manufactured by irradiating a polarization ultraviolet-ray, it is preferable that the photoreactive group is introduce|transduced into the diamine component used as the raw material of the polyimide precursor which a liquid crystal aligning agent contains.

When an orientation treatment method in which a photodimerization reaction or a photoisomerization reaction advances and generates anisotropy is used by irradiation of polarized ultraviolet light, the structures of the above formulas [4-1] to [4-5] are It may be introduced into a chain or a side chain.

As a polymer made into a liquid crystal aligning agent, when using a polyimide precursor and the polyimide obtained by imidating it, the tetra which contains the structure of said Formula [4-1] - [4-5] in a principal chain or a side chain Although there exists the method of using carboxylic dianhydride or diamine, it is preferable to use the diamine which contains the structure of the said Formula [4-1] - [4-5] in a side chain from a synthetic|combination easiness viewpoint. In addition, the side chain of diamine is a structure branched from the structure which connects two amino groups of diamine. Although the compound represented by a following formula is mentioned as a specific example of such diamine, It is not limited to this.

[Formula 38]

(Wherein, X is a single bond, or a bonding group selected from -O-, -COO-, -NHCO-, and -NH-, Y is a single bond or unsubstituted or substituted C1-C20 represents an alkylene group of R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms unsubstituted or substituted with a fluorine atom, or an alkyl ether group.)

[Formula 39]

(Wherein, X is a single bond, or a bonding group selected from -O-, -COO-, -NHCO-, and -NH-, Y is a single bond or unsubstituted or substituted C1-C20 represents an alkylene group of R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms unsubstituted or substituted with a fluorine atom, or an alkyl ether group.)

<Tetracarboxylic dianhydride>

In order to obtain the polyamic acid which is a polyimide precursor contained in a liquid crystal aligning agent, a diamine component and tetracarboxylic dianhydride made to react are not specifically limited. The specific example is given below.

Examples of the tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure include 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,2-dimethyl-1,2,3,4-cyclobutane. Tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclo Butanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,2,4,5 -Cyclohexanetetracarboxylic dianhydride, 3,4-dicarboxy-1-cyclohexylsuccinic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride; 1,2,3,4-Butanetetracarboxylic dianhydride, bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride, 3,3',4,4 '-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, cis-3,7-dibutylcycloocta-1,5-diene-1,2,5,6 -tetracarboxylic dianhydride, tricyclo[4.2.1.0 ^2,5 ]nonane-3,4,7,8-tetracarboxylic acid-3,4:7,8-2 anhydride, hexacyclo[6.6.0.1 ^2,7 .1 ^9,14 .0 ^3,6 .0 ^10,13] hexadecane -4,5,11,12- tetracarboxylic acid 4,5: 11,12-2 anhydride, 4- (2 and 5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride.

Furthermore, in addition to the said tetracarboxylic dianhydride which has an alicyclic structure or an aliphatic structure, when aromatic tetracarboxylic dianhydride is used, since liquid-crystal orientation improves and the accumulation|storage charge of a liquid crystal cell can be reduced, it is preferable do. Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxyl Acid dianhydride, 2,3,3',4-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,3,3',4- Benzophenonetetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, etc. are mentioned.

According to characteristics, such as the liquid-crystal orientation at the time of setting it as a liquid crystal aligning film, the sensitivity to light, a pretilt angle, voltage retention characteristic, and accumulated electric charge, tetracarboxylic dianhydride can be used together 1 type or 2 or more types.

In order to obtain the polyamic acid ester which is a polyimide precursor contained in a liquid crystal aligning agent, a diamine component and the tetracarboxylic-acid dialkyl ester made to react are not specifically limited. The specific example is given below.

Specific examples of the aliphatic tetracarboxylic acid diester include 1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester , 1,2,3,4-cyclopentanetetracarboxylic acid dialkyl ester, 2,3,4,5-tetrahydrofurantetracarboxylic acid dialkyl ester, 1,2,4,5-cyclohexanetetracarboxylic acid dialkyl ester Alkyl ester, 3,4-dicarboxy-1-cyclohexyl succinic acid dialkyl ester, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid dialkyl ester, 1,2,3 ,4-Butanetetracarboxylic acid dialkyl ester, bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic acid dialkyl ester, 3,3',4,4'-dicyclohexyl Tetracarboxylic acid dialkyl ester, 2,3,5-tricarboxycyclopentylacetic acid dialkyl ester, cis-3,7-dibutylcycloocta-1,5-diene-1,2,5,6-tetracarboxyl Acid dialkyl ester, tricyclo [4.2.1.0 ^2,5 ] nonane-3,4,7,8-tetracarboxylic acid-3,4:7,8-dialkyl ester, hexacyclo [6.6.0. ^12,7 0.0 ^3,6 .1 ^9,14 .0 ^10,13] hexadecane -4,5,11,12- tetracarboxylic acid 4,5: 11,12- di-alkyl ester, 4- ( 2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarbondialkyl ester and the like.

Examples of the aromatic tetracarboxylic acid dialkyl ester include pyromellitic acid dialkyl ester, 3,3′,4,4′-biphenyltetracarboxylic acid dialkylester, and 2,2′,3,3′-biphenyltetracarboxylic acid. Acid dialkyl ester, 2,3,3',4-biphenyltetracarboxylic acid dialkyl ester, 3,3',4,4'-benzophenonetetracarboxylic acid dialkyl ester, 2,3,3',4 -benzophenone tetracarboxylic acid dialkyl ester, bis (3,4-dicarboxyphenyl) ether dialkyl ester, bis (3,4-dicarboxyphenyl) sulfone dialkyl ester, 1,2,5,6-naphthalenetetra Carboxylic acid dialkyl ester, 2,3,6,7- naphthalene tetracarboxylic-acid dialkyl ester, etc. are mentioned.

<Polysiloxane>

When the polymer which a liquid crystal aligning agent contains contains polysiloxane, polysiloxane is obtained by making an alkoxysilane component react (for example, polycondensation reaction) in an organic solvent. An alkoxysilane component means the alkoxysilane which has 1-4 alkoxy groups in a molecule|numerator. For example, polysiloxane is obtained by making the alkoxysilane component shown by following formula [14] react.

[Formula 40]

In the formula [14], R ¹¹ represents a monovalent organic group, R ¹² is alkyl of 1 to 5 carbon atoms, preferably from 1-3. More preferably, R ¹² is a methyl group or an ethyl group.

<Alkoxysilane having a vertically oriented side chain>

Examples of the alkoxysilane having a side chain that vertically aligns liquid crystals, in formula [14], R ¹¹ is a long-chain alkyl group, a group having a ring structure or a branched structure in the middle of the long-chain alkyl group, a hydrocarbon group such as a steroid group, The diamine which has the side chain shown by the alkoxysilane which has the group which substituted one part or all of the hydrogen atoms of these groups by the fluorine atom as a side chain, for example, said Formula [5] is mentioned. More specifically, for example, diamine having a hydrocarbon group having 8 to 30 carbon atoms or the like in which a hydrogen atom may be substituted with fluorine, and an alkoxysilane represented by the following formula [15] are mentioned, but it is not limited thereto .

[Formula 41]

(The definitions of a, b, c, and R ¹ to R ⁵ in Formula [15] are the same as those of Formula [5]. In Formula [15], R ⁹ is a single bond or -(CH ₂ ) _n1 O- ( n1 is an alkyl group having 0 to 5 carbon atoms), and R ¹² is an alkyl group having 1 to 5 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms.

Here, although Formula [14-1] - [14-13] are given as a specific example of the alkoxysilane which has the side chain structure of the perpendicular|vertical orientation shown by Formula [14] below, it is not limited to this. In addition, the formula [14-1] - for R ¹² in the [14-13] is the same as R ¹² in the formula [14], and, R ⁹ is the same as R ⁹ in the formula [15].

[Formula 42]

[Formula 43]

(In formula [14-7] - formula [14-9], R ¹³ is a C1-C22 alkyl group, an alkoxy group, a fluorine-containing alkyl group, or a fluorine-containing alkoxy group)

[Formula 44]

(In formulas [14-10] and [14-11], R ¹⁴ is a fluorine group, a cyano group, a trifluoromethane group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group, or a hydroxyl group)

[Formula 45]

(In formulas [14-12] and [14-13], R ¹⁵ is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is the trans isomer, respectively)

The alkoxysilane represented by Formula [14] is solubility with respect to the solvent when it is set as a siloxane polymer (polysiloxane), liquid crystal orientation when it is set as a liquid crystal aligning film, the sensitivity to light, a pretilt angle, voltage retention characteristics, accumulation|storage charge, etc. According to a characteristic, the response speed of a liquid crystal when it is set as a liquid crystal display element, etc., you can also use it in mixture of 1 type or 2 or more types. Moreover, combined use with the alkoxysilane containing a C10-18 long-chain alkyl group is also possible.

Thus, the alkoxysilane represented by Formula [14] can be manufactured by a well-known method as described in Unexamined-Japanese-Patent No. 61-286393, for example.

<Alkoxysilane which has a photopolymerizable side chain>

Moreover, the alkoxysilane which has a photopolymerizable group as shown, for example by following formula [16] as an alkoxysilane component used in order to obtain polysiloxane can also be used.

[Formula 46]

In formula [16], R ²¹ is an alkyl group in which a hydrogen atom is substituted with an acryl group, an acryloxy group, a methacryl group, a methacryloxy group, or a styryl group. The number of substituted hydrogen atoms is one or more, preferably one. As for carbon number of an alkyl group, 1-30 are preferable, More preferably, it is 1-20. More preferably, it is 1-10. R ²² is an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, and particularly preferably 1 to 2 carbon atoms.

Although the specific example of the alkoxysilane shown by Formula [16] is given, it is not limited to these. For example, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, 3-acryloxypropyltri Methoxysilane, 3-acryloxypropyltriethoxysilane, acryloxyethyltrimethoxysilane, acryloxyethyltriethoxysilane, styrylethyltrimethoxysilane, styrylethyltriethoxysilane, 3-(N -Styrylmethyl-2-aminoethylamino)propyltrimethoxysilane.

<Other alkoxysilanes>

Moreover, the alkoxysilane shown by following formula [17] can also be used as an alkoxysilane component used in order to obtain polysiloxane, for example.

[Formula 47]

^{R 23} of the alkoxysilane represented by the formula [17] is a hydrogen atom or a hydrogen atom having 1 to 10 carbon atoms which may be substituted with a hetero atom, a halogen atom, an amino group, a glycidoxy group, a mercapto group, an isocyanate group, or a ureide group It is a hydrocarbon group, Preferably, they are an amino group, a glycid group, and a ureide group. R ²⁴ is an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, n2 is 0 to 3, preferably an integer of 0 to 2 is represented.

Although the specific example of the alkoxysilane shown by such Formula [17] is given, it is not limited to this. For example, 3-(2-aminoethylaminopropyl)trimethoxysilane, 3-(2-aminoethylaminopropyl)triethoxysilane, 2-aminoethylaminomethyltrimethoxysilane, 2-(2- Aminoethylthioethyl)triethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, vinyltriethoxysilane, 3-isocyanatepropyltriethoxysilane, trifluoropropyltrimethoxy Silane, chloropropyltriethoxysilane, bromopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane, diethyldiethoxysilane, diethyldimethoxysilane, di Phenyldimethoxysilane, diphenyldiethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyldimethylethoxysilane, trimethylethoxysilane, trimethylmethoxysilane, γ-ureidopropyltriethoxysilane, γ -Ureidopropyltrimethoxysilane and γ-ureidopropyltripropoxysilane, and the like.

The alkoxysilane represented by Formula [17] WHEREIN: The alkoxysilane whose n2 is 0 is tetraalkoxysilane. Since tetraalkoxysilane is easy to carry out a polycondensation reaction with the alkoxysilane shown by the said Formula [14] - Formula [16], in order to obtain polysiloxane, it is preferable.

As the alkoxysilane in which n2 is 0 in the formula [17], tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane or tetrabutoxysilane is more preferable, and in particular, tetramethoxysilane or tetraethoxysilane Preference is given to oxysilane.

The method of obtaining the polysiloxane which a liquid crystal aligning agent contains is not specifically limited, For example, the alkoxysilane component containing the alkoxysilane shown by said Formula [14] - Formula [17] is reacted in an organic solvent (for example, polycondensation reaction) is obtained. Usually, polysiloxane polycondensates such an alkoxysilane component, and it is obtained as a solution which melt|dissolved in the organic solvent uniformly. In addition, the compounding ratio of the alkoxysilane in the alkoxysilane component containing alkoxysilanes, such as said Formula [14] - [17], is not specifically limited.

As a method of polycondensing an alkoxysilane in order to obtain polysiloxane, the method of hydrolyzing and condensing an alkoxysilane in organic solvents, such as alcohol or glycol, is mentioned, for example. In that case, any of partial hydrolysis and complete hydrolysis may be sufficient as a hydrolysis/condensation reaction.

Polysiloxane demonstrated above has group which orientates a liquid crystal perpendicularly|vertically in a side chain, when a liquid crystal aligning agent is used for the liquid crystal display element of a vertical alignment system, and may have a photopolymerizable group in a side chain. Moreover, when a liquid crystal aligning agent is used for the liquid crystal display element of a horizontal alignment system, you may have a photoreactive group. For this reason, in the alkoxysilane component which is a monomer, it is preferable that the group or photopolymerizable group which orientates a liquid crystal perpendicularly|vertically is introduce|transduced into the side chain, and the photoreactive group is introduce|transduced into the main chain or the side chain. Polysiloxane which has group which orientates such a liquid crystal perpendicularly|vertically, a photopolymerizable group, or a photoreactive group is useful as a polymer for obtaining the liquid crystal aligning film which expresses the orientation fixing ability of a liquid crystal.

<Poly(meth)acrylate>

When the polymer which a liquid crystal aligning agent contains contains poly(meth)acrylate, poly(meth)acrylate is obtained by polymerizing-reacting monomers, such as an acrylic acid ester compound and a methacrylic acid ester compound, and a polymerization initiator. .

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 acrylic 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 rate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, Methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2- and propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate and 8-ethyl-8-tricyclodecyl methacrylate.

The poly(meth)acrylate demonstrated above has group which orientates a liquid crystal perpendicularly|vertically in a side chain, when a liquid crystal aligning agent is used for the liquid crystal display element of a vertical alignment system, and may have a photopolymerizable group in a side chain. Moreover, when a liquid crystal aligning agent is used for the liquid crystal display element of a horizontal alignment system, poly(meth)acrylate may have a photoreactive group. For this reason, in the acrylic acid ester compound, a methacrylic acid ester compound, etc. which are a monomer, it is preferable that the group or photopolymerizable group which orientates a liquid crystal perpendicularly|vertically is introduce|transduced into the side chain, and the photoreactive group is introduce|transduced into the main chain or the side chain. Poly(meth)acrylate which has a group which orientates such a liquid crystal perpendicularly|vertically, a photopolymerizable group, or a photoreactive group is useful as a polymer for obtaining the liquid crystal aligning film which expresses the orientation fixing ability of a liquid crystal.

Here, as an acrylic acid ester compound and a methacrylic acid ester compound which have a side chain, the acrylic acid ester compound and methacrylic acid ester compound which have a side chain shown, for example by the said Formula [5] are mentioned. More specifically, although an acrylic acid ester compound and a methacrylic acid ester compound shown by following formula [18] and following formula [19-1] - [19-3] are mentioned, for example, It is not limited to this .

[Formula 48]

(The definitions of a, b, c, and R ¹ to R ⁵ in Formula [18] are the same as in Formula [5]. R is a hydrogen atom or a methyl group, and S is an alkylene group having 2 to 11 carbon atoms.)

[Formula 49]

(R is a hydrogen atom or a methyl group, S is an alkylene group having 2 to 11 carbon atoms, X is an ether, ester, or amide bond, R ¹⁰ is a hydrogen atom or an unsubstituted or substituted fluorine atom having 1 to 5 carbon atoms is an alkyl group of

<solvent>

The solvent which a liquid crystal aligning agent contains will not be specifically limited if the said polymer is melt|dissolved uniformly. Moreover, when a liquid crystal aligning agent contains the said polymeric compound, if a polymer and a polymeric compound are melt|dissolved uniformly, it will not specifically limit. To give specific examples, when a polyimide precursor or polyimide is used as the polymer, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N-methyl- 2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-vinyl-2-pyrrolidone, dimethyl sulfoxide, dimethyl sulfone, γ-butyrolactone , 1,3-dimethyl-imidazolidinone, 3-methoxy-N,N-dimethylpropanamide, and the like. Moreover, when using polysiloxane as a polymer, for example, polyhydric alcohol compounds, such as ethylene glycol and 1,2-propylene glycol, N-methylformamide, amide compounds, such as N,N- dimethylformamide, etc. can be heard Moreover, when using poly(meth)acrylate as a polymer, an alcohol compound, a ketone compound, an amide compound, an ester compound, or another aprotic compound etc. are mentioned, for example. You may use these 1 type or in mixture of 2 or more types. Moreover, even if it is a solvent which cannot melt|dissolve a polymer or a polymeric compound uniformly individually, as long as it is a range in which a polymer and a polymeric compound do not precipitate, you may mix with said organic solvent.

A liquid crystal aligning agent may contain the solvent for improving the coating-film uniformity at the time of apply|coating a liquid crystal aligning agent to a board|substrate other than the solvent for melt|dissolving a polymer and a polymeric compound. As such a solvent, a solvent having a lower surface tension than that of the organic solvent is generally used. If specific examples are given, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 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, butyl cellosolve 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 isoa Myl ester etc. are mentioned. These solvents may use two or more types together.

Moreover, in a liquid crystal aligning agent, if it is a range in which the effect of this invention is not impaired other than the above, the dielectric or electrically-conductive substance for the purpose of changing electrical characteristics, such as a dielectric constant and electroconductivity of polymers other than the above-mentioned polymer, liquid crystal aligning film, liquid crystal aligning film, liquid crystal aligning film A silane coupling agent for the purpose of improving the adhesion between the substrate and the compound, a compound for improving the film thickness uniformity and surface smoothness when a liquid crystal aligning agent is applied, and crosslinking for the purpose of increasing the hardness and density of the film when a liquid crystal aligning film is used When baking a compound and also a coating film, you may add the imidation promoter etc. for the objective of advancing imidation of a polyimide precursor efficiently.

As a compound which improves the uniformity of a film thickness and surface smoothness, a fluorine-type surfactant, silicone type surfactant, nonionic surfactant, etc. are mentioned. More specifically, for example, EFTOP EF301, EF303, EF352 (manufactured by Tochem Products), Megapac F171, F173, R-30 (manufactured by Dainippon Ink Corporation), Florad FC430, FC431 (manufactured by Sumitomo 3M) ), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Company), and the like. To [ the usage ratio / 100 mass parts of total amounts of the polymer contained in a liquid crystal aligning agent ] when using these surfactant, Preferably it is 0.01-2 mass parts, More preferably, it is 0.01-1 mass part.

As a specific example of the compound which improves the adhesiveness of a liquid crystal aligning film and a board|substrate, a functional silane containing compound, an epoxy group containing compound, etc. 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-diazanonylacetate, 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, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol di Glycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl ether Cydyl-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, 3-(N-allyl-N-glycidyl)aminopropyltrimethoxysilane, 3-( N,N-diglycidyl) aminopropyl trimethoxysilane, etc. are mentioned. Moreover, in order to raise the film strength of a liquid crystal aligning film further, you may add phenolic compounds, such as 2,2'-bis (4-hydroxy-3,5-dihydroxymethylphenyl) propane and tetra (methoxymethyl) bisphenol. When using these compounds, it is preferable that it is 0.1-30 mass parts with respect to 100 mass parts of total amounts of the polymer contained in a liquid crystal aligning agent, More preferably, it is 1-20 mass parts.

<Liquid crystal alignment film>

The liquid crystal aligning film used for the liquid crystal display element of this invention apply|coats the said liquid crystal aligning agent to a board|substrate, and after drying as needed, it is obtained by orientation-processing to the coating film surface obtained by baking.

The substrate on which the liquid crystal aligning agent is applied is not particularly limited as long as it is a substrate with high transparency, and a glass substrate, a silicon nitride substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used, and ITO (Indium Tin Oxide (ITO) for liquid crystal driving) ) It is preferable from the point of simplification of a process to use the board|substrate with which the electrode etc. were formed. In a reflective liquid crystal display element, an opaque material such as a silicon wafer can also be used as long as it is a single-side substrate, and in this case, a light-reflecting material such as aluminum can also be used for the electrode.

Although the application method of a liquid crystal aligning agent is not specifically limited, 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, the spray method, etc., You may use these according to the objective.

After apply|coating a liquid crystal aligning agent on a board|substrate, 30-300 degreeC, according to the solvent used for a liquid crystal aligning agent, by heating means, such as a hot plate, a heat circulation type oven, or IR (infrared) type oven, Preferably can evaporate a solvent at the temperature of 30-250 degreeC, and can be set as a liquid crystal aligning film. When the thickness of the liquid crystal aligning film after baking is too thick, it becomes disadvantageous from the point of power consumption of a liquid crystal display element, and since reliability of a liquid crystal display element may fall when too thin, Preferably it is 5-300 nm, More preferably, it is 10 ∼ 100 nm.

<Orientation processing>

In the liquid crystal display element of horizontal alignment systems, such as an IPS system and an FFS system, in the manufacturing process, the orientation process by what is called a photo-alignment method by irradiating a polarization|polarized-light ultraviolet-ray to a liquid crystal layer and a liquid crystal aligning film is performed. Moreover, in the liquid crystal display element of vertical alignment systems, such as a VA system, the orientation process by applying an electric field to a liquid crystal layer and a liquid crystal aligning film, and irradiating an ultraviolet-ray in the state which inclined a liquid crystal is performed. Even if the alignment treatment by such a photo-alignment method and a vertical alignment use does not perform a rubbing process, the alignment direction of a liquid crystal can be fixed.

In the present invention, not only the polymer in the liquid crystal aligning film is reacted by irradiation of polarized ultraviolet rays or ultraviolet rays, but also the polymerizable compound contained in the liquid crystal layer described above is photopolymerized or photocrosslinked. carried out more reliably.

As a preferable specific example of the orientation treatment by the photo-alignment method, ultraviolet rays with a wavelength of 200 nm or more and 400 nm or less, preferably 210 nm or more and 380 nm or less, for example, 300 nm or more and 350 nm or less, are applied to the surface of the coating film. The method of irradiating a polarization|polarized-light ultraviolet-ray to the fixed direction to contain, and also heat-processing at the temperature of 150-250 degreeC in some cases, and providing the orientation fixing ability of a liquid crystal is mentioned. Moreover, in order to improve orientation fixing ability, you may irradiate an ultraviolet-ray, heating a coating film board|substrate at 50-250 degreeC. It is preferable to exist in the range of 1-10,000 mJ/cm<2>, and, as for the irradiation amount of the said ultraviolet-ray, it is especially preferable to exist in the range of 1-2,000 mJ/cm<2>.

In addition, you may contact-process the film|membrane which irradiated the polarization|polarized-light ultraviolet-ray above with water or the solution containing a specific organic solvent then. The organic solvent is not particularly limited, but water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, 1-methoxy-2-propanol acetate, butyl cellosolve, lactic acid Ethyl, methyl lactate, diacetone alcohol, 3-methoxymethyl propionate, 3-ethoxy ethyl propionate, propyl acetate, butyl acetate, cyclohexyl acetate, etc. are mentioned. Among the above solvents, since anisotropy is high and it is easy to obtain a liquid crystal aligning film without unevenness, 1-methoxy-2-propanol, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, methyl lactate, At least 1 sort(s) selected from the group which consists of diacetone alcohol, 3-methoxymethyl propionate, 3-ethoxy ethyl propionate, propyl acetate, butyl acetate, and cyclohexyl acetate is preferable. In particular, at least one selected from the group consisting of 1-methoxy-2-propanol and ethyl lactate is preferable.

The contact process of the film|membrane irradiated with polarization|polarized-light ultraviolet-ray, and the solution containing an organic solvent, such as an immersion process and a spraying (spray) process, are performed by the process which preferably fully contacts a film|membrane and a liquid. Especially, the method of immersing a film|membrane in the solution containing an organic solvent, Preferably it is 10 second - 1 hour, More preferably, it is 1 minute - 30 minutes is preferable. Although normal temperature or heating may be sufficient as a contact process, Preferably it is 10-80 degreeC, More preferably, it is 20-50 degreeC. Moreover, if necessary, a means for increasing the contact such as an ultrasonic wave can be provided.

After the contact treatment, either or both of rinsing (rinsing) or drying with a low-boiling solvent such as water, methanol, ethanol, 2-propanol, acetone, or methyl ethyl ketone is performed for the purpose of removing the organic solvent in the used solution. may be carried out. As temperature in the case of drying, 80-250 degreeC is preferable and 80-150 degreeC is more preferable.

The liquid crystal aligning film obtained by making it above can orientate a liquid crystal stably in a fixed direction.

<Method for manufacturing liquid crystal display element for driving of transverse electric field>

As the liquid crystal display device of the present invention, the liquid crystal display device for horizontally aligned horizontal electric field driving such as IPS system or FFS system is a liquid crystal display device for transverse electric field driving by a known method after obtaining the above-mentioned liquid crystal aligning film-attached substrate. A cell was manufactured and it was set as the liquid crystal display element for a transverse electric field drive using the liquid crystal cell. In addition, the liquid crystal display element of a transverse electric field drive system is a liquid crystal display element of the system of switching liquid crystal molecules by applying an electric field in the horizontal direction (horizontal direction) with respect to a board|substrate.

As an example of a method of manufacturing a liquid crystal display device for driving a lateral electric field, a liquid crystal display device having a passive matrix structure will be described as an example. Moreover, the liquid crystal display element for lateral electric field drive of the active-matrix structure which formed switching elements, such as TFT (Thin Film Transistor) in each pixel part which comprises an image display may be sufficient.

Although it will not specifically limit if it is a board|substrate with high transparency as a board|substrate used for the liquid crystal display element for a transverse electric field drive, Usually, it is a board|substrate with the transparent electrode for driving a liquid crystal on a board|substrate. As a specific example, the thing similar to the board|substrate described in the said <liquid crystal aligning film> is mentioned.

Moreover, after apply|coating the said liquid crystal aligning agent on this board|substrate, a liquid crystal aligning film is baked, and forms by irradiating radiations, such as a rubbing process and a polarization|polarized-light ultraviolet-ray, as needed. Next, the other board|substrate is superimposed on one board|substrate so that a mutual liquid crystal aligning film surface may oppose, and the periphery is adhere|attached with a sealing material. A spacer is usually mixed in the sealing material in order to control the board|substrate clearance gap. Moreover, it is preferable to spread|distribute the spacer for board|substrate gap|interval control also to the in-plane part in which the sealing material is not provided. An opening in which liquid crystal can be filled from the outside is formed in a part of the sealing material.

Next, a liquid crystal layer is formed by injecting a liquid crystal composition containing a liquid crystal and a polymerizable compound into a space surrounded by the two substrates and the sealing material through the opening formed in the sealing material. Although the liquid crystal contained in a liquid crystal composition is not specifically limited, For example, liquid crystal MLC-2041 (made by Merck Corporation) etc. can be used. As a polymeric compound, the compound etc. which are shown by said Formula [1-1] - [1-4], said Formula [2-1] - [2-3], etc. can be used, for example. In addition, you may contain a polymeric compound in a liquid crystal aligning agent.

After that, this opening is sealed with an adhesive. A vacuum injection method may be used for injection|pouring, and the method which utilized the capillary phenomenon in air|atmosphere may be used. Thereby, the liquid crystal cell for a lateral electric field drive is manufactured.

Next, light, such as an ultraviolet-ray, is irradiated to this liquid crystal cell for a lateral electric field drive. Here, the irradiation amount of ultraviolet rays is, for example, 1 to 60 J, preferably 40 J or less, and the less ultraviolet irradiation amount can suppress a decrease in reliability caused by destruction of members constituting the liquid crystal display element, and also ultraviolet rays It is preferable because the production efficiency is increased by being able to reduce the irradiation time. The wavelength of the ultraviolet-ray to irradiate is 200 nm - 400 nm, for example.

Thus, when light, such as an ultraviolet-ray is irradiated to a liquid crystal cell, that is, when light, such as an ultraviolet-ray is irradiated to a liquid crystal layer or a liquid crystal aligning film, the polymeric unsaturated bond group which the polymeric compound in a liquid crystal layer has, and the light which the polymer in a liquid crystal aligning film has. A reactive group causes a reaction, and the orientation of the liquid crystal located in the surface of the liquid crystal in a liquid crystal layer and a liquid crystal aligning film is fixed. Next, a polarizing plate is installed. Specifically, a pair of polarizing plates are affixed to the surface on the opposite side to the liquid crystal layer of two board|substrates. By passing through the above process, the liquid crystal display element for a transverse electric field drive is obtained.

<Manufacturing method of liquid crystal display element for vertical electric field drive>

As the liquid crystal display element of the present invention, the liquid crystal display element for vertical electric field driving of a vertical alignment system such as a VA system can be obtained by preparing a liquid crystal cell by a known method after obtaining the substrate to which the liquid crystal aligning film is adhered. Specifically, a liquid crystal aligning film is formed by applying a liquid crystal aligning agent on two substrates and baking, and two substrates are arranged so that this liquid crystal aligning film is opposed, and a liquid crystal and a polymerizable compound are contained between the two substrates. A liquid crystal layer is formed by injecting a liquid crystal composition. And the liquid crystal display element for vertical field drive of the vertical alignment system provided with a liquid crystal cell is obtained by irradiating an ultraviolet-ray, applying a voltage to a liquid crystal layer and a liquid crystal aligning film.

As a board|substrate used for the liquid crystal display element for a vertical electric field drive, the thing similar to the board|substrate described by the said <liquid crystal aligning film> is mentioned. Moreover, you may use the board|substrate with which the conventional electrode pattern or protrusion pattern was formed. In addition, in high-function elements such as TFT-type elements, those in which elements such as transistors are formed between an electrode for driving a liquid crystal and a substrate are used. About the formation method of a liquid crystal aligning film and a liquid crystal layer, it is the same as that in the case of said liquid crystal display element for a transverse electric field drive.

The step of irradiating ultraviolet rays while applying a voltage is, for example, a method of applying a voltage to the liquid crystal layer and the liquid crystal alignment film by applying a voltage between the electrodes installed on the substrate, and irradiating ultraviolet rays while maintaining this voltage. can be heard Here, as a means for applying a voltage, a function generator can be used, and as a means for irradiating ultraviolet rays, an existing device such as a high-pressure mercury lamp can be used. The voltage applied between the electrodes is, for example, 5 to 30 Vp-p, preferably 5 to 20 Vp-p. The wavelength of an ultraviolet-ray becomes like this. Preferably it is 250-400 nm, More preferably, it is 300-400 nm. The irradiation amount of ultraviolet rays is, for example, 1 to 60 J/cm 2 , preferably 40 J/cm 2 or less, and the smaller the amount of ultraviolet ray irradiation, the lower the reliability due to destruction of the members constituting the liquid crystal display can be suppressed, and the ultraviolet rays It is preferable because the production efficiency is increased by being able to reduce the irradiation time.

By the step of irradiating an ultraviolet ray while applying a voltage, a polymerizable unsaturated bond group in the polymerizable compound in the liquid crystal layer, a group or photopolymerizable group that vertically aligns the liquid crystal that the polymer in the liquid crystal aligning film has causes a reaction, and in the liquid crystal layer The direction in which the liquid crystal located on the surface of a liquid crystal and a liquid crystal aligning film inclines is memorized.

The liquid crystal display element for a transverse electric field drive and the liquid crystal display element for a longitudinal electric field drive manufactured by the manufacturing method of the liquid crystal display element of this invention demonstrated above is equipped with the liquid crystal layer containing a polymeric compound. When such a polymerizable compound has a highly polar group, such as a carboxyl group and a hydroxyl group, that is, a functional group which bonds with hydrogen, the solubility to a liquid crystal improves. Thereby, an unreacted polymeric compound ceases to remain|survive as an impurity, and the sensitivity with respect to the light of a liquid crystal layer becomes high. Further, the polymerizable compound has an aromatic ring in the vicinity of the functional group to be hydrogen-bonded, and forms a pseudo-large mesogenic structure in the liquid crystal composition or in the liquid crystal layer together with the functional group to be hydrogen-bonded. As a result, as shown in Examples to be described later, the sensitivity to long-wavelength ultraviolet irradiation is increased, and alignment and fixation are possible even with weak energy ultraviolet irradiation, and a liquid crystal display element with a fast response speed and suppression of afterimage generation is realized. do. Such a liquid crystal display element can be suitably used for a high-definition liquid crystal television etc. with a large screen.

Example

Hereinafter, although it describes in more detail based on an Example, this invention is not limited at all by this Example.

<Synthesis of polymerizable compound>

The abbreviation of the polymeric compound contained in the liquid crystal composition in this invention is as follows. In addition, polymeric compound [RM1] - [RM3] are the same as the polymeric compound of said Formula [2-1] - [2-3].

[Formula 50]

<Synthesis Example 1>

The known polymerizable compound represented by the following formula was referred to as the polymerizable compound [RM1].

[Formula 51]

<Synthesis Example 2>

Synthesis of polymerizable compound [RM2]

[Formula 52]

In a 2 ℓ 4-neck flask, 6-bromo-2-naphthol [H] (150 g, 672 mol), tert-butyl acrylate [B] (103.4 g, 807 mmol), palladium acetate (3.02 g, 13.5 mmol) ), tri(o-tolyl)phosphine (8.19 g, 26.9 mmol), tripropylamine (289.0 g, 2.02 mol), and DMAc (700 g) were added, followed by heating and stirring at 100°C. Reaction tracking was performed by HPLC, and after confirming completion|finish of reaction, the reaction solution was cooled to room temperature vicinity, and it poured into 3 L of 1 M aqueous hydrochloric acid solution. Ethyl acetate (2 L) was added thereto, and the aqueous layer was removed by liquid separation operation. After the organic layer was washed with 1 L of a 10% aqueous hydrochloric acid solution twice and 3 times with 1 L of saturated brine, the organic layer was dried over magnesium sulfate. Then, 181 g of compound [I] was obtained by filtration and distilling off a solvent with an evaporator (yield 99%).

The measurement results of nuclear magnetic resonance (NMR) of compound [I] were as follows.

In a 2 liter 4-neck flask equipped with a mechanical stirrer and stirring blades, the compound [I] obtained above (181 g, 672 mmol), 6-chloro-1-hexanol (110.2 g, 806 mol), potassium carbonate ( 111.5 g, 806 mmol), potassium iodide (1.12 g, 6.7 mmol), and DMF (900 g) were added, and heating and stirring were performed at 80 degreeC. Reaction tracking was performed by HPLC, 2 L of distilled water was poured into the reaction solution after confirming completion|finish of reaction, ethyl acetate (2 L) was added, and liquid separation operation removed the water layer. Then, the organic layer was wash|cleaned twice with saturated brine (1L), the organic layer was dried with magnesium sulfate, the solvent was distilled off after filtration, and the crude substance was obtained. The obtained crude substance was recrystallized with ethyl acetate/hexane mixed solvent, and 185g of compound [J] was obtained (yield 74%).

The measurement results of nuclear magnetic resonance (NMR) of compound [J] were as follows.

The compound [J] obtained above (130.5 g, 352 mmol), triethylamine (42.76 g, 423 mmol), and THF (950 g) were added to a 3 L 4-neck flask, and the reaction solution was cooled. THF (100 g) solution of methacrylic acid chloride (44.2 g, 423 mmol) was dripped there, being careful not to exceed 10 degreeC of internal temperature. After completion|finish of dripping, the reaction solution was made into 23 degreeC, and it reacted further. Reaction tracking was performed by HPLC, and after confirming completion|finish of reaction, distilled water 6L was poured into the reaction solution, ethyl acetate 2L was added, and the water layer was removed by liquid separation operation. Then, the organic layer was washed sequentially with 5% aqueous potassium hydroxide solution, 1 M aqueous hydrochloric acid solution, and saturated brine, and the organic layer was dried over magnesium sulfate. Then, the solvent was distilled off by filtration and an evaporator, and 140.9g of compound [K] were obtained (yield 92%).

The measurement results of nuclear magnetic resonance (NMR) of compound [K] were as follows.

The compound [K] (140.9 g, 321 mmol) and formic acid (700 g) obtained above were added to a 3 L 4 neck flask, and heating and stirring were performed at 40 degreeC. Reaction tracking was performed by HPLC, and after confirming completion|finish of reaction, 4.5 L of distilled water was poured into the reaction solution, and it filtered. The obtained solid was washed with an IPA/hexane mixed solvent and the solid was dried to obtain 95.9 g of a polymerizable compound [RM2] (yield 78%).

The measurement results of nuclear magnetic resonance (NMR) of the polymerizable compound [RM2] were as follows.

<Synthesis Example 3>

Synthesis of polymerizable compound [RM3]

[Formula 53]

The same operation as in Example 1 was carried out except that 6-chloro-1-hexanol used for synthesizing compound [J], which is an intermediate of the polymerizable compound [RM2], was changed to 8-chloro-1-hexanol, 171 g of polymerizable compound [RM3] was obtained.

The measurement results of nuclear magnetic resonance (NMR) of the polymerizable compound [RM3] were as follows.

<Comparative Synthesis Example 1>

The known polymerizable compound represented by the following formula was referred to as the polymerizable compound [RM4].

[Formula 54]

<Preparation of liquid crystal composition>

<Preparation Example 1>

0.03 g (0.3 wt%) of a polymerizable compound [RM1] is added to 10.0 g of negative liquid crystal MLC-6608 manufactured by Merck Corporation (trade name manufactured by Merck Corporation), heated on a 130°C hot plate, and RM1 is completely dissolved to prepare a liquid crystal composition (LC1).

<Preparation Example 2>

0.03 g (0.3% by weight) of a polymerizable compound [RM2] was added to 10.0 g of negative liquid crystal MLC-6608 manufactured by Merck Co., Ltd. (trade name, manufactured by Merck Corporation), and heated on a 130°C hot plate to completely dissolve RM2 to prepare a liquid crystal composition (LC2).

<Preparation Example 3>

0.03 g (0.3 wt%) of a polymerizable compound [RM3] is added to 10.0 g of negative liquid crystal MLC-6608 manufactured by Merck Corporation (trade name, manufactured by Merck Corporation), heated on a 130°C hot plate to completely dissolve RM3 to prepare a liquid crystal composition (LC3).

<Comparative Preparation Example 1>

0.03 g (0.3% by weight) of a polymerizable compound [RM4] was added to 10.0 g of negative liquid crystal MLC-6608 manufactured by Merck Corporation (trade name, manufactured by Merck Corporation), and heated on a 130°C hot plate to completely dissolve RM4 to prepare a liquid crystal composition (LC4).

<Preparation Example 4>

0.03 g (0.3 weight%) of a polymeric compound [RM2] was added with respect to 10.0 g of Merck company positive type liquid crystal MLC-2041 (merck company brand name), and it heated on a 130 degreeC hotplate, and RM2 was completely dissolved. to prepare a liquid crystal composition (LC5).

<Comparative Preparation Example 2>

0.03 g (0.3% by weight) of a polymerizable compound [RM4] was added to 10.0 g of positive liquid crystal MLC-2041 manufactured by Merck Corporation (trade name, manufactured by Merck Corporation), and heated on a 130°C hot plate to completely dissolve RM4 to prepare a liquid crystal composition (LC6).

<Preparation of liquid crystal aligning agent>

The abbreviation used by preparation of a liquid crystal aligning agent is as follows.

BODA: bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride

CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride

DBA: 3.5-diaminobenzoic acid

m-PCH7: 1,3-diamino-5-((4-(4-heptylcyclohexyl)phenoxy)methyl)benzene represented by the following formula

[Formula 55]

PCH7: 1,3-diamino-4-[4-(4-heptylcyclohexyl)phenoxy]benzene represented by the following formula

[Formula 56]

BEM-S: 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate represented by the following formula

[Formula 57]

NMP: N-methyl-2-pyrrolidone

BCS : Butyl Cellosolve

<Additives>

3AMP: 3-picolylamine

<Liquid crystal aligning agent synthesis example 1>

BODA (10.0 g, 40.0 mmol), DBA (5.3 g, 35.0 mmol), m-PCH7 (12.0 g, 30.0 mmol), BEM-S (9.2 g, 35.0 mmol) in NMP (144.5 g) After dissolving and making it react at 60 degreeC for 5 hours, CBDA (11.5 g, 58.5 mmol) and NMP (48.2 g) were added, and it was made to react at 40 degreeC for 10 hours, and the polyamic-acid solution was obtained. After adding NMP to this polyamic-acid solution (200g) and diluting to 6 mass %, acetic anhydride (17.0g) and pyridine (65.8g) were added as an imidation catalyst, and it was made to react at 50 degreeC for 3 hours. This reaction solution was thrown into methanol (3000 ml), and the obtained deposit was separated by filtration. Methanol wash|cleaned this deposit, and it dried under reduced pressure at 60 degreeC, and obtained polyimide powder (A1). The imidation ratio of this polyimide was 60 %, the number average molecular weight was 14,000, and the weight average molecular weight was 47,000.

NMP (44.0g) was added to the obtained polyimide powder (A1) (6.0g), and it stirred at 50 degreeC for 5 hours, and was made to melt|dissolve. The liquid crystal aligning agent (A) was obtained by adding 3AMP (1 wt% NMP solution) 6.0g, NMP (14.0g), BCS (30.0g) to this solution, and stirring at room temperature for 5 hours.

<Liquid crystal aligning agent synthesis example 2>

After reacting CBDA (1.92 g, 10.0 mmol) and DA1 (3.97 g, 10.0 mmol) in NMP (23.6 g) at room temperature for 10 hours, NMP (39.3 g) and BCS (29.3 g) were added, and room temperature The liquid crystal aligning agent (B) was obtained by stirring in 5 hours. The number average molecular weight of this polyamic acid was 15,000, and the weight average molecular weight was 61,000.

The molecular weight measurement conditions of the polyimide contained in the liquid crystal aligning agent obtained by the said liquid crystal aligning agent synthesis examples 1 and 2 are as follows.

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

Column: Column manufactured by Shodex (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 and anhydrous crystals (o-phosphoric acid) are 30 mmol/L, tetrahydro furan (THF) is 10 ml/L)

Flow rate: 1.0 ml/min

Standard samples for calibration curve production: TSK standard polyethylene oxide (molecular weights about 9,000,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation, and polyethylene glycol manufactured by Polymer Laboratories (molecular weights of about 12,000, 4,000, 1,000).

In addition, the imidation ratio of a polyimide was measured as follows. Put 20 ㎎ polyimide powder in the NMR sample tube (Kusano history of science produced NMR sample tube Standard φ5), deuterated dimethyl sulfoxide _{(DMSO-d 6, 0.05%} TMS mixed product) was added to 1.0 ㎖, and completely dissolved by adding an ultrasonic made it Proton NMR of 500 MHz was measured for this solution with the NMR measuring machine (JNW-ECA500) by the Nippon Electronics Datum company. The imidation rate determines a proton derived from a structure that does not change before and after imidization as a reference proton, and the peak integrated value of this proton and the proton peak integrated value derived from the NH group of the amic acid appearing in the vicinity of 9.5 to 10.0 ppm. was obtained by the following formula using In addition, in the following formula, x is the proton peak integrated value derived from the NH group of an amic acid, y is the peak integrated value of a reference proton, and α is a polyamic acid (imidation rate is 0%) NH of the amic acid It is the ratio of the number of reference protons to one proton of the group.

Imidization rate (%) = (1 - α·x/y) × 100

<Production of liquid crystal cell for PSA mode (method)>

(Example 1)

The liquid crystal cell was manufactured in the procedure as shown below using the liquid crystal composition (LC1) obtained by the preparation example 1, and the liquid crystal aligning agent (A) obtained by the liquid crystal aligning agent synthesis example 1. A liquid crystal aligning agent (A) is spin-coated on the ITO surface of the ITO electrode substrate in which the pixel size is 100 micrometers x 300 micrometers and the ITO electrode pattern of which line/space is 5 micrometers is formed, 90 degreeC hotplate, After drying for second, it baked for 30 minutes with 200 degreeC hot-air circulation type oven, and formed the liquid crystal aligning film with a film thickness of 100 nm.

Moreover, after spin-coating a liquid crystal aligning agent (A) on the ITO surface in which the electrode pattern is not formed and drying it for 90 second on an 80 degreeC hotplate, 200 degreeC hot air circulation type oven performs baking for 30 minutes, The liquid crystal aligning film with a film thickness of 100 nm was formed.

After spread|dispersing a 6 micrometers bead spacer on the liquid crystal aligning film of one board|substrate with respect to said two board|substrates, the sealing compound (solvent type thermosetting type epoxy resin) was printed from the top. Then, after turning inside the surface by the side in which the liquid crystal aligning film of the other board|substrate was formed and bonding together with the board|substrate in front, the sealing compound was hardened and the empty cell was manufactured. The liquid crystal composition (LC1) obtained by the preparation example 1 was inject|poured into this empty cell by the reduced pressure injection method, and the liquid crystal cell was manufactured.

(Example 2)

A liquid crystal cell was produced in the same manner as in Example 1 except that the liquid crystal composition (LC2) containing the polymerizable compound [RM2] obtained in Preparation Example 2 (LC2) was used instead of the liquid crystal composition (LC1).

(Example 3)

A liquid crystal cell was produced in the same manner as in Example 1 except that the liquid crystal composition (LC3) containing the polymerizable compound [RM3] obtained in Preparation Example 3 (LC3) was used instead of the liquid crystal composition (LC1).

(Example 4)

Instead of the liquid crystal aligning agent (A), except having used the liquid crystal vertical aligning agent (Nissan Chemical Industry make: SE-5561), operation similar to Example 1 was performed and the liquid crystal cell was manufactured.

(Comparative Example 1)

A liquid crystal cell was manufactured in the same manner as in Example 1 except that the liquid crystal composition (LC4) containing the polymerizable compound [RM4] obtained in Comparative Preparation Example 1 was used instead of the liquid crystal composition (LC1).

<Measurement of response speed>

The response speed of the liquid crystal cell obtained in Examples 1-4 and the comparative example 1 was measured by the following method.

First, the measuring apparatus comprised in the order of a backlight and a set of polarizing plates made into the state of cross nicol, and a light quantity detector WHEREIN: The liquid crystal cell was arrange|positioned between one set of polarizing plates. At this time, the pattern of the ITO electrode in which the line/space was formed was made to have an angle of 45° with respect to the cross nicol. Then, a square wave with a voltage of ±6 V and a frequency of 1 kHz is applied to the liquid crystal cell, and the change until the luminance observed by the light quantity detector is saturated is put into the oscilloscope, and the luminance when no voltage is applied 0% and a voltage of ±4V was applied to make the value of the saturated luminance 100%, and the time required for the luminance to change from 10% to 90% was set as the response speed.

After measuring a response speed, in the state which applied the AC voltage of ±10V to this liquid crystal cell, 5J of UV which passed a 365 nm band pass filter from the outer side of this liquid crystal cell was irradiated. After that, the response speed was measured again, and the response speed before and after UV irradiation was compared.

<Measurement of pretilt angle>

About the liquid crystal cell obtained by Examples 1-4 and the comparative example 1, the pretilt angle of the pixel part after the said UV irradiation was measured. As the measuring device, LCD analyzer LCA-LUV42A manufactured by Meiryo Technica was used.

Table 2 shows the measurement results of the response speed and pretilt angle before and after UV irradiation.

As shown in Table 2, the liquid crystal cell of Examples 1-4 using the polymeric compound which has a functional group (carboxyl group) which hydrogen-bonds, ie, the polymeric compound [RM1] - [RM3] which form a hydrogen bond between molecules. Compared with Comparative Example 1 using the polymerizable compound [RM4] having no silver carboxyl group, the response speed became very fast. This is because the polymerizable compounds [RM1] to [RM3] have a highly polar carboxyl group, so that solubility in liquid crystal is improved, and the carboxyl group and one or more aromatic rings located in the vicinity of the carboxyl group pseudo-intermolecularly It is thought to originate from the formation of a large mesogenic structure. The liquid crystal cell of Examples 1-4 was sensitive also to the ultraviolet-ray (365 nm) of a long wavelength side by formation of this gigantic mesogenic structure, and a sufficiently fast response speed was achieved also by irradiation of a 365-nm ultraviolet-ray. Moreover, a favorable pretilt angle was obtained and it became the thing excellent also in orientation fixation ability.

On the other hand, when the polymerizable compound [RM4] of Comparative Example 1 was used, since the mesogenic moiety had a simple biphenyl structure, there was almost no sensitivity at 365 nm, and a sufficient response speed could not be obtained by irradiation at 365 nm.

As a result, it can be seen that the liquid crystal display element containing the polymerizable compound that forms hydrogen bonds between molecules in the liquid crystal layer has high sensitivity to light, has excellent alignment fixation ability, and can realize fast response speed. there was.

<Production of liquid crystal cell for optical IPS mode>

(Example 5)

The liquid crystal cell was manufactured in the procedure as shown below using the liquid crystal composition (LC5) obtained by the synthesis example 4, and the liquid crystal aligning agent (B) obtained by the synthesis example 2 of liquid crystal aligning agent. The substrate was a glass substrate having a size of 30 mm x 40 mm and a thickness of 0.7 mm, in which a comb-tooth-shaped pixel electrode formed by patterning an ITO film was disposed. A pixel electrode has the comb-tooth-shaped shape comprised 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 a bold letter bent in the central part like the electrode element. It has a shape similar to the letter が. And each pixel is divided|segmented up and down with the bent part in the center as a boundary, and has a 1st area|region above a bending part, and a 2nd area|region below.

Comparing the 1st area|region and 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 (clockwise) of -15°. 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 surface of the liquid crystal caused by the voltage application between the pixel electrode and the counter electrode are opposite to each other. Consists of. The liquid crystal aligning agent (B) obtained by the liquid crystal aligning agent synthesis example 2 was spin-coated to the said board|substrate with an electrode prepared.

Then, after drying for 90 second with an 80 degreeC hotplate, 200 degreeC hot-air circulation type oven performed baking for 30 minutes, and the liquid crystal aligning film with a film thickness of 100 nm was formed. Next, 50 mJ/cm<2> of polarized ultraviolet rays of 313 nm were irradiated to the coating film surface via a polarizing plate. 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 hardened and the empty cell was manufactured. The liquid crystal cell containing the polymerizable compound (LC5) obtained in Preparation Example 5 was injected into this empty cell by a reduced pressure injection method, the injection port was sealed, and the liquid crystal cell provided with the structure of an IPS (In-Planes Switching) mode liquid crystal display element got it

The reorientation process was performed for 60 minutes in 120 degreeC oven after manufacture of a liquid crystal cell. Then, in the state which short-circuited between the pixel electrode of a liquid crystal cell, and a counter electrode, 5 J/cm<2> irradiation (secondary irradiation) of the ultraviolet-ray which passed a 365 nm band pass filter was carried out to the liquid crystal cell.

(Comparative Example 2)

A liquid crystal cell was manufactured in the same manner as in Example 5 except that the liquid crystal composition (LC6) containing the polymerizable compound [RM4] obtained in Comparative Preparation Example 2 (LC6) was used instead of the liquid crystal composition (LC5).

(Comparative Example 3)

A liquid crystal cell was manufactured in the same procedure as in Example 5 except that secondary irradiation was not performed.

<Afterimage evaluation>

The liquid crystal cell for IPS mode prepared in Example 5 and Comparative Examples 2 and 3 was installed between two polarizing plates arranged so that the polarization axes were orthogonal to each other, and the backlight was turned on in a state where no voltage was applied, so that the luminance of transmitted light was the smallest. The arrangement angle of the liquid crystal cell was adjusted. And the rotation angle when the liquid crystal cell was rotated from the angle at which the 2nd area|region of a pixel becomes the darkest to the angle at which the 1st area|region becomes the darkest was computed as an initial stage orientation azimuth. Then, an alternating voltage of 30 Hz and 8 V _{PP was applied at room temperature for 72 hours.} Then, it was set as the state made short between the pixel electrode of a liquid crystal cell, and a counter electrode, and it was left to stand at room temperature as it is for 1 hour. After leaving it to stand, the orientation azimuth was measured similarly, and the difference of orientation azimuth before and behind an alternating current drive was computed as angle (DELTA) (deg.).

Table 3 shows the result of afterimage evaluation. As shown in Table 3, the liquid crystal cell of Example 5 using the polymerizable compound [RM2] having a hydrogen-bonding functional group (carboxyl group) is Comparative Example 2 or 2 using the polymerizable compound [RM4] having no carboxyl group Compared with the liquid crystal cell of the comparative example 3 which does not perform differential irradiation, the difference of the orientation azimuth before and behind an alternating current drive was very small. This is similar to the measurement result of the above-described response speed, the polymerizable compound [RM2] has a highly polar carboxyl group, so that solubility in liquid crystal is improved, and the carboxyl group and one or more aromatic rings are used between molecules pseudo- It is thought to originate from the formation of a large mesogenic structure.

Therefore, the liquid crystal display element containing the polymerizable compound that forms hydrogen bonds between molecules in the liquid crystal layer can make very small the difference in orientation and azimuth even after secondary irradiation of long-wavelength ultraviolet (365 nm), and the residual It was found that the occurrence can be suppressed.

Industrial Applicability

INDUSTRIAL APPLICATION This invention is applicable to the manufacturing method of the liquid crystal display element and liquid crystal display element of the PSA system which adds a polymeric compound in a liquid crystal layer, and controls the orientation direction of a liquid crystal by superposition|polymerization of a polymeric compound. By combining this PSA type liquid crystal display device with a photo-alignment method, it is applicable not only to the vertical electric field drive method (VA method, TN method, OCB method, etc.) but also to the liquid crystal display device of the transverse electric field drive method (IPS method, FFS method) becomes Since the liquid crystal display element of this invention has the highly sensitive orientation fixation ability and the outstanding residual image characteristic, it can use suitably for a high-definition liquid crystal television etc. with a large screen.

Claims (13)

A liquid crystal display element comprising a pair of substrates facing each other, a liquid crystal layer sandwiched between the substrates, and a liquid crystal aligning film obtained from a liquid crystal aligning agent containing a polymer on at least one liquid crystal layer side of the substrate,
The liquid crystal layer is formed of a polymerizable compound and a liquid crystal composition containing liquid crystal,
The polymerizable compound has a polymerizable unsaturated bond group, a hydrogen-bonded functional group, and at least one or more aromatic rings in the vicinity of the functional group, and is at least one selected from the following formulas [2-1] to [2-3], , A liquid crystal display device, characterized in that the functional group forms a mesogenic structure by forming a hydrogen bond between molecules.

The method of claim 1,
The polymer is a liquid crystal display device, characterized in that it has a group in the side chain for vertically aligning the liquid crystal. 3. The method of claim 2,
The said polymer further has a photopolymerizable group in a side chain, The liquid crystal display element characterized by the above-mentioned. 4. The method of claim 3,
The said photopolymerizable group is at least 1 sort(s) chosen from following formula [3-1] - [3-7], The liquid crystal display element characterized by the above-mentioned.

The method of claim 1,
The polymer is a liquid crystal display device, characterized in that it has a photoreactive group. 6. The method of claim 5,
The said photoreactive group is at least 1 sort(s) selected from following formula [4-1] - [4-5], The liquid crystal display element characterized by the above-mentioned.

The method of claim 1,
The polymer contains at least one selected from a polyimide precursor and a polyimide obtained by imidizing it, polysiloxane or poly(meth)acrylate. 3. The method of claim 2,
and a liquid crystal cell manufactured by irradiating ultraviolet rays while applying a voltage to the liquid crystal layer. 6. The method of claim 5,
A liquid crystal display device comprising a liquid crystal cell manufactured by irradiating the liquid crystal layer with polarized ultraviolet light. A liquid crystal aligning film is formed in at least one of a pair of board|substrates from the liquid crystal aligning agent containing a polymer,
The pair of substrates are arranged to face each other so that the liquid crystal aligning film is inside,
It has a polymerizable unsaturated bond group between the substrates, a functional group that forms a mesogenic structure by forming a hydrogen bond between molecules, and at least one or more aromatic rings in the vicinity of the functional group, the following formulas [2-1] to [ 2-3] to form a liquid crystal layer by sandwiching at least one polymerizable compound selected from the group consisting of, and a liquid crystal composition containing liquid crystal,
A method of manufacturing a liquid crystal display device, characterized in that the polymerizable compound is polymerized by irradiating the liquid crystal layer with ultraviolet rays.

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