JP2005250244A - Liquid crystal alignment agent and film, and liquid crystal display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid crystal aligning agent capable of forming a liquid crystal alignment film which prevents display defects, has an excellent after-image characteristic even after long-time driving, does not decrease the capability of aligning liquid crystal, and has a small decrease in voltage holding rate against light and heat. <P>SOLUTION: Disclosed is a liquid crystal aligning agent composition containing a tetrafunctional silicon composition like tetrachalcoxylan, a trifunctional composition like trialcoxylan, and a product of reaction with 0.8 to 3.0 mol water for a 1 mol functional group like an alxoky group, and a glycol-ether-based solvent. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film, and a liquid crystal display element. More specifically, the liquid crystal orientation is good, and the liquid crystal orientation state is maintained well without damaging electrical characteristics such as voltage holding ratio even under severe conditions such as light irradiation and high temperature or after long-time driving. In addition, the present invention relates to a liquid crystal alignment layer that hardly causes an afterimage phenomenon, a liquid crystal alignment agent that can form the liquid crystal alignment layer, and a liquid crystal display element.

  Currently, as a liquid crystal display element, a liquid crystal alignment film made of polyamic acid, polyimide, or the like is formed on the surface of a substrate on which a transparent conductive film is provided to form a liquid crystal display element substrate. A nematic liquid crystal layer having positive dielectric anisotropy is formed in a cell having a sandwich structure so that the major axis of the liquid crystal molecules is continuously twisted 90 degrees from one substrate to the other. A TN type liquid crystal display element having a so-called TN type (Twisted Nematic) liquid crystal cell is known. In addition, an STN (Super Twisted Nematic) type liquid crystal display element capable of realizing a high contrast ratio as compared with a TN type liquid crystal display element, an IPS (In-Plane Switching) type liquid crystal display element having less viewing angle dependency, and a VA (Vertical Alignment). Type liquid crystal display elements have been developed.

The operating principles of these various liquid crystal display elements are broadly divided into transmission types and reflection types.
The transmissive liquid crystal display element performs display using a change in transmitted light intensity of a backlight light source from the back of the element when the element is driven. Reflective liquid crystal display elements do not use a light source for backlights, but display using changes in reflected light intensity of external light such as sunlight when the elements are driven, and consume less power than transmissive displays. Therefore, it is considered particularly advantageous for outdoor use.

  In a transmissive liquid crystal display element, the liquid crystal alignment film is always exposed to light from a backlight light source. In particular, in addition to business use, in liquid crystal projector applications where demand for home theaters has been increasing in recent years, light sources with extremely high irradiation intensity such as metal halide lamps are used. Reflective liquid crystal display elements are highly likely to be used outdoors. In this case, sunlight including strong ultraviolet light is used as a light source. In the reflective type, the distance that light passes through the element is longer than the transmissive type in principle.

  In the manufacturing process of a liquid crystal display element, a liquid crystal dropping method, that is, an ODF (One Drop Fill) method, has started to be used from the viewpoint of process shortening and yield improvement. Unlike the conventional method in which liquid crystal is injected into an empty liquid crystal cell that has been pre-assembled using a thermosetting sealant, the ODF method is UV curable at a required location on a single-side substrate coated with a liquid crystal alignment film. After applying the sealing agent, the liquid crystal is dropped on a necessary portion and the other substrate is bonded, and then the entire surface is irradiated with ultraviolet light to cure the sealing agent to produce a liquid crystal cell. The ultraviolet light irradiated at this time is usually as strong as several joules per square centimeter. That is, in the liquid crystal display element manufacturing process, the liquid crystal alignment film is exposed to the intense ultraviolet light together with the liquid crystal.

  In a transmissive liquid crystal display element, it is conceivable that the temperature of the liquid crystal display element system itself increases during driving due to intense light irradiation. In addition to the versatility of liquid crystal display elements, in addition to the transmissive type, the reflective type can also be used outdoors at high temperatures compared to normal room temperature, such as when used outdoors or installed in a private car while parked. Possible installation environment.

  As described above, in liquid crystal display elements, liquid crystal orientation and voltage retention after being exposed to harsh environments such as light and heat or after being driven for a long time due to its higher functionality and versatility. The electrical characteristics such as the rate or the afterimage characteristics are required to be better than before.

  Conventionally, resins such as polyimide, polyamide, and polyester are known as materials for the liquid crystal alignment film constituting the liquid crystal display element. In particular, polyimides have been used in many liquid crystal display elements because they exhibit excellent physical properties such as heat resistance, affinity with liquid crystals, and mechanical strength among organic resins.

  However, liquid crystal display elements in recent years have become highly functional and versatile, and as described above, there are increasing opportunities for installation and use in harsh environments such as high-temperature environments and light irradiation. In addition, while further shortening of the process and improvement of yield are demanded, liquid crystal display elements have been demanded to have a longer life. As a result, display defects and afterimages caused by insufficient resistance to high-temperature environments and light irradiation that were conventionally within the allowable range have become unacceptable.

  Therefore, organic resins such as polyamic acid and polyimide that have been widely used as liquid crystal alignment films have not yet been sufficiently resistant to light and heat. Therefore, there is a need for a new material that has good resistance to light and heat without degrading the ability to orient liquid crystals uniformly within the plane of the liquid crystal display element.

  In JP-A-9-281502, a silicon compound (A) having four alkoxy groups such as tetraethoxysilane and a silicon compound (B) having three alkoxy groups such as octadecyltriethoxysilane are mixed with alcohol. By heating and reacting at 50 ° C. to 180 ° C. under a oxalic acid catalyst in a solvent, a cocondensate polysiloxane solution of (A) and (B) is produced, and this solution is applied to the electrode substrate surface as a coating solution. A vertical alignment film obtained by thermally curing the obtained coating film at 80 to 400 ° C. is disclosed. This publication further explains that the vertical alignment film is excellent in vertical alignment, reproducibility, heat resistance and uniformity, and also excellent in stability as a coating solution.

  However, such a vertical alignment film or a method for forming the vertical alignment film is still not sufficient. In the vertical alignment film described in JP-A-9-281502, unreacted siloxane groups may remain in the resulting coating film. The unreacted siloxane group is unstable, and the siloxane group is hydrolyzed by a trace amount of water contained in the liquid crystal or water that has entered through the sealing agent of the liquid crystal cell to produce an alcohol molecule. It may cause a display defect or the like due to diffusion.

  The present invention has been made in view of the circumstances as described above, and an object of the present invention is to sufficiently perform a hydrolysis reaction to convert 99% or more of siloxane groups to prevent such display defects. To provide a liquid crystal aligning agent that can form a liquid crystal aligning film that has good afterimage characteristics even after long-time driving, does not decrease the ability to align liquid crystal, and has little decrease in voltage holding ratio against light and heat. It is in.

  Another object of the present invention is to provide a liquid crystal alignment film having the above-mentioned various performances using the liquid crystal aligning agent of the present invention and a method for producing the same.

  Still another object of the present invention is to provide a liquid crystal display device comprising the liquid crystal alignment film of the present invention.

  Still other objects and advantages of the present invention will become apparent from the following description.

According to the present invention, the above objects and advantages of the present invention include, firstly, (I) the reaction product of two specific siloxanes with water and (II) a solvent, specifically, (I)
Following formula (1)
Si (OR ¹ ) ₄ (1)

Here, R ¹ is a hydrogen atom, a fluorine atom or a monovalent organic group.
A silicon compound represented by the following formula (2)
RSi (OR ² ) ₃ (2)

Where R is a monovalent organic group and R ² is a hydrogen atom, a fluorine atom or a monovalent organic group.
A reaction product of a silicon compound and water represented by the following (hereinafter sometimes referred to as “reaction product (1)”) and (II)

Wherein R ³ is a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group or a t-butyl group, m is 0 or 1, and n is 1, 2 or 3. is there,
It achieves by the liquid crystal aligning agent characterized by containing the solvent represented by these.

  According to the present invention, the above objects and advantages of the present invention include, secondly, a step of applying the liquid crystal aligning agent of the present invention to a substrate and a step of curing the coating film by heating the applied substrate. This is achieved by a method of forming a characteristic liquid crystal alignment film.

  According to the present invention, the above objects and advantages of the present invention are thirdly achieved by the liquid crystal alignment film formed by the above method of the present invention.

  According to the present invention, the above objects and advantages of the present invention are finally achieved by a liquid crystal display device comprising the liquid crystal alignment film of the present invention.

  According to the present invention, by using a liquid crystal aligning agent using a silicon-based material, it can be driven for a long time even after being exposed to a harsh environment such as light irradiation or heat treatment compared to conventional materials. Even after the formation of the liquid crystal display device, it is possible to manufacture a liquid crystal display element that does not significantly deteriorate the excellent liquid crystal orientation, voltage holding ratio, and afterimage characteristics.

  The liquid crystal display element produced using the liquid crystal aligning agent of the present invention can be suitably used for TN type and STN type liquid crystal display elements. In addition, by selecting the liquid crystal to be used, an SH (Super Homeotropic) type, IPS It can also be suitably used for (In-Plane Switching) type, VA (Vertical Alignment) type, ferroelectric and antiferroelectric liquid crystal display elements and the like.

    Furthermore, the liquid crystal display element having an alignment film formed using the liquid crystal aligning agent of the present invention is excellent in the alignment and reliability of the liquid crystal, and can be used effectively in various devices, for example, a desk calculator, a wristwatch, a table clock, a coefficient Used in display devices such as display boards, word processors, personal computers, liquid crystal data projectors, liquid crystal televisions, and electronic paper.

[Liquid crystal aligning agent]
The liquid crystal aligning agent of this invention contains (I) reaction product (1) and (II) solvent. (I) The reaction product (1) is represented by the following formula (1)
Si (OR ¹ ) ₄ (1)

Here, R ¹ is a hydrogen atom, a fluorine atom or a monovalent organic group.
Represented by the following formula (2):
RSi (OR ² ) ₃ (2)

Where R is a monovalent organic group and R ² is a hydrogen atom, a fluorine atom or a monovalent organic group.
A reaction product of a silicon compound (hereinafter sometimes referred to as compound (2)) and water.

In the formula (1), examples of the monovalent organic group represented by R ¹ include an alkyl group, an aryl group, an allyl group, an acyl group, and a glycidyl group. Here, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. Preferably it is a C1-C5 alkyl group. These alkyl groups may be chain-like or branched, and a hydrogen atom may be substituted with a fluorine atom or the like. Examples of the aryl group include a phenyl group, a naphthyl group, a methylphenyl group, an ethylphenyl group, a chlorophenyl group, a bromophenyl group, and a fluorophenyl group.

  Examples of the acyl group include an acetyl group, a benzoyl group, a formyl group, and a propionyl group.

  Specific examples of the compound (1) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, and tetra-tert. -Butoxysilane, tetraphenoxysilane, tetraacetoxysilane, tetraglycidyloxysilane and the like. These may be used alone or in combination of two or more.

In the formula (2), R is a monovalent organic group and R ² is a hydrogen atom, a fluorine atom or a monovalent organic group. Examples of the monovalent organic group for R ² include the same as those for R ¹ .

  Examples of the monovalent organic group of R include, for example, an alkyl group having 1 to 4 carbon atoms, a vinyl group, and a phenyl group, which may be substituted with an amino group, a glycidoxy group, or a trifluoromethyl group; A monovalent organic group optionally substituted and having at least one norbornane ring; a monovalent organic group optionally substituted and having at least one steroid skeleton; fluorine atom Preferred examples include a monovalent organic group having an aromatic ring having a trifluoromethyl group or a trifluoromethoxy group as a substituent and having 8 or more carbon atoms; and a photosensitive group which is a cinnamoyl group or a chalconyl group. Can do.

  Of a compound wherein R is an amino group, a glycidoxy group or a trifluoromethyl group and is an alkyl group having 1 to 4 carbon atoms, a vinyl group or a phenyl group (hereinafter sometimes referred to as compound (A)) Specific examples include methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, methyltri-n-butoxysilane, methyltri-sec-butoxysilane, methyltri-tert-butoxy. Silane, methyltriphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-iso-propoxysilane, ethyltri-n-butoxysilane, ethyltri-sec-butoxysilane, ethyltri-te t-butoxysilane, ethyltriphenoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltri-iso-propoxysilane, vinyltri-n-butoxysilane, vinyltri-sec-butoxysilane, vinyltri- tert-butoxysilane, vinyltriphenoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltri-n-propoxysilane, n-propyltri-iso-propoxysilane, n-propyltri-n -Butoxysilane, n-propyltri-sec-butoxysilane, n-propyltri-tert-butoxysilane, n-propyltriphenoxysilane, i-propyltrimethoxysilane, i-propyltrieth Sisilane, i-propyltri-n-propoxysilane, i-propyltri-iso-propoxysilane, i-propyltri-n-butoxysilane, i-propyltri-sec-butoxysilane, i-propyltri-tert-butoxy Silane, i-propyltriphenoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-butyltri-n-propoxysilane, n-butyltri-iso-propoxysilane, n-butyltri-n-butoxysilane, n-butyltri-sec-butoxysilane, n-butyltri-tert-butoxysilane, n-butyltriphenoxysilane, sec-butyltrimethoxysilane, sec-butyl-i-triethoxysilane, sec-butyl-tri-n- Propoxysilane, sec -Butyl-tri-iso-propoxysilane, sec-butyl-tri-n-butoxysilane, sec-butyl-tri-sec-butoxysilane, sec-butyl-tri-tert-butoxysilane, sec-butyl-triphenoxysilane T-butyltrimethoxysilane, t-butyltriethoxysilane, t-butyltri-n-propoxysilane, t-butyltri-iso-propoxysilane, t-butyltri-n-butoxysilane, t-butyltri-sec-butoxysilane , T-butyltri-tert-butoxysilane, t-butyltriphenoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltri-iso-propoxysilane, phenyltri-n-butoxy , Phenyltri-sec-butoxysilane, phenyltri-tert-butoxysilane, phenyltriphenoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ -Glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-trifluoropropyltrimethoxysilane, γ-trifluoropropyltriethoxysilane and the like. Of these, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane and the like are preferable.

In the above formula (2), R is
(A) a linear alkyl group having 16 or more carbon atoms,
(A) a monovalent organic group which may be substituted and has at least one norbornane ring;
(C) a monovalent organic group which may be substituted and has at least one steroid skeleton,
(D) a monovalent organic group having an aromatic ring having a substituent selected from the group consisting of a fluorine atom, a trifluoromethyl group and a trifluoromethoxy group, or (e) a cinnamoyl group or a chalconyl group Examples of the photosensitive group which is a group (hereinafter sometimes referred to as compound (B)) include, for example, hexadecyltrimethoxysilane, heptadecyltrimethoxysilane, octadecyltrimethoxysilane, nonadecyltrimethoxysilane, hexa Decyltriethoxysilane, heptadecyltriethoxysilane, octadecyltriethoxysilane, nonadecyltriethoxysilane, etc. (wherein R is (a));

  A compound wherein R is a structure selected from the following formulas (4) to (16) (where R is (i));

  A compound wherein R is a structure selected from the following formulas (17) to (26) (where R is (u));

  A compound wherein R is a structure selected from the following formulas (27) to (30) (where R is (d));

  4′-calconyltrimethoxysilane, 4′-calconyltriethoxysilane, cinnamoyltrimethoxysilane, cinnamoyltriethoxysilane, cinnamoyloxytrimethoxysilane, cinnamoyloxytriethoxysilane (R is (O ))).

  These may be used alone or in combination of two or more.

As the compound (2), it is preferable to use a combination selected from one or more of each of the compound (A) and the compound (B).
As a use ratio of the compound (1) and the compound (2), the compound (2) is preferably 10 to 99 mol%, more preferably 50 to 50% based on the total amount of the compounds (1) and (2). 99 mol%.

The reaction product (1) can be obtained by reacting the compound (1), the compound (2) and water, followed by hydrolysis and partial condensation. In order to hydrolyze and partially condense the compound (1) and the compound (2), the siloxane bond (the sum of —OR ¹ of the formula ( ¹ ) and —OR ² of the formula (2)) is preferably 1. 0-1.5 mol of water is used. If the amount of water is 1.0 mol or more, the possibility that the siloxane bond remains unreacted is reduced, there is no possibility that the uniformity of the coating film is lowered, and the storage stability of the liquid crystal aligning agent is lowered. This is preferable because there is less risk of doing so. Water is intermittently or continuously added to the organic solvent in which the compound (1) and the compound (2) are dissolved. At this time, a reaction catalyst can be used, and when used, the catalyst may be added in advance to an organic solvent, or may be dissolved or dispersed in water when water is added. As reaction temperature in this case, Preferably it is 0-100 degreeC, More preferably, it is 15-80 degreeC.

  The organic solvent for hydrolyzing and partially condensing the compound (1) and the compound (2) is preferably selected from the group of alcohol solvents, ketone solvents, amide solvents, ester solvents and aprotic solvents. At least one of these can be used.

  Here, examples of the alcohol solvent include methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2 -Methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, heptanol-3, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol Call, phenol, cyclohexanol, methyl cyclohexanol, 3,3,5-trimethyl cyclohexanol, benzyl alcohol, mono-alcohol solvents such as diacetone alcohol;

Ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, pentanediol-2,4, 2-methylpentanediol-2,4, hexanediol-2,5, heptanediol-2,4, 2- Polyhydric alcohol solvents such as ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol;

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, polyhydric alcohol partial ether solvents such as dipropylene glycol monopropyl ether;
And so on.

  These alcohol solvents may be used alone or in combination of two or more.

  Examples of ketone solvents include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n. -Hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, acetophenone, fenchon, acetylacetone, 2,4-hexanedione 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione, 2,4-nonanedione, 3,5-nonanedione, 5-methyl-2,4-hexane Dione, 2,2,6,6-tetramethyl 3,5-heptanedione, 1,1,1,5,5,5 beta-diketones such as hexafluoro-2,4-heptane dione and the like.

  These ketone solvents may be used alone or in combination of two or more.

  Examples of the amide solvent include formamide, N-methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N- Ethylacetamide, N, N-diethylacetamide, N-methylpropionamide, N-methylpyrrolidone, N-formylmorpholine, N-formylpiperidine, N-formylpyrrolidine, N-acetylmorpholine, N-acetylpiperidine, N-acetylpyrrolidine Etc.

  These amide solvents may be used alone or in combination of two or more.

  Examples of the ester solvent include diethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, I-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methyl pentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, N-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, acetic acid Diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, diacetic acid Glycol, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate , Diethyl malonate, dimethyl phthalate, diethyl phthalate and the like.

  These ester solvents may be used alone or in combination of two or more.

  Examples of aprotic solvents include acetonitrile, dimethyl sulfoxide, N, N, N ′, N′-tetraethylsulfamide, hexamethylphosphoric triamide, N-methylmorpholone, N-methylpyrrole, and N-ethylpyrrole. N-methyl-Δ3-pyrroline, N-methylpiperidine, N-ethylpiperidine, N, N-dimethylpiperazine, N-methylimidazole, N-methyl-4-piperidone, N-methyl-2-piperidone, N-methyl -2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyltetrahydro-2 (1H) -pyrimidinone and the like. Among these, polyhydric alcohol solvents, polyhydric alcohol partial ether solvents, and ester solvents are particularly preferable.

  In the hydrolysis and partial condensation reaction of the compound (1) and the compound (2), a catalyst is preferably used. Examples of the catalyst include the following metal chelate compounds, organic acids, inorganic acids, organic bases, and inorganic bases.

  Examples of the metal chelate compound include triethoxy mono (acetylacetonato) titanium, tri-n-propoxy mono (acetylacetonato) titanium, tri-i-propoxy mono (acetylacetonato) titanium, tri-n-butoxy. Mono (acetylacetonato) titanium, tri-sec-butoxy mono (acetylacetonato) titanium, tri-t-butoxy mono (acetylacetonato) titanium, diethoxybis (acetylacetonato) titanium, di-n -Propoxy bis (acetylacetonato) titanium, di-i-propoxy bis (acetylacetonato) titanium, di-n-butoxy bis (acetylacetonato) titanium, di-sec-butoxy bis (acetylacetonate) ) Titanium, di-t-butoxy bis Acetylacetonato) titanium, monoethoxy-tris (acetylacetonato) titanium, mono-n-propoxy-tris (acetylacetonato) titanium, mono-i-propoxy-tris (acetylacetonato) titanium, mono-n-butoxy -Tris (acetylacetonato) titanium, mono-sec-butoxy-tris (acetylacetonato) titanium, mono-t-butoxy-tris (acetylacetonato) titanium, tetrakis (acetylacetonato) titanium,

Triethoxy mono (ethyl acetoacetate) titanium, tri-n-propoxy mono (ethyl acetoacetate) titanium, tri-i-propoxy mono (ethyl acetoacetate) titanium, tri-n-butoxy mono (ethyl acetoacetate) Titanium, tri-sec-butoxy mono (ethyl acetoacetate) titanium, tri-t-butoxy mono (ethyl acetoacetate) titanium, diethoxy bis (ethyl acetoacetate) titanium, di-n-propoxy bis (ethyl aceto) Acetate) titanium, di-i-propoxy bis (ethyl acetoacetate) titanium, di-n-butoxy bis (ethyl acetoacetate) titanium, di-sec-butoxy bis (ethyl acetoacetate) titanium, di-t- Butoxy bis (ethylacetate Acetate) titanium, monoethoxy tris (ethyl acetoacetate) titanium, mono-n-propoxy tris (ethyl acetoacetate) titanium, mono-i-propoxy tris (ethyl acetoacetate) titanium, mono-n-butoxy tris (Ethyl acetoacetate) titanium, mono-sec-butoxy tris (ethyl acetoacetate) titanium, mono-t-butoxy tris (ethyl acetoacetate) titanium, tetrakis (ethyl acetoacetate) titanium, mono (acetylacetonate) tris Titanium chelate compounds such as (ethyl acetoacetate) titanium, bis (acetylacetonato) bis (ethylacetoacetate) titanium, tris (acetylacetonato) mono (ethylacetoacetate) titanium;

Triethoxy mono (acetylacetonato) zirconium, tri-n-propoxy mono (acetylacetonato) zirconium, tri-i-propoxy mono (acetylacetonato) zirconium, tri-n-butoxy mono (acetylacetonate) Zirconium, tri-sec-butoxy mono (acetylacetonato) zirconium, tri-t-butoxy mono (acetylacetonato) zirconium, diethoxybis (acetylacetonato) zirconium, di-n-propoxybis (acetylacetate) Nato) zirconium, di-i-propoxy bis (acetylacetonato) zirconium, di-n-butoxy bis (acetylacetonato) zirconium, di-sec-butoxy bis (acetylacetonato) ziru Ni, di-t-butoxy bis (acetylacetonato) zirconium, monoethoxy tris (acetylacetonato) zirconium, mono-n-propoxytris (acetylacetonato) zirconium, mono-i-propoxytris (acetyl) Acetonato) zirconium, mono-n-butoxy-tris (acetylacetonato) zirconium, mono-sec-butoxy-tris (acetylacetonato) zirconium, mono-t-butoxy-tris (acetylacetonato) zirconium, tetrakis (acetyl) Acetonate) zirconium,

Triethoxy mono (ethyl acetoacetate) zirconium, tri-n-propoxy mono (ethyl acetoacetate) zirconium, tri-i-propoxy mono (ethyl acetoacetate) zirconium, tri-n-butoxy mono (ethyl acetoacetate) Zirconium, tri-sec-butoxy mono (ethyl acetoacetate) zirconium, tri-t-butoxy mono (ethyl acetoacetate) zirconium, diethoxy bis (ethyl acetoacetate) zirconium, di-n-propoxy bis (ethyl aceto) Acetate) zirconium, di-i-propoxy bis (ethyl acetoacetate) zirconium, di-n-butoxy bis (ethyl acetoacetate) zirconium, di-sec-butoxy bis (ethyl) Cetoacetate) zirconium, di-t-butoxy bis (ethyl acetoacetate) zirconium, monoethoxy tris (ethyl acetoacetate) zirconium, mono-n-propoxy tris (ethyl acetoacetate) zirconium, mono-i-propoxy Tris (ethyl acetoacetate) zirconium, mono-n-butoxy tris (ethyl acetoacetate) zirconium, mono-sec-butoxy tris (ethyl acetoacetate) zirconium, mono-t-butoxy tris (ethyl acetoacetate) zirconium, Tetrakis (ethylacetoacetate) zirconium, mono (acetylacetonato) tris (ethylacetoacetate) zirconium, bis (acetylacetonato) bis (ethylacetoacetate) Over G) zirconium, tris (acetylacetonato) mono (ethylacetoacetate) zirconium chelate compounds such as zirconium;

Aluminum chelate compounds such as tris (acetylacetonate) aluminum and tris (ethylacetoacetate) aluminum;
And so on.

  Examples of organic acids include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallic acid , Butyric acid, melicic acid, arachidonic acid, mikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid Monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid and the like.

  Examples of inorganic acids include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.

  Examples of the organic base include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicycloocrane, diazabicyclononane. , Diazabicycloundecene, tetramethylammonium hydroxide and the like.

  Examples of the inorganic base include ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide and the like.

  Of these catalysts, metal chelate compounds, organic acids, and inorganic acids are preferable, and titanium chelate compounds and organic acids are more preferable. These may be used alone or in combination of two or more.

  The amount of the catalyst used is preferably 0.001 to 10 parts by weight, more preferably 0.001 to 100 parts by weight of the combination of the compound (1) and the compound (2) (in terms of complete hydrolysis condensate). It is in the range of ˜1 part by weight.

  The liquid crystal aligning agent of the present invention is obtained by dissolving or dispersing the reaction product (1) in an organic solvent.

  As an organic solvent, following formula (3)

Wherein R ³ is a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group or a t-butyl group, m is 0 or 1, and n is 1, 2 or 3. is there,
The solvent represented by these is used.

  Specific examples of such organic solvents include ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol mono (n-propyl) ether, propylene glycol mono (n-propyl) ether. , Ethylene glycol mono (i-propyl) ether, propylene glycol mono (i-propyl) ether, ethylene glycol mono (n-butyl) ether, propylene glycol mono (n-butyl) ether, ethylene glycol mono (t-butyl) ether And propylene glycol mono (t-butyl) ether.

  These solvents are used alone or in combination of two or more. In addition, a poor solvent that is difficult to dissolve the material to be used can be used in an amount within a range in which the solid content does not precipitate.

  Specific examples of such poor solvents include, for example, n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i-octane, Cyclohexane, methylcyclohexane, decane, dicyclopentadiene, benzene, toluene, xylene, durene, indene, tetrahydronaphthalene, decahydronaphthalene, squalane, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, Hydrocarbon solvents such as i-butylbenzene, triethylbenzene, di-i-propylbenzene, n-amylnaphthalene, trimethylbenzene; methanol, ethanol, n-propanol, i-propanol, n-butyl Nord, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2- Methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, heptanol-3, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n -Decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol Monoalcohol solvents such as benzyl alcohol, phenylmethyl carbinol, diacetone alcohol, cresol; ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, pentanediol-2,4, 2-methylpentanediol- Polyhydric alcohol solvents such as 2,4, hexanediol-2,5, heptanediol-2,4,2-ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin Acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, methyl amyl ketone, ethyl-n-butyl ketone, Methyl-n-hexyl ketone, dipropyl ketone, di-i-butyl ketone, trimethylnonanone, cyclopentanone, cyclohexanone, methylcyclohexanone, cycloheptanone, 2,4-pentanedione, acetonylacetone, acetophenone, fenchon, etc. Ketone solvents: diethyl ether, di-i-propyl ether, di-n-propyl ether, di-n-butyl ether, di-n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane Ether solvents such as 4-methyldioxolane, dioxane, dimethyldioxane, phenetole, diphenyl ether tetrahydrofuran, 2-methyl tetrahydrofuran; diethyl carbonate, propylene carbonate, -Butyrolactone, γ-valerolactone, methyl acetate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, acetic acid 3-methoxybutyl, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, n-hexyl acetate, cyclohexyl acetate, octyl acetate, amyl acetate, isoamyl acetate, methylcyclohexyl acetate, n-nonyl acetate, acetoacetic acid Methyl, ethyl acetoacetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, Diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene acetate Glycol monoethyl ether, glycol diacetate, methoxytriglycol acetate, ethyl phenylacetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl propionate, ethyl propionate, n-propyl propionate, isopropyl propionate, N-butyl propionate, isobutyl propionate, i-amyl propionate, propio Benzyl acid, ethoxyethyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, n-amyl lactate, methyl formate, ethyl formate, N-propyl formate, isopropyl formate, n-butyl formate, isobutyl formate, n-amyl formate, isoamyl formate, methyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, isobutyl butyrate, diethyl malonate, Ester solvents such as dimethyl phthalate, diethyl phthalate, ethyl pyruvate; N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropionamide, N-me Examples include amide solvents such as tilpyrrolidone; sulfur-containing solvents such as dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, and 1,3-propane sultone.

  Such a poor solvent is used in an amount of, for example, 50 parts by weight or less, preferably 30 parts by weight or less with respect to 100 parts by weight of the organic solvent represented by the above formula (3).

  You may add the following (beta) -diketone to the liquid crystal aligning agent of this invention further.

  Acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione, 2,4-nonanedione, 3,5-nonanedione, 5 -Methyl-2,4-hexanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1,1,1,5,5,5-hexafluoro-2,4-heptanedione, etc. 1 type or 2 types or more.

  Components such as colloidal silica, colloidal alumina, organic polymer, and surfactant may be further added to the liquid crystal aligning agent obtained in the present invention.

  Colloidal silica is, for example, a dispersion in which high-purity silicic acid is dispersed in the hydrophilic organic solvent. Usually, the average particle size is 5 to 30 mμ, preferably 10 to 20 mμ, and the solid content concentration is 10 to 40. It is about wt%. Examples of such colloidal silica include Nissan Chemical Industries, Ltd., methanol silica sol and isopropanol silica sol; Catalyst Kasei Kogyo Co., Ltd., Oscar.

  Examples of the colloidal alumina include Alumina Sol 520, 100 and 200 manufactured by Nissan Chemical Industries, Ltd .; Alumina Clear Sol, Alumina Sol 10 and 132 manufactured by Kawaken Fine Chemical Co., Ltd., and the like.

  Examples of organic polymers include compounds having a polyalkylene oxide structure, compounds having a sugar chain structure, vinylamide polymers, (meth) acrylate compounds, aromatic vinyl compounds, dendrimers, polyimides, polyamic acids, polyarylenes, polyamides, poly Examples thereof include quinoxaline, polyoxadiazole, and a fluorine-based polymer.

  Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants, and further include silicone surfactants, polyalkylene oxide surfactants. And fluorine-containing surfactants.

  The liquid crystal aligning agent of the present invention may contain a functional silane-containing compound or an epoxy group-containing compound from the viewpoint of improving the adhesion to the substrate surface. Examples of such functional silane-containing compounds include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, and N- (2-aminoethyl). -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-amino Propyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl- , 4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N -Bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, etc. can be mentioned. Examples of the epoxy group-containing compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentylglycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ′, N ′,-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N ′,-tetraglycidyl , And the like as preferred 4,4'-diaminodiphenylmethane.

The ratio of the reaction product (1) and the solvent in the liquid crystal aligning agent of the present invention is selected in consideration of viscosity, volatility, etc., but the ratio of the reaction product (1) in the liquid crystal aligning agent (solid content) concentration), the SiO ₂ concentration in terms of silicon atoms contained in the reaction product (1) to the SiO _2, preferably 0.01 to 70 wt%, more preferably 0.05 to 60 wt%, further The ratio is preferably 1 to 30% by weight. As will be described later, the liquid crystal aligning agent of the present invention is preferably applied to the substrate surface by, for example, a roll coater method, a spinner method, a printing method, etc., and then heated and dried to form a liquid crystal aligning film. However, when the solid content concentration is less than 0.01% by weight, the film thickness of this coating film may be too small to obtain a good liquid crystal alignment film. Is more than 70% by weight, it is difficult to obtain a good liquid crystal alignment film due to excessive film thickness, and the viscosity of the liquid crystal aligning agent may increase, resulting in poor coating characteristics. .

  The ratio of the solvent (II) in the liquid crystal aligning agent of the present invention is preferably 1 to 100% by weight, more preferably 30 to 100% by weight, and further preferably 70 to 70% by weight in the total solvent. 100% by weight.

  Using the liquid crystal aligning agent of this invention, a liquid crystal display element can be manufactured, for example with the following method.

(1) The liquid crystal aligning agent of the present invention is applied to one surface of a substrate provided with a patterned transparent conductive film by a method such as a roll coater method, a spinner method, a printing method, an ink jet method, etc. Is heated to form a coating film. The atmosphere of the coating and heating process can be performed in an inert gas such as nitrogen, helium, or argon, and can be performed in an atmosphere mixed with a reducing gas such as hydrogen as necessary. Here, as the substrate, for example, glass such as float glass or soda glass; a transparent substrate made of a plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polymethyl methacrylate, or polycarbonate can be used. As the transparent conductive film provided on one surface of the substrate, an NESA film (registered trademark of PPG, USA) made of tin oxide (SnO ₂ ), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ —SnO ₂ ), etc. For patterning these transparent conductive films, a photo-etching method or a method using a mask in advance is used. When applying the liquid crystal aligning agent, in order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film, a functional silane-containing compound, a functional titanium-containing compound, or the like is previously applied to the surface of the substrate. You can also The heating temperature after application of the liquid crystal aligning agent is a temperature that does not cause deformation of the substrate material, and is preferably 20 to 300 ° C, more preferably 120 to 300 ° C. Examples of the heat source for the heat treatment include a hot air drying furnace, an infrared heating furnace, and a hot plate. The film thickness of the formed coating film is preferably 0.001-1 μm, more preferably 0.005-0.5 μm.

(2) The liquid crystal alignment angle can be controlled by rubbing the surface of the formed coating film surface. Also, the liquid crystal alignment angle can be controlled by a step of impacting the surface such as electromagnetic radiation or particle beam. As the particle beam used here, an ion beam, a neutral atom beam, an electron beam, a molecular beam, an elementary particle beam, or the like can be used. Irradiation energy, irradiation angle, and irradiation time can be adjusted to appropriate values depending on the type of liquid crystal alignment film and the value of the pretilt angle to be applied. In the case of using an ion beam, it is preferable to use an ion beam of an inert gas such as nitrogen, helium, argon, or neon as the ion species of the ion beam. Further, it is preferable to supply electrons for ion neutralization during or after ion beam irradiation.

  A technique for imparting liquid crystal alignment ability to an irradiated surface using an ion beam is disclosed in Japanese Patent Application Laid-Open No. 11-271773. However, in this publication, a covalent bond material such as hydrogenated diamond-like carbon (DLC) is used as a material for forming the liquid crystal alignment layer, and the liquid crystal alignment layer is formed by a non-aqueous gas environment adhesion method such as chemical vapor deposition. The coating process such as a roll coater method, a spinner method, a printing method, an ink jet method and the like that have been widely used and conventionally used as a method for forming a liquid crystal alignment layer is not targeted. In the present invention, since the liquid crystal aligning agent is provided in the form of a solution, there is an advantage that an apparatus conventionally used for coating a liquid crystal aligning film such as a spinner method and a printing method can be used as it is.

  Specific examples of the liquid crystal aligning agent effective for the ion beam method include Japanese Patent Application Laid-Open Nos. 8-313912, 8-313913, 8-313916, and the like using polyamic acid or soluble polyimide as the liquid crystal aligning agent. No. 11-237638. As described above, the present invention relates to liquid crystal orientation and afterimage characteristics after being exposed to a severe environment such as light and heat, or after being driven for a long time. Or the good characteristic which is not in soluble polyimide was realized.

  A technique for imparting liquid crystal alignment ability to an irradiated surface using an electron beam is disclosed in Japanese Patent Laid-Open No. 06-130389. However, even in the same issue, since the conventional polyamic acid or soluble polyimide is used as the substance for forming the liquid crystal alignment layer, there is little decrease in the voltage holding ratio against light and heat as disclosed in the present invention. It is difficult to form a liquid crystal alignment layer.

  A technique for orienting the irradiated surface using a molecular beam, a neutral atom beam, an elementary particle beam, and electromagnetic radiation is disclosed in Japanese Patent Laid-Open No. 10-96928. However, since the conventional polyimide is used as a material for forming the liquid crystal alignment layer, the liquid crystal alignment layer as disclosed in the present invention has little decrease in voltage holding ratio against light and heat. It is difficult to form.

In the liquid crystal aligning agent according to the present invention, ultraviolet rays and the like can be obtained by using 1.0 to 50 mol% of the compound (2) as a compound in which R ² is a photosensitive group such as a chalconyl group or a cinnamoyl group. By irradiating the electromagnetic radiation, the liquid crystal alignment angle can be controlled.

  Further, a method of partially irradiating the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention with ultraviolet rays as disclosed in, for example, JP-A-6-222366 and JP-A-6-281937, Alternatively, as disclosed in JP-A-10-96928, a method of irradiating the surface of the liquid crystal alignment film with an ion beam in a position-selective manner over a plurality of steps, or as disclosed in JP-A-11-242225. By providing a structure that regulates the orientation direction, it is possible to improve the visual field characteristics of the liquid crystal display element.

(3) Two substrates on which the liquid crystal alignment film is formed as described above are produced, and a thermosetting sealant is applied in an appropriate pattern to the periphery of one substrate. Two substrates are arranged opposite each other with a gap (cell gap) so that the liquid crystal alignment directions in the respective liquid crystal alignment films are orthogonal or antiparallel, and the two substrates are bonded together, and then heated. Cure the sealant. Liquid crystal is injected and filled in the cell gap defined by the substrate surface and the sealing agent, and the injection hole is sealed to form a liquid crystal cell.

  A liquid crystal dropping method, that is, an ODF (One Drop Fill) method, can be used for the steps from the bonding of the two substrates to the liquid crystal injection. Apply a liquid crystal alignment film, apply UV curable sealant in an appropriate pattern to one substrate with liquid crystal alignment capability as described above, drop the liquid crystal on the required location, and then bond it to the other substrate The sealant is cured by ultraviolet light irradiation. Irradiation with ultraviolet light is not limited to the entire surface exposure, and an appropriate method such as mask exposure or scan exposure can be used.

  Then, a polarizing plate is provided on the outer surface of the liquid crystal cell, that is, the other surface side of each substrate constituting the liquid crystal cell, and the polarization direction thereof coincides with or orthogonal to the liquid crystal alignment direction of the liquid crystal alignment film formed on one surface of the substrate. A liquid crystal display element is obtained by pasting together.

  Examples of the liquid crystal include nematic liquid crystal and smectic liquid crystal. Among them, nematic liquid crystal is preferable. For example, Schiff base liquid crystal, azoxy liquid crystal, biphenyl liquid crystal, phenyl cyclohexane liquid crystal, ester liquid crystal, terphenyl liquid crystal. Liquid crystals, biphenylcyclohexane liquid crystals, pyrimidine liquid crystals, dioxane liquid crystals, bicyclooctane liquid crystals, cubane liquid crystals, and the like can be used. Further, for these liquid crystals, for example, cholesteric liquid crystals such as cholestyl chloride, cholesteryl nonate, cholesteryl carbonate, and chiral agents such as those sold under the trade names “C-15” and “CB-15” (manufactured by Merck). Etc. can also be used. Furthermore, a ferroelectric liquid crystal such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate can also be used.

  As a polarizing plate to be bonded to the outer surface of the liquid crystal cell, a polarizing film called an H film that absorbs iodine while stretching and aligning polyvinyl alcohol is sandwiched between cellulose acetate protective films or the H film itself. The polarizing plate which can be mentioned can be mentioned.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples unless it exceeds the gist. In the following examples, all parts are parts by weight.

Synthesis example 1
106.3 g of methyltriethoxysilane, 6.82 g of octadecyltriethoxysilane, and 12.67 g of tetramethoxysilane were dissolved in 261.1 g of ethylene glycol monobutyl ether, and then stirred with a three-one motor to bring the solution temperature to 60 ° C. Stabilized. Next, 46.8 g of ion-exchanged water in which 1.06 g of maleic acid was dissolved was added to the solution over 1 hour. Thereafter, reacted for 4 hours at 60 ° C., the reaction product (1) is to obtain a solution 435g of a 10% by weight SiO ₂ concentration. After cooling this solution to room temperature, the mixed solution of methanol and ethanol was removed from the solution at 50 ° C. by evaporation. Then, 65.3 g of ethylene glycol monobutyl ether was added and filtered through a membrane filter having a pore size of 0.2 μm. A liquid crystal aligning agent (A) was obtained.

Synthesis example 2
After dissolving 106.3 g of methyltriethoxysilane, 6.64 g of 1-trimethylsilyl-3,3-difluoro-4,4-dimethylnorbornane, and 12.67 g of tetramethoxysilane in 260.8 g of ethylene glycol monobutyl ether, The solution temperature was stabilized at 60 ° C. by stirring with a three-one motor. Next, 47.3 g of ion-exchanged water in which 1.07 g of maleic acid was dissolved was added to the solution over 1 hour. Thereafter, reacted for 4 hours at 60 ° C., the reaction product (1) is to obtain a solution 430g of a 10% by weight SiO ₂ concentration. After cooling this solution to room temperature, the mixed solution of methanol and ethanol was removed from the solution at 50 ° C. by evaporation, 65.2 g of ethylene glycol monobutyl ether was added, and the mixture was filtered with a membrane filter having a pore size of 0.2 μm. A liquid crystal aligning agent (B) was obtained.

Synthesis example 3
After dissolving 106.3 g of methyltriethoxysilane, 5.79 g of 3-trimethylsiloxycholestane, and 12.67 g of tetramethoxysilane in 262.2 g of ethylene glycol monobutyl ether, the mixture was stirred with a three-one motor, and the solution temperature was set to 60. Stabilized at ℃. Next, 46.5 g of ion-exchanged water in which 1.06 g of maleic acid was dissolved was added to the solution over 1 hour. Thereafter, reacted for 4 hours at 60 ° C., the reaction product (1) is to obtain a solution 420g of a 10% by weight SiO ₂ concentration. After cooling this solution to room temperature, after removing the methanol / ethanol mixed solution from the solution by evaporation at 50 ° C., 65.5 g of ethylene glycol monobutyl ether was added and filtered through a membrane filter having a pore size of 0.2 μm. A liquid crystal aligning agent (C) was obtained.

Synthesis example 4
After dissolving 92.98 g of methyltriethoxysilane, 6.64 g of 4′-trimethylsiloxychalcone, 6.82 g of octadecyltriethoxysilane, and 12.67 g of tetramethoxysilane in 259.6 g of ethylene glycol monobutyl ether, The solution temperature was stabilized at 60 ° C. by stirring with a motor. Next, 49.4 g of ion-exchanged water in which 1.12 g of maleic acid was dissolved was added to the solution over 1 hour. Thereafter, reacted for 4 hours at 60 ° C., the reaction product (1) is to obtain a solution 430g of a 10% by weight SiO ₂ concentration. After cooling this solution to room temperature, the mixed solution of methanol and ethanol was removed from the solution at 50 ° C. by evaporation, 65.0 g of ethylene glycol monobutyl ether was added, and the mixture was filtered through a membrane filter having a pore size of 0.2 μm. A liquid crystal aligning agent (D) was obtained.

Comparative Synthesis Example 1
218.1 g (1.0 mol) of pyromellitic dianhydride and 198.27 g (1.0 mol) of 4,4′-diaminodiphenylmethane were dissolved in 1600 g of N-methyl-2-pyrrolidone. For 6 hours. Next, the obtained reaction solution was poured into a large excess of acetone to precipitate the reaction product, and then the reaction product was separated, washed and dried to obtain 400.3 g of a polyamic acid polymer. This polymer was dissolved in γ-butyrolactone and filtered through a membrane filter having a pore size of 0.2 μm to obtain a liquid crystal aligning agent (E) having a solid content concentration of 4%.

[Orientation of liquid crystal]
The presence or absence of an abnormal domain in the liquid crystal cell when the voltage is turned on / off of the liquid crystal display element is observed with a microscope, and the case where there is no abnormal domain is judged as “good”. It investigated immediately after liquid crystal display element preparation, after light irradiation mentioned later, and after heat processing, respectively.

[Afterimage erasing time of liquid crystal display element]
A 30 Hz, 3.0 V rectangular wave with 3.0 V DC and 6.0 V AC (peak-peak) superimposed on the liquid crystal display element was applied at an ambient temperature of 70 ° C. for 20 hours to drive the liquid crystal display element, and then the voltage was applied. The time until the afterimage was erased was measured by visual inspection.

[Voltage holding ratio of liquid crystal display element]
A voltage of 5 V was applied to the liquid crystal display element with an application time of 60 microseconds and a span of 167 milliseconds, and then the voltage holding ratio after 167 milliseconds from the release of application was measured. The measuring apparatus used was VHR-1 manufactured by Toyo Corporation, and was performed at 60 ° C. Measurements were made immediately after the production of the liquid crystal display element, after light irradiation described later, and after heat treatment.

[Light irradiation]
After producing the liquid crystal display element, the entire surface of the element was irradiated with light using a metal halide lamp as a light source. The irradiation wavelength was 300-450 nm by using a filter, and the irradiation energy was ² J / cm ² .

[Heat treatment]
The produced liquid crystal display element was left in an oven at 100 ° C. for 3 weeks, then taken out and gradually cooled to room temperature.

Example 1
The liquid crystal aligning agent (A) is applied to the transparent electrode surface of the glass substrate with a transparent electrode made of an ITO film using a spinner, dried by heating on a 300 ° C. hot plate for 30 minutes, and a coating film having a dry average film thickness of 700 Å Formed.

  Two substrates on which the liquid crystal alignment film was formed as described above were prepared, and an epoxy resin adhesive containing aluminum oxide spheres was applied to the outer edge of each substrate by a screen printing method. The substrate was placed so that the coating surfaces face each other through a gap, and the outer edge portions were brought into contact with each other and pressed to cure the adhesive. A negative type nematic liquid crystal is injected and filled into the cell gap defined by the adhesive on the surface and outer edge of the substrate, and then the injection hole is sealed with an epoxy adhesive to produce a vertical alignment type liquid crystal display device. did.

  With respect to the liquid crystal display element immediately after fabrication thus obtained, the liquid crystal orientation was observed and the voltage holding ratio was measured. Also, three liquid crystal display elements prepared as described above using the liquid crystal aligning agent (A) were prepared, and after one point was irradiated with light, the liquid crystal alignment was observed and the voltage holding ratio was measured. After the heat treatment, the liquid crystal orientation was observed and the voltage holding ratio was measured. The remaining one point was measured for the afterimage erasing time by the method described above. The results are shown in Table 1.

Examples 2-3
A liquid crystal display element was produced in the same manner as in Example 1 using the liquid crystal aligning agent obtained in Synthesis Examples 2-3. With respect to each of the obtained liquid crystal display elements, as shown in Example 1, liquid crystal orientation, voltage holding ratio, and afterimage erasing time were evaluated. The results are shown in Table 1.

Example 4
The liquid crystal aligning agent (A) is applied to the transparent electrode surface of the glass substrate with a transparent electrode made of an ITO film using a spinner, dried by heating on a 300 ° C. hot plate for 30 minutes, and a coating film having a dry average film thickness of 700 Å Formed.

  This coating film was irradiated with an argon ion beam at an acceleration voltage of 200 V for 10 seconds from a direction where the angle from the substrate was 40 °.

  Next, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm is screen-printed on the outer edges of the pair of ion beam-treated liquid crystal sandwich substrates having the liquid crystal alignment film, and then the pair of liquid crystal sandwich substrates is liquid crystal The adhesive film was cured by overlapping and pressing so that the alignment film surfaces face each other and the ion beam irradiation directions were orthogonal.

  Next, a nematic liquid crystal (MLC-6221, manufactured by Merck & Co., Inc.) is filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port is sealed with an acrylic photo-curing adhesive, and both sides outside the substrate are sealed. The polarizing plate was bonded to the polarizing plate so that the polarizing direction of the polarizing plate coincided with the ion beam irradiation direction of the liquid crystal alignment film of each substrate.

    Each liquid crystal display element thus obtained was evaluated for liquid crystal orientation, voltage holding ratio, and afterimage erasing time as shown in Example 1. The results are shown in Table 1.

Examples 5-6
A liquid crystal display element was produced in the same manner as in Example 4 using the liquid crystal aligning agent obtained in Synthesis Examples 2-3. With respect to each of the obtained liquid crystal display elements, as shown in Example 1, liquid crystal orientation, voltage holding ratio, and afterimage erasing time were evaluated. The results are shown in Table 1.

Example 7
The liquid crystal aligning agent (D) is applied to the transparent electrode surface of the glass substrate with a transparent electrode made of an ITO film using a spinner, dried by heating on a 300 ° C. hot plate for 30 minutes, and a coating film having a dry average film thickness of 700 Å Formed.
Using a Hg-Xe lamp on this coating film surface, a light having a wavelength shorter than 320 nm is cut by passing through a Pyrex (registered trademark) glass polarizing plate SPF-50C-32 (manufactured by Sigma Kogyo Co., Ltd.). Was irradiated with 1.0 J / cm ² from the normal direction of the substrate surface.

  Two substrates on which the above-mentioned irradiation-treated liquid crystal alignment film was formed were prepared, and an epoxy resin adhesive containing aluminum oxide spheres was applied to the outer edge of each substrate by a screen printing method. Were laminated so that the directions of the polarization planes of the ultraviolet rays irradiated through the gaps were parallel to each other, the outer edges were brought into contact with each other, and the adhesive was cured. The cell gap defined by the adhesive on the surface and outer edge of the substrate is filled with nematic liquid crystal (MLC-6221, manufactured by Merck & Co.), and then the injection hole is sealed with an epoxy adhesive. A display element was produced.

  Each liquid crystal display element thus obtained was evaluated for liquid crystal orientation, voltage holding ratio, and afterimage erasing time as shown in Example 1. The results are shown in Table 1.

Comparative Example 1
The liquid crystal aligning agent (E) obtained in Comparative Synthesis Example 1 was applied to the transparent electrode surface of a glass substrate with a transparent electrode made of an ITO film using a spinner, dried on a hot plate at 200 ° C. for 20 minutes, and dried. A coating film having an average film thickness of 600 Å was formed.

  A rubbing machine having a roll in which a rayon cloth was wound around this coating film was rubbed at a roll rotation speed of 400 rpm, a stage moving speed of 30 mm / second, and a hair foot indentation length of 0.4 mm. Each liquid crystal display element thus obtained was evaluated for liquid crystal orientation, voltage holding ratio, and afterimage erasing time as shown in Example 1. The results are shown in Table 1.

Claims (12)

(I) The following formula (1)
Si (OR ¹ ) ₄ (1)
Here, R ¹ is a hydrogen atom, a fluorine atom or a monovalent organic group.
A silicon compound represented by the following formula (2)
RSi (OR ² ) ₃ (2)
Where R is a monovalent organic group and R ² is a hydrogen atom, a fluorine atom or a monovalent organic group.
And (II) the following formula (3):

Wherein R ³ is a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group or a t-butyl group, m is 0 or 1, and n is 1, 2 or 3. is there,
The liquid crystal aligning agent characterized by containing the solvent represented by these. The silicon compound represented by the above formula (2) is
(A) R in the above formula (2) may be substituted with a substituent selected from the group consisting of an amino group, a glycidoxy group and trifluoromethyl, an alkyl group having 1 to 4 carbon atoms, a vinyl group or phenyl A silicon compound as a group, and (B) R in the above formula (2) is
(A) a linear alkyl group having 16 or more carbon atoms,
(A) a monovalent organic group which may be substituted and has at least one norbornane ring;
(C) a monovalent organic group which may be substituted and has at least one steroid skeleton,
(D) a monovalent organic group having an aromatic ring having a substituent selected from the group consisting of a fluorine atom, a trifluoromethyl group and a trifluoromethoxy group, or (e) a cinnamoyl group or a chalconyl group The liquid crystal aligning agent according to claim 1, wherein the liquid crystal aligning agent is at least one selected from the group consisting of a photosensitive group as a group and a silicon compound as a group. The (a) monovalent organic group which may be substituted and has at least one norbornane ring is represented by the following formulas (4) to (16);

The liquid crystal aligning agent of Claim 2 which is either group represented by each of these. The monovalent organic group which may be substituted and has at least one steroid skeleton is represented by the following formulas (17) to (26);

The liquid crystal aligning agent of Claim 2 which is either group represented by each of these. (E) a monovalent organic group having an aromatic ring having a substituent selected from the group consisting of a fluorine atom, a trifluoromethyl group and a trifluoromethoxy group and having a carbon number of 8 or more is represented by the following formulas (27) to ( 30);

The liquid crystal aligning agent of Claim 2 which is either group represented by each of these. The liquid crystal aligning agent according to claim 2, wherein the compound represented by the formula (2) is a combination of a silicon compound (A) and a silicon compound (B). The liquid crystal aligning agent of Claim 1 which the compound represented by said Formula (2) occupies 1-50 mol% in which R is a photosensitive group (e) in Formula (2). A liquid crystal alignment film is formed, comprising: a step of applying the liquid crystal aligning agent according to claim 1 to a substrate; and a step of heating the applied substrate to cure the coating film. Method. A method for forming a liquid crystal alignment film with a controlled liquid crystal alignment angle, wherein a rubbing treatment is performed on the film surface of the liquid crystal alignment film according to claim 8. The surface of the liquid crystal alignment film according to claim 8 is selected from the group consisting of electromagnetic radiation, ion beam, neutral atom beam, electron beam, molecular beam and elementary particle beam selected from the group consisting of X-rays and ultraviolet rays. A method of forming a liquid crystal alignment film with a controlled liquid crystal alignment angle, characterized by performing irradiation with a particle beam or both of these electromagnetic radiation and particle beam. The liquid crystal aligning film manufactured by the method in any one of Claims 8-10. A liquid crystal display element comprising the liquid crystal alignment film according to claim 11.