TW200537211A - Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element - Google Patents

Abstract

The present invention is to provide a liquid crystal alignment agent which prevents the deterioration of display, has a good residual image property even after being long-time driven, will not reduce the capability of aligning a liquid crystal, and may form a liquid crystal film having litter decrease in voltage retentivity due to light and heat. A liquid crystal alignment agent composition comprises a reaction product of a tetra-functional silicon compound such as a tetraalkyl silane, a tri-functional silicon compound such as a trialkyl silane and 0.8 to 3.0 moles of water per mole of a functional group such as an alkoxy group, and a glycol ether-based solvent.

Description

200537211 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element. More specifically, the present invention relates to a liquid crystal alignment layer, a liquid crystal alignment agent capable of forming the liquid crystal alignment layer, and a liquid crystal. Display elements, in which the liquid crystal alignment layer has excellent liquid crystal alignment, and does not damage electrical characteristics such as voltage residual rate under the harsh environment of light and high temperature or after long-term driving, and it is also difficult to produce residues while maintaining a good liquid crystal alignment state. Image development. [Background Art] At present, known liquid crystal display elements include a TN type liquid crystal display element having a TN type (twisted nematic) liquid crystal cell, and the element forms a polyamic acid and a polyimide on a surface of a substrate provided with a transparent conductive film. A liquid crystal alignment film such as fluorene imine is used as a substrate of a liquid crystal display element. Two substrates are disposed opposite to each other, and a nematic liquid crystal layer having positive dielectric anisotropy is formed in the gap to form a unit cell of a sandwich structure. The long axis is continuously twisted 90 degrees from one substrate to another. In addition, STN (Super Twisted Nematic) type liquid crystal display elements capable of achieving a %% higher contrast than TN type liquid crystal display elements and IPS (in-plane switching) type liquid crystal display elements and VA (vertical alignment) with less viewing angle dependence are being developed. Type liquid crystal display element. The operating principles of such various liquid crystal display elements are classified into a transmissive type and a reflective type. When a transmissive liquid crystal display element is driven, the display uses a change in the transmitted light intensity of the light source for the back surface light on the back of the element. Reflective liquid crystal display elements do not use a light source for backlighting. When the element is driven, changes in the reflection intensity of light such as sunlight 200537211 are used to display. Because it consumes less power than the transmissive type, it is considered to be outdoor. Use is particularly advantageous. In a transmissive liquid crystal display element, the liquid crystal alignment film is always irradiated with light from a back light source. Especially in commercial and recent home theater applications where liquid crystal projectors are in high demand, light sources such as metal halide lamps with very high illumination intensity are used. The reflective liquid crystal display element is highly likely to be used outdoors. In this case, sunlight containing strong ultraviolet light is used as a light source. In addition, when the reflective type is used, in principle, the distance through which light passes through the inside of the element is longer than that of the transmissive type.

In the manufacturing process of liquid crystal display elements, from the perspective of shortening the manufacturing process and improving productivity, the preferred method is to use the ODF (One)

Drop Fill) method. The ODF method is different from the conventional method of injecting liquid crystal into an empty liquid crystal cell assembled with a thermosetting sealant in advance. After applying a UV-curable sealant to a necessary portion of a single-sided substrate coated with a liquid crystal alignment film, the ODF method is applied to the necessary portion. The liquid crystal is dropped, and then another substrate is bonded, and then the entire ultraviolet light is irradiated to cure the sealant to make a liquid crystal cell. The intensity of the ultraviolet light irradiated at this time is usually several joules / cm2. That is, in the manufacturing process of the liquid crystal display element, the liquid% crystal alignment film and the liquid crystal are simultaneously irradiated with such strong ultraviolet light. When a transmissive liquid crystal display element is used, it is considered that the temperature of the liquid crystal display element system itself may increase during driving with high intensity light irradiation. In addition, as liquid crystal display devices become more versatile, use and installation environments at temperatures higher than normal room temperature, such as outdoor use or installation in private cars in parking lots, are also considered. With this type of liquid crystal display element, along with its high performance and versatility, there is a need for electrical characteristics such as liquid crystal alignment and voltage residual rate after being exposed to the harsh environment of light and heat or after being driven for a long time. 200537211 It has better image characteristics than existing devices. As materials for the liquid crystal alignment film constituting the liquid crystal display device, resins such as polyimide, polyimide, and polyester are known according to the prior art. In particular, polyimide has been used in many liquid crystal display elements because of its excellent physical properties in resins in terms of heat resistance, affinity with liquid crystals, and mechanical strength. However, in recent years, liquid crystal display elements have been developed with high performance and versatility. The probability of setting and using in the above-mentioned high-temperature environment and harsh environment of light is increasing, and further shorten the process and increase production in the manufacturing process. On the other hand, the life of the liquid crystal display element is required to be longer. At the same time, surface defects or afterimages are not allowed due to insufficient resistance to high temperature environments and light that have been allowed in the past. Therefore, the polyamidic acid and polyimide organic resins conventionally used as liquid crystal alignment films have insufficient resistance to light and heat. Therefore, there is a need for a new material that does not reduce the ability of a liquid crystal display element to uniformly align liquid crystals in a plane and has good resistance to light and heat. Japanese Patent Application Laid-Open No. 9-281502 discloses a vertical alignment film which is obtained by allowing a silicon compound (A) containing four alkoxy groups such as tetraethoxysilane and 3 An alkoxy silicon compound (B) is heated in an alcohol solvent in the presence of an oxalic acid catalyst at 50 ° C to 180t to form a solution of (A) and (B) co-condensation polysiloxane. As a coating solution, this was coated on the surface of an electrode substrate, and the obtained coating film was prepared by thermal curing at 80 to 400 ° C. This bulletin further explains that the vertical alignment film sag 200537211 is excellent in direct alignment, reproducibility, heat resistance and uniformity, and is also excellent in the stability of the coating liquid. However, such a vertical alignment film or a method of forming the same is not yet perfect. Regarding the vertical alignment film described in Japanese Patent Application Laid-Open No. 9-28 1 502, unreacted siloxy groups may remain in the obtained coating film. The unreacted siloxy group is unstable, and the trace moisture contained in the liquid crystal or the moisture brought by the liquid crystal cell sealant hydrolyzes the siloxy group to generate alcohol molecules, which diffuse into the liquid crystal, resulting in poor display. Wait. [Summary of the Invention] The present invention is made in view of the above-mentioned circumstances, and an object of the present invention is to provide a liquid crystal alignment agent, which undergoes sufficient hydrolysis reaction to convert 99% or more of the siloxane group, Therefore, it is possible to form a liquid crystal alignment film that prevents such poor display, has good afterimage characteristics after long-time driving, does not reduce the ability to align liquid crystals, and has a small reduction in light and thermal voltage residual ratios. Another object of the present invention is to provide a liquid crystal alignment film using the liquid crystal alignment agent of the present invention and having excellent properties as described above, and a method for manufacturing the same. Another object of the present invention is to provide a liquid crystal display element having the liquid crystal alignment film of the present invention. Other objects and advantages of the present invention will be apparent from the following description. According to the present invention, the above-mentioned objects and advantages of the present invention are first achieved by a liquid crystal alignment agent, which is characterized by including (I) a reaction product of specific two siloxanes and water and (II) The solvent, specifically, includes (I) a silicon compound represented by the following formula (1), a reaction product of a silicon compound 200537211 represented by the following formula (2), and water (hereinafter referred to as "reaction product (1 ) ,,) and (II) the solvent represented by the formula (3),

Si (〇R1) 4 ........ (1) where R1 is a hydrogen atom, a fluorine atom or a monovalent organic group, RSi (OR2) 3 ... ............... (2) where R is a monovalent organic group, and R2 is a hydrogen atom, a fluorine atom, or a monovalent organic group,

R30 (CH) m (CH2) nOH .... (3) where R3 is methyl, ethyl, n-propyl, isopropyl, n-butyl or third butyl, m Is 0 or 1, and n is 1, 2 or 3. According to the present invention, the above-mentioned objects and advantages of the present invention are secondly achieved by a method for forming a liquid crystal alignment film, which method is characterized by including a step of applying the liquid crystal alignment film of the present invention to a substrate and heating the coated substrate so that ^ The step of curing the coating film. According to the present invention, the above-mentioned objects and advantages of the present invention are thirdly achieved by the liquid crystal alignment film formed by the method of the present invention. According to the present invention, the above-mentioned objects and advantages of the present invention are finally achieved by a liquid crystal display device having a liquid crystal alignment film of the present invention. According to the present invention, compared with existing materials, by using a liquid crystal alignment agent using a silicon-based material, it is possible to manufacture a liquid crystal display element that is subjected to a harsh environment in which light irradiation and heat treatment are performed, or for a long period of time. -After 200537211 driving, its excellent liquid crystal alignment, voltage retention and afterimage characteristics will not be greatly reduced. The liquid crystal display element produced by using the liquid crystal alignment agent of the present invention can be applied to not only TN type and STN type liquid crystal display elements, but also SH (super vertical alignment) type and IPS (in-plane switching) depending on the liquid crystal used. Type, VA (vertical alignment) type, ferroelectric and antiferroelectric liquid crystal display elements, etc. And 'a liquid crystal display element having an alignment film formed using the liquid crystal alignment agent of the present invention has excellent liquid crystal alignment and reliability, and can be effectively used in various devices, such as desktop computers, watches, wall clocks, and counting displays. , Word processor, personal computer, LCD TV, LCD TV, electronic paper and other display devices. [Embodiment] Liquid crystal alignment agent The liquid crystal alignment agent of the present invention includes (I) a reaction product (1) and (II) a solvent. (I) The reaction product (1) is a silicon compound represented by the following formula (1) (hereinafter referred to as "silicon compound (1)"), and a silicon compound represented by the following formula (2) (hereinafter referred to as "silicon compound ( 2) ") and the reaction product of water

Si (〇R1) 4 ........ (1) where R1 is a hydrogen atom, a fluorine atom or a monovalent organic group, RSi (OR2) 3 ... ......... (2) where R is a monovalent organic group, and R2 is a hydrogen atom, a fluorine atom, or a monovalent organic group. Examples of the monovalent organic group of R1 in the formula (1) include an alkyl group, an -10-200537211 aryl group, an allyl group, a fluorenyl group, and an epoxypropyl group. Examples of the alkyl group include methyl, ethyl, propyl, and butyl. Alkyl groups having 1 to 5 carbon atoms are preferred. These alkyl groups may be chained or branched, and hydrogen atoms may be substituted with fluorine atoms or the like. Examples of the aryl group include phenyl, naphthyl, tolyl, ethylphenyl, chlorophenyl, bromophenyl, and fluorophenyl. Examples of the fluorenyl group include ethyl fluorenyl, benzyl fluorenyl, methyl fluorenyl, and propyl fluorenyl compounds (1). Specific examples include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, Tetraisopropoxysilane, tetra-n-butoxysilane, tetra-second butoxysilane, tetra-third butoxysilane, tetraphenoxysilane, tetraethoxysilane, tetraglycidoxysilane Wait. They can be used singly or in combination of two or more. In the formula (2), R is a monovalent organic group, and R2 is a hydrogen atom, a fluorine atom, or a monovalent organic group. Examples of the monovalent organic group for R2 include the same groups as for R1. In addition, as the monovalent organic group of R, for example, a C1 to C4 alkyl group, a vinyl group, and a phenyl group which may be substituted with an amine group, a glycidyloxy group, or a trifluoromethyl group;% of carbon atoms is 16 or The above straight-chain alkyl group; a monovalent organic group which may be substituted and have at least one probornyl ring; a monovalent organic group which may be substituted and have at least one steroid skeleton; having a fluorine atom, a trifluoromethyl group or A trifluoromethoxy substituent is a monovalent group having an aromatic ring and having 8 or more carbon atoms; a photosensitive group having a cinnamyl group or a chalcone group; and the like. Specific examples of the compound in which R is a C1-4 alkyl group, a vinyl group, and a phenyl group (hereinafter referred to as a compound (A)) which may be optionally substituted with an amine group, a glycidoxy group, or a trifluoromethyl group include methyl groups. Trimethoxysilane, methyltriethoxysilane, methyltri-11 · 200537211 n-propoxysilane, methyltriisopropoxysilane, methyltri-n-butoxysilane, methyltributane Oxysilane, methyl terbutoxysilane, methyltriphenoxysilane, ethylmethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltriisopropyl Oxysilane, ethyltri-n-butoxysilane, ethyltri-second-butoxysilane, ethyltri-third-butoxysilane, ethyltriphenoxysilane, vinyltrimethoxysilane, vinyl Triethoxysilane, vinyltri-n-propoxysilane, vinyltriisopropylsilane, vinyltri-n-butoxysilane, vinyltri-second-butoxysilane, vinyltri-third φbutoxy Silane, vinyltriphenoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltri-n-methoxysilane Oxysilane, n-propyltriisopropoxysilane, n-propyltri-n-butoxysilane, n-propyltri-second-butoxysilane, n-propyl-third-butoxysilane, n-propyltriphenyl Oxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, isopropyltri-n-propoxysilane, isopropyltriisopropoxysilane, isopropyltri-n-butoxysilane , Isopropyltributoxysilane, isopropyltributoxysilane, isopropyltriphenoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane,% n Butyltri-n-propoxysilane, n-butyltriisopropoxysilane, n-butyltri-n-butoxysilane, n-butyl-tributoxysilane, n-butyl third-butoxysilane, N-butyltriphenoxysilane, second butyltrimethoxysilane, second butyl-i-triethoxysilane, second butyltri-n-propoxysilane, second butyltriisopropyl Oxysilane, second butyl tri-n-butoxysilane, second butyl tri-second butoxy silane, second butyl third butoxy silane, second butyl triphenoxy silane, first Tributyltrimethoxysilane, tertiary butyltriethoxysilane, tertiary butyltri-n-propoxysilane, tertiary butyltriisopropoxysilane, -12- 200537211 Butoxysilane, third butyltributoxysilane, third butyltributoxysilane, third butyltriphenoxysilane, phenyltrimethoxysilane, phenyltriethoxy Silane, phenyltri-n-propoxysilane, phenyltriisopropoxysilane, phenyltri-n-butoxysilane, phenyltri-n-butoxysilane, phenyl-tertiary-butoxysilane, benzene Triphenyloxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-epoxypropylene Oxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-trifluoropropyltrimethoxy0-silane, γ-trifluoropropyltriethoxysilane, and the like. Among them, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, and the like are preferred. In addition, in formula (2), R is (a) a straight-chain alkyl group having 16 or more carbon atoms; (b) a monovalent organic group which may be substituted and has at least one orbornbornane ring; (c) may A substituted monovalent organic group having at least one steroid skeleton;

(d) a monovalent group having an aromatic ring having a substituent selected from a fluorine atom, a trifluoromethyl group, and a trifluoromethoxy group and having 8 or more carbon atoms; or (e) a cinnamyl group or Examples of the ketone group-based photosensitive group compound (hereinafter referred to as compound (B)) include cetyltrimethoxysilane, heptadecyltrimethoxysilane, octadecyltrimethoxysilane, and deca Nonadecyltrimethoxysilane, hexadecyltriethoxysilane, heptadecyltriethoxysilane, octadecyltriethoxysilane, nonadecanyltriethoxysilane, etc. (above Is a compound in which R is (a)); 200537211 R is a compound in which a structure selected from the following formulae (4) to (16) (a compound in which R is (b)) ·,

ch3 ch3 c-c ch3 (4) coo —c ~ ch3

(5) ch3 h2c--c-ch3 ch3

(6) Fn rF F 〇wCF2CF2CF3

(7) CH3 H 2〇 " * C Hg

SiH (OCH2CH3) 2

F F

cf3 ch3 coo- (9) -c-ch3 ch3

COO-C-CH3 ch3

(11) H2C-C-OH C I cf3

(12) F 〇 " CF2CF2CF2CH2〇H

F OH cf3

ό (15) F- ^ pf-CHa F CH,

(16)

FT 「F

F 〇, CF2CF2CH2OH% -14-200537211 R is a compound having a structure selected from the following formulae (17) to (2 6) (R is a compound of (c));

HaC H3C CH- (CH2) 3CH (CHs) 2 H3CH3CH- (CH2) 3CH (CH3) 2 / >

(25)

(26) -15- 200537211 R is a compound having a structure selected from the following formulae (27) to (30) (R is a compound of (d));

P7) (28)》 -〇Ό " 〇 ^ Ό · " ocf3 (29) (30) 4'-chalcone-based trimethoxysilane, 4'-chalcone-based triethoxysilane, cinnamon Trimethoxysilyl, cinnamyltriethoxysilane, cinnamyltrimethoxysilane, cinnamyltrimethoxysilane (the above are compounds where R is (0), etc.).

They can be used singly or in combination of two or more kinds. As the compound (2), one or more kinds of the compound (A) and the compound (B) are preferably selected and used in combination. The use ratio of the compound (1) and the compound (2) is preferably 10 to 99 mol%, more preferably 50 to 99 mol relative to the total amount of the compounds (丨) and (2). %. The reaction product (1) can be prepared by reacting the compound (1), the compound (2) with water, and 'partially condensing it' by hydrolysis. In order to hydrolyze and partially condense the compound (丨) and the compound 200537211 (2), it is preferable to use per mole of siloxane bond (the sum of -OR1 of formula (1) and -OR2 of formula (2)) ^ ~丨 · 5 Mol water. When the amount of water reaches 1 mol or more, the possibility that the siloxane bond remains unreacted decreases, there is no possibility that the uniformity of the coating film is reduced, and the possibility that the storage stability of the liquid crystal alignment agent is also reduced, Therefore, it is preferable. Water may be added intermittently or continuously to an organic solvent in which the compound (1) and the compound (2) are dissolved. In this case, a reaction catalyst may be used. When a catalyst is used, the catalyst may be added to an organic solvent in advance, or it may be dissolved or dispersed in water when water is added. The reaction temperature at this time is preferably 0 to 100 ° C, and more preferably 15 to 80 ° Co. The organic solvent used when the compound (1) and the compound (2) are hydrolyzed and partially condensed. At least one of an alcohol solvent, a ketone solvent, an amidine solvent, an ester solvent, and an aprotic solvent. Here, examples of the alcohol solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, second butanol, third butanol, n-pentanol, isoamyl alcohol, and 2- Methyl butanol, second pentanol, third pentanol, 3-methoxy% butanol, n-hexanol, 2-methylpentanol, second hexanol, 2-ethylbutanol, second heptanol , 3-heptanol, n-octanol, 2-ethylhexanol, second octanol, n-nonanol, 2,6-dimethyl-4-heptanol, n-decanol, twenty-first alcohol, Trimethylnonanol, twenty-fourth alcohol, twenty-seven alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, diacetone Monohydric alcohol solvents such as alcohols; ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2,4-pentanediol, 2.methyl 2,4-pentanediol, 2,5-hexanediol , 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol and other polyhydric alcohol solvents; -17- 200537211 ethylene glycol Monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monobenzene 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, Polyol partial ether solvents such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and dipropylene glycol monopropyl ether; and many more. These alcohol solvents may be used singly or in combination of two or more kinds.

Examples of ketone solvents include acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone, and ethyl. N-butyl ketone, methyl n-hexyl ketone, diisobutyl ketone, trimethyl nonanone, cyclohexanone, 2-hexanone, methyl cyclohexanone, 2,4-pentanedione, acetone, In addition to acetophenone and acetophenone, acetone, 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 -Heptanediones, 1,1,1,5,5,5,5-hexafluoro-2,4-heptanedione, etc. These ketone solvents may be used singly or in combination of two or more kinds. Examples of the amide-based solvents include formamide, N-methylformamide, N, N-dimethylformamide, N-ethylformamide, and N, N-diethylformamide. , Acetamide, N-methylacetamide, N, N-dimethylacetamide, N-ethylacetamide, N, N-diethylacetamide, N-methylpropylamine , N-methylpyrrolidone, N-formamylmorpholine, N-formamylpiperidine, N-formamylpyrrolidine, N-ethylamylmorpholine, N-acetamylpiperidine, N-ethyl Fluorenyl pyrrolidine and the like. These amidine solvents may be used singly or in combination of two or more kinds. -18- 200537211 Examples of the ester solvent include diethyl carbonate, ethyl carbonate, propylene carbonate, diethyl carbonate, methyl acetate, ethyl acetate, lactone, 7-valerolactone, and n-acetate Propyl ester, isopropyl acetate, n-butyl acetate, isobutyl acetate, second butyl acetate, n-amyl acetate, second amyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl ethyl acetate, ethyl ethyl acetate, Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether Diethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, ethylene glycol diacetate, methoxytriethylene glycol acetate, propionic acid Ethyl ester, n-butyl propionate, isoamyl propionate, diethyl oxalate, di-n-butyl oxalate Esters, methyl lactate, ethyl lactate, n-butyl lactate, n-pentyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate, and the like. These ester solvents may be used singly or in combination of two or more kinds.

Examples of the aprotic solvent include acetonitrile, dimethyl sulfoxide, N, N, N'N'-tetraethylsulfonamide, trimethylamine hexamethylphosphate, N-methylmorpholine, and N-formaldehyde. N-methylpyrrole, N-ethylpyrrole, N-methyl-Δ3-pyrroline, N-methylpiperidine, N-ethylpiperidine, N, N-dimethylpiperidine, N-methylimidazole, N -Methyl-4-piperidone, N-methyl-2-piperidone, N-methyl-2-pyrrolidinone, ι, 3-dimethyl-2-imidazolinone, 1,3 · Dimethyltetrahydro-2 (1H) -pyrimidone and the like. Among them, particularly preferred are polyhydric alcohol solvents, polyhydric alcohol partial ether solvents, and ester solvents. In addition, in the hydrolysis and partial condensation reaction 200537211 of the compound (1) and the compound (2), a catalyst is preferably used. Examples of such a catalyst include the following metal adducts, organic acids, inorganic acids, organic bases, and inorganic bases. Examples of metal adducts include triethoxy · mono (acetamidineacetone) titanium, tri-n-propoxy · mono (acetamidineacetone) titanium, triisopropoxy · mono (acetamidineacetone) titanium, Tri-n-butoxy • mono (acetamidineacetone) titanium, tri-second butoxy • titanium (acetamidineacetone) titanium, tri-tert-butoxy • mono (acetamidine-acetone) titanium, diethoxy • di (Ethyl Acetone) Titanium, Di-n-propoxy • Di (Ethyl Acetone) Titanium, Diisopropoxy • Di (Ethyl Acetone) Titanium, Di-N-butoxy • Di (Ethyl Acetone) Titanium, Two Second butoxy · φ titanium bis (acetamidineacetone) titanium, second third butoxy • titanium bis (acetamidine acetone) titanium, monoethoxy • tri (acetamidine acetone) titanium, mono-n-propoxy group · (Acetylacetone) titanium, monoisopropoxy • tris (acetamidoacetone) titanium, mono-n-butoxy • tris (acetamidoacetone) titanium, mono-butoxy • tris (acetamidoacetone) titanium, Mono-tertiary butoxy • titanium (acetamidineacetone) titanium, tetrakis (acetamidineacetone) titanium, triethoxy • mono (ethylacetonate) titanium, tri-n-propoxy • mono (ethylacetate) acetate Ester) titanium Triisopropoxy • mono (ethyl ethyl acetate) titanium, tri-n-butoxy · mono (ethyl ethyl acetate) titanium, tri-butoxy • mono (ethyl ethyl acetate) titanium,% Thirty-three butoxy • mono (ethyl acetate) titanium, diethoxy • di (ethyl acetate) titanium, di-n-propoxy • di (ethyl acetate) titanium, diiso Propoxy · titanium (ethyl acetate), di-n-butoxy • titanium (ethyl acetate), second butoxy • titanium (ethyl acetate), second third Butoxy • di (ethyl acetate) titanium, monoethoxy • tri (ethyl acetate) titanium, mono-n-propoxy · tri (ethyl acetate) titanium, monoisopropoxy • Titanium (ethyl acetate), mono-n-butoxy • Titanium (ethyl acetate), second butoxy • Titanium (ethyl acetate), third butoxy • Titanium (ethyl acetate), tetrakis (acetic acid acetate-20-200537211) tris (triacetone), propyltitanium (i) (ZKJ monoacid, ethyl methane ester (Z ethylenedione, etc.)酉 (Z ethanedioic acid, ethylene titanium 醯 i) ethyl Γν Monoacid 丨 Ethyl Acetyl Acetate Propionate Ethyl Titanium Admixture; Triethoxy • mono (acetamidineacetone) zirconium, Tri-n-propoxy • mono (acetamidineacetone) 鍩, Triisopropoxy • mono ( Acetylacetone) Zirconium, Tri-n-butoxy • mono (acetamidineacetone) Chromium, Tri-second butoxy • mono (acetamidine) pin, Third tertiary butoxy • mono (acetamidine) pin, Diethoxy • di (acetamidineacetone) pin, di-n-propoxy • di (acetamidineacetone) chromium, diisopropoxy • di (acetamidineacetone) chromium, di-n-butoxy • di (ethyl) φ 醯 Acetone) Zirconium, second and second butoxy • di (acetamidine acetone) pin, second and third butoxy · di (acetamidine acetone) zirconium, monoethoxy • tri (acetamidine acetone) hafnium, single N-propoxy · tri (acetamidineacetone) pin, monoisopropoxy • tri (acetamidineacetone) zirconium, mono-n-butoxy • tri (acetamidine) pin, single second butoxy • tri ( Acetylacetone) Zirconium, mono-tert-butoxy • tris (ethinylacetone) pin, tetra (ethinylacetone) pin, triethoxy • mono (ethylacetonate) zirconium, tri-n-propoxy group • Mono (acetic acid) (Ester) zirconium, triisopropoxy • mono (ethyl ethyl acetate) chromium, tri-n-butoxy · mono (ethyl ethyl acetate) chromium, tri-second butoxy • mono (ethyl ethyl acetate) ) 鍩,% Tri-tertiary butoxy • mono (ethyl acetate) zirconium, diethoxy • di (ethyl acetate) pin, di-n-propoxy • di (ethyl acetate) Chromium, diisopropoxy · di (ethyl acetate) pin, di-n-butoxy • di (ethyl acetate) pin, second second butoxy • di (ethyl acetate) pin , Second and third butoxy • di (ethyl acetoacetate) zirconium, monoethoxy • tri (ethyl acetoacetate) chromium, mono-n-propoxy · tri (ethyl acetoacetate) chromium, mono Isopropoxy • tris (ethyl acetate) 醯, mono-n-butoxy • tris (ethyl acetate) chromium, second butoxy • tri (ethyl acetate) pin, single Tributoxy • tris (ethylacetate) pin, tetrakis (ethylacetate 200537211 ethyl) zirconium, mono (ethylacetone) tris (ethylacetate) chromium, di (ethylacetone) di ( Ethyl Acetate) Zirconium Tris (acetyl acetone) mono (ethyl acetate-acetylamino) chromium chelates such as chromium; tris (acetyl acetone) Jin, tris (acetyl ethyl acetate) and the like Jin-Ming chelates; and the like. Examples of the organic acid include acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, caprylic acid, nonanoic acid, capric acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, Gallic acid, butyric acid, mellitic acid, arachidonic acid, φ 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 the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid. Examples of the organic base include pyridine, pyrrole, piperine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethyl mono% ethanolamine, monomethyl diethanolamine, and triethanolamine. , Diazabicyclooctane, diazabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, and the like. Examples of the inorganic base include amine, sodium hydroxide, potassium hydroxide, barium hydroxide, and calcium hydroxide. Among these catalysts, metal adducts, organic acids, and inorganic acids are preferred, and titanium adducts and organic acids are more preferred. They can be used singly or in combination of two or more kinds. The amount of the above-mentioned catalyst is preferably 0.001 to 10 parts by weight, and more preferably 100 parts by weight of the compound (丨) and the chemical compound 22-200537211 compound (2) (equivalent to the conversion of the fully hydrolyzed condensate). It is O.OOhi parts by weight. The liquid crystal alignment agent of the present invention is formed by dissolving or dispersing a reaction product (1) in an organic solvent. As the organic solvent, a solvent represented by the following formula (3) is used.

3 Η c I (3)

R30 (CH) m (CH2) n〇H Among them, R3 tributyl, m is this organic monomethyl ether, ethylene dipropylene glycol mono-n-propanol mono-n-butyl ether propylene glycol single third these solvents will not cause solid analysis Weak solvent. As such pentane, n-hexane, n-octane, benzene, toluene, dioxane, ethylbenzene, Ξ diethylbenzene, iso

Is methyl, ethyl, n-propyl, isopropyl, n-butyl or 0 or 1 and η is 1, 2 or 3. Specific examples of the solvent include ethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ether, ethylene glycol monoisopropyl ether, propylene glycol monoisopropyl ether, ethylene glycol, and propylene glycol monoethyl ether. N-butyl ether, ethylene glycol mono-third butyl ether, butyl ether. They can be used alone or in combination of two or more. In addition, within the range of the amount, specific examples of weak solvents that are difficult to dissolve the materials used can also be used, and examples include n-pentane, iso, isohexane, n-heptane, isoheptane, 2,2,4- Trimethylpentanectane, cyclohexane, methylcyclohexane, decane, biscene, toluene, mesitylene, indene, tetrahydronaphthalene, decahydronaphthalene, squalose trimethylbenzene, methyl ethyl Hydrocarbon solvents such as benzene, n-propylbenzene, cumene, butylbenzene, triethylbenzene, diisopropylbenzene, n-pentylnaphthalene, -23-200537211 trimethylbenzene; methanol, ethanol, N-propanol, isobutanol, second butanol, third butanol, n-pentylbutanol, second pentanol, third pentanol, 3-methoxymethylpentanol, second hexanol, 2 -Ethyl butanol, second octanol, 2-ethylhexanol, second octanol, second nonanol alcohol, n-decanol, twenty-first alkyl alcohol, trimethyl nonanol, twentieth Mono-alcohol solvents such as pentaalkyl alcohol, phenol, cyclohexanol, methyltrimethylcyclohexanol, benzyl alcohol, phenylmethyl methanol, and φ; ethylene glycol, 1,2-propanediol, pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanedione Polyethyl alcohol solvents such as 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, glycerol; acetone, methyl ketone, methyl n-butyl ketone, diethyl ketone , Methyl isoyl ketone, methyl amyl ketone, ethyl n-butyl ketone, methyl ketone, diisopropyl ketone, trimethyl nonanone, cyclopentanone, ketone, cycloheptanone, 2, 4- Glutaredione, acetone acetone,% solvents; diethyl ether, diisopropyl ether, di-n-propyl 3 di-n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, oxapentane, 4 -Methyldioxolane, dioxane, phenyl ether, diphenyl ether, tetrahydrofuran, 2-methyltetrahydrodiethyl carbonate, propylene carbonate, 1-butyrolactone, 1-pentylacetate, n-acetate Propyl, isopropyl acetate, butyl acetate, second butyl acetate, n-pentyl acetate, acetic acid: methoxybutyl, methylpentyl acetate, 2-ethyl alcohol, isopropyl alcohol, n-butyl Alcohol, isoamyl alcohol, 2-methyl butanol, n-hexanol, 2-heptanol, 3-heptanol, n-, 2,6 · dimethyl-4-heptanol, tetradecyl cyclohexanol , 3,3,5-diacetone alcohol, cresol 1,3-butanediol, 2,4-, 2,4-diheptane Ketone ethers such as alcohols, alcohols, triethylene glycol, tripropyl ethyl ketone, methyl n-propyl butyl ketone, methyl n-pentyl-n-hexyl ketone, dipropyl cyclohexanone, methyl cyclohexyl acetophenone, and fluorenone, Ether solvents such as di-n-butyl ether, 1,2-propylene oxide, dimethyl dioxane, and furan;: lactone, methyl acetate, n-butyl acid, isosecondyl acetate, acetic acid 3-butyl ester, 2-ethyl-24- 200537211 phenylhexyl acetate, benzyl acetate, n-hexyl acetate, cyclohexyl acetate, octyl acetate, amyl acetate, isoamyl acetate, methyl cyclohexyl acetate, N-nonyl acetate, methyl ethyl acetate, ethyl ethyl acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, acetic acid Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, ethylene glycol diacetate, methoxytriethylene glycol vinegar 0 acid esters, ethyl phenylacetate, methyl 3-methoxypropionate, ethyl triethoxypropionate, methyl propionate, ethyl propionate, n-propyl propionate, isopropyl propionate, N-butyl propionate, isobutyl propionate, isoamyl propionate, benzyl propionate, ethoxyethyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, Lactic acid

Propyl, 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, diphthalate Ester solvents such as methyl ester, diethyl phthalate, ethyl pyruvate; N · methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamidine Amines, N-methylacetamide, N, N-di-N-methylpyrrolidone, and other amine solvents such as hydrogen thiophene, dimethylarsine, cyclobutane, methylacetamide, and N-methylpropylamine Sulfur-containing solvents, such as methyl sulfide, ethyl sulfide, thiophene, tetra-I, 3-propane sultone, etc., m 2 plumes W to π i "return part by weight of the agent represented by the above formula (3) ' Using, for example, 50 parts by weight or less, preferably 30 parts by weight, or 25-200537211, the liquid crystal alignment agent of the present invention may further add the following diketone: 1. one or two or more kinds of acetone, 2 , 4-hexanedione, 2,4-heptane , 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. To the liquid crystal alignment agent obtained by the present invention, components such as colloidal silica, colloidal alumina, organic polymer, surfactant, and the like may be further added. The term "colloidal silica" refers to, for example, dispersion of high-purity silica. The dispersion in the above-mentioned hydrophilic organic solvent is usually a dispersion having an average particle size of 5 to 30 μm, preferably 10 to 2 Om / x, and a solid content concentration of 10 to 40% by weight. Examples of colloidal silica include methanol silica sol and isopropanol silica sol manufactured by Nissan Chemical Industry Co., Ltd .; OSCAL manufactured by Catalytic Chemical Industry Co., Ltd., and the like. Examples of colloidal alumina include Nissan Chemical Industry Co., Ltd. Alumina sol 520, alumina sol 100, alumina sol 200; alumina transparent sol, alumina sol 10, alumina sol, etc. manufactured by Kawasaki Precision Chemical Co., Ltd. Organic polymerization Examples thereof include a compound having a polyalkylene oxide structure, a compound having a sugar chain structure, a vinylamine polymer, a (meth) acrylate compound, an aromatic vinyl compound, a dendrimer, a polyimide, a polymer Phenylamine, polypropyne, polyamidoamine, polyquinoxaline, polyoxadiazole, fluoropolymer, etc. Examples of the surfactant include nonionic surfactants, anionic surfactants, and cationic surfactants. , Amphoteric surfactants, etc. In the step of -26- 200537211, polysiloxane surfactants, polyalkylene oxide surfactants, fluorine-containing surfactants, etc. can be listed. In addition, from the perspective of improving the adhesion to the substrate surface The liquid crystal alignment agent of the present invention may further include a compound containing a functional silane or a compound containing an epoxy group. Examples of such functional silane-containing compounds include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, and 2-aminopropyl Triethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyl 0 methyldi Methoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl -3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1 , 4,7-tridecane, 10-triethoxysilyl-1,4,7-tridecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-tri Ethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane N-phenyl-3-aminopropyl% trimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-di (hydroxyethyl) -3-aminopropyl Top three Silane-yl, N- bis (hydroxyethyl) -3-aminopropyl triethoxy silane-like. Examples of the epoxy group-containing compound preferably 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, glycerol diglycidyl ether, 2,2-dibromo neopentyl glycol diglycidyl ether, 1,3,5,6- Tetraglycidyl-2,4-hexanediol; ^, 1 ^, 1 ^ ', \'-tetraglycidyl-m-xylylene-27- 200537211 amine, 1,3-bis (N, N-di-glycidyl Glycerylaminomethyl) cyclohexane, N, N, N ', N, -tetraglycidyl-4,4'-diaminodiphenylphosphonium and the like. The ratio of the reaction product (1) to the solvent in the liquid crystal alignment agent of the present invention is selected from the aspects of viscosity and volatility. The silicon atoms contained in the reaction product (1) are converted into silicon dioxide, and the liquid crystal alignment agent reacts. The ratio (solid content concentration) of the product (1) is such that the concentration of silicon dioxide is preferably from 0.001 to 70% by weight, more preferably from 0.05 to 60% by weight, even more preferably from 1 to 30% by weight. ratio. As described below, the liquid crystal alignment agent of the present invention is preferably applied to a substrate by, for example, a roll coating method, a spin coating method, a printing method, and the like, and then heated and dried to form a coating film as a liquid crystal alignment film. When the solid content concentration is less than 0.01% by weight, the film thickness of the coating film becomes too small, and a good liquid crystal alignment film may not be obtained. When the solid concentration exceeds 70% by weight, the film thickness of the coating film becomes excessively large. In some cases, it may be difficult to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent may increase, resulting in poor coating performance. The ratio of the solvent (II) in the liquid crystal alignment agent of the present invention is preferably 1 to 100% by weight, more preferably 30 to 100% by weight, and the percentage is preferably 70 to 100%. 100% by weight. By using the liquid crystal alignment agent of the present invention, a liquid crystal display element can be produced by, for example, the following method. (1) The liquid crystal alignment agent of the present invention is applied to a coated body provided with a patterned transparent conductive film by a method such as a roll coating method, a spin coating method, a printing method, or an inkjet method. The inert gas film is isotropically coated with argon, the hot gas is added with helium and hydrogen, and the nitrogen is mixed into the inlet to be coated so that it can pass through the body. In order to perform the above steps, the walking board is heated into the atmosphere of Kigali and He-28-28200537211. Here, the substrate can be made of glass such as float glass, soda lime glass; plastics such as polyethylene terephthalate, polybutylene terephthalate, polyether, polymethyl methacrylate, polycarbonate, etc. Making a transparent substrate. As the transparent conductive film provided on one surface of the substrate, an NES A film (registered trademark of PPG, USA) made of tin oxide (Sn02), an ITO film made of indium oxide-tin oxide (In203-Sn02), or the like can be used. These transparent conductive films can be formed by a photolithography method and a method using a mask in advance. In the application of the liquid crystal alignment agent, in order to improve the adhesion between the substrate surface and the transparent conductive film and the coating film, it is also possible to apply a functional silane-containing compound, a functional titanium-containing compound, etc. on the surface of the substrate in advance. After the liquid crystal alignment agent is applied, the heating temperature is a temperature that does not cause deformation of the base material, preferably 20 to 300 ° C, and 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 heating plate. The thickness of the coating film to be formed is preferably 〇 "～;!, More preferably 0.005 to 0.5 / xm. (2) In addition, the surface of the formed coating film is subjected to surface abrasion to control the alignment angle of the liquid crystal In addition, through the step of electromagnetic radiation and particle beam hitting t surface, the alignment angle of liquid crystal can also be controlled. The particle beam used here can be ion beam, neutral atom beam, electron beam, molecular beam, elementary particle beam, etc. Irradiation energy The irradiation angle and irradiation time can be appropriately adjusted according to the type of liquid crystal alignment film and the pre-tilt angle given. When using an ion beam, the ion type of the ion beam is preferably nitrogen, helium, argon, neon, etc. An ion beam of an inert gas. In addition, it is preferable to provide electrons to neutralize ions during or after the ion beam irradiation. A method of using an ion beam to make the irradiation surface have liquid crystal alignment properties is disclosed in JP-29-200537211, Hei 1 1 -2 7 1 7 7 3 etc. have been disclosed. However, in this publication, a covalent bonding material such as hydrogenated diamond-like carbon (DLC) is used as the alignment for forming the liquid crystal. The material of the layer is a liquid crystal alignment layer formed by a non-aqueous gas environment adhesion method such as chemical vapor adhesion, instead of coating by a roll coating method, a spin coating method, a printing method, an inkjet method, or the like widely used as a conventional liquid crystal alignment layer forming method. The steps are targeted. Since the liquid crystal alignment agent of the present invention is provided in the form of a solution, it has the advantage of being able to directly use an existing device for coating liquid crystal alignment films such as a spin coating method and a printing method.

Specific examples of the liquid crystal alignment agent effective for ion beams include JP-A-8-3 139 No. 12 using polyfluoric acid or soluble polyimide in the liquid crystal alignment agent, JP-A-8-313913, and Kaiping Publication No. 8-313916 and JP-A Publication No. 1 1 -23 7 63 8. For the liquid crystal alignment and afterimage characteristics after being subjected to the harsh environment of light and heat as described above or after prolonged driving, in the present invention, by using a silicon-based material, it is possible to achieve the advantages of existing polyamic acid or soluble polyimide. Has good performance. A method of making an irradiated surface have liquid crystal alignment performance using an electron beam is disclosed in Japanese Patent Application Laid-Open No. 06-130389 and the like. However, since this publication also uses conventional polyamidic acid or soluble polyimide as a substance for forming a liquid crystal alignment layer, it is difficult to form a material having a small reduction in light and thermal voltage residual ratio as disclosed in the present invention. Liquid crystal alignment layer. A method of aligning the irradiation surface using a molecular beam, a neutral atomic beam, an elementary particle beam, and electromagnetic radiation has been disclosed in Japanese Patent Application Laid-Open No. 10-96928 and the like. However, since the existing polyfluorene imide is also used as a substance for forming the liquid crystal alignment layer in this publication, it is difficult to form a liquid crystal alignment having a low reduction in light and thermal voltage residual ratio as disclosed in the present invention. Floor. In the use of the liquid crystal alignment agent according to the present invention, 1.0 to 50 mole% of the entire compound (2) is a compound in which R2 is a photosensitive group such as a chalcone group or a cinnamyl group. Radiation can control the alignment angle of the liquid crystal. In addition, the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention is irradiated with ultraviolet rays, for example, as disclosed in Japanese Patent Application Laid-Open No. 6-222366 or Japanese Patent Application Laid-Open No. 6-281937, or Japanese Patent Application No. 10-96928 0 A method for selectively selectively irradiating an ion beam on a surface of a liquid crystal alignment film through multiple steps disclosed in the gazette, or a structure in which an alignment control method is provided as disclosed in Japanese Patent Application Laid-Open No. 1 1-242225 can improve the liquid crystal. Field of view characteristics of the display element. (3) Two substrates for forming a liquid crystal alignment film as described above are manufactured, and a thermosetting sealant is applied to the peripheral edge portion of one of the substrates in an appropriate pattern. The liquid crystal alignment directions in the respective liquid crystal alignment films are made vertical or counter-parallel, and the two substrates are placed opposite each other through a gap (cell gap). After the two substrates are bonded, the sealant is cured by heating. Liquid crystal is injected into the gap between the substrate surface and the cell space divided by the sealant, and the injection hole is closed to form a liquid crystal cell. From the step of bonding two substrates to the liquid crystal injection, a liquid crystal drop method, namely, an ODF (One Drop Fill) method can be used. A single substrate coated with a liquid crystal alignment film and provided with the above-mentioned liquid crystal alignment performance is coated with an ultraviolet curable sealant in an appropriate pattern, and after the liquid crystal is dripped at a necessary portion, it is bonded to another substrate, and the sealant is made of ultraviolet rays. Curing. Ultraviolet light irradiation is not limited to overall exposure, and appropriate methods such as mask exposure and scanning exposure can be used. • 3 1- 200537211 Then, attach the outer surface of the liquid crystal cell, that is, the other side of each substrate constituting the liquid crystal cell. The polarizer is made to have a polarization direction that is the same as or perpendicular to a liquid crystal alignment direction of a liquid crystal alignment film forming the other surface of the substrate, so as to obtain a liquid crystal display element. Examples of the liquid crystal include nematic liquid crystals and dish-shaped liquid crystals. Among them, nematic liquid crystals are preferred. For example, Schiff base liquid crystals, azo oxide liquid crystals, biphenyl liquid crystals, and phenyl ring-based liquid crystals can be used. , Ester-based liquid crystals, terphenyl-based liquid crystals, biphenyl ring-based liquid crystals, denser-based liquid crystals, dioxane-based liquid crystals, Φ bicyclic octane-based liquid crystals, and cubic liquid crystals. In addition, cholesteric liquid crystals such as chlorinated cholesterol, cholesterol nonanoate, and cholesterol carbonate may be added to these liquid crystals, and those sold under the trade names "C-15" and "CB-15" (manufactured by Miruko) It is used on palms. In addition, a ferroelectric liquid crystal such as decoxybenzylidene-P-amino-2-methylbutyl cinnamate can also be used. The polarizer attached to the outer surface of the liquid crystal can be a polarizer made of a polarizing film called a holmium film obtained by extending the alignment of polyvinyl alcohol while absorbing iodine, or a polarizer made of a holmium film itself. . Examples The present invention will be described in more detail through examples below, but the present invention is not limited to these examples in any way as long as it does not exceed the gist thereof. In the following examples, parts refer to 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 used in a laboratory. Stir with a blender to stabilize the solution temperature at 60 ° C. Then -32- 200537211 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. Then, it was reacted at 60 ° C. for 4 hours to obtain a solution of 43.5 g of a reaction product (1) having a concentration of SiO 2 of 10% by weight. After the solution was cooled to room temperature, the mixed solution of methanol and ethanol in the solution was removed by evaporation at 50 ° C, and then 65.3 g of ethylene glycol monobutyl ether was added and filtered through a filter membrane having a pore size of 0.2 / xm to obtain a liquid crystal. Alignment agent (Α). Synthesis Example 2 106.3 g of methyltriethoxysilane, 6.64 g of 1-trimethylsilanyl-3,3-difluoro-4,4-dimethylorbornorane, and 12.67 g of tetramethoxysilane After dissolving in 260.8 g of ethylene glycol monobutyl ether, stir with a laboratory stirrer to stabilize the solution temperature at 60 ° C. 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. Then, it was reacted at 60 ° C. for 4 hours to obtain 430 g of a solution containing 10% by weight of the reaction product (1) in terms of SiO 2 concentration. After the solution was cooled to room temperature, the mixed solution of methanol and ethanol was removed by evaporation at 50 ° C, and then 65.2 g of ethylene glycol monobutyl ether was added and filtered through a filter membrane with a pore size of 0.2 / xm to obtain a liquid crystal alignment. Agent (B). % Synthesis Example 3 After dissolving 106.3 g of methyltriethoxysilane, 5.79 g of 3-trimethylsilylcholestane, and 12.67 g of tetramethoxysilane in 262.2 g of ethylene glycol monobutyl ether, Stir with a stirrer in the laboratory to stabilize the solution temperature at 60 ° C. 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. Then, it was reacted at 60 ° C. for 4 hours to obtain 420 g of a solution of the reaction product (1) in a weight% based on the concentration of SiO 2. After the solution was cooled to room temperature, the methanol and ethanol mixed with 200537211 solution were removed by evaporation at 50 ° C, and then 65_5 g of ethylene glycol monobutyl ether was added and filtered through a filter membrane with a pore size of 0.2 / lm to obtain Liquid crystal alignment agent (C). Synthesis Example 4: 92.98 g of methyltriethoxysilane, 6.64 g of 4, -trimethylsilyloxy chalcone, 6.82 g of octadecyltriethoxysilane, and 12.67 g of tetramethoxysilane After dissolving in 259.6 g of ethylene glycol monobutyl ether, it was stirred with a laboratory stirrer to stabilize the solution temperature at 60 ° C. 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. Then, it was reacted at 60 ° C. for 4 hours to obtain 430 g of a 10% by weight solution of the reaction product (1) in terms of SiO 2 concentration. After the solution was cooled to room temperature, the mixed solution of methanol and ethanol was removed by evaporation at 5 ° C, and then 65.0 g of ethylene glycol monobutyl ether was added and filtered through a filter membrane having a pore size of 0.2 μm to obtain a liquid crystal alignment. (D). Comparative Synthesis Example 1 218.1 g (1.0 mole) pyromellitic dianhydride and 198.27 g (1 mole) of 4,4 '· diaminodiphenylmethane were dissolved in 1 600 g of N-formaldehyde After the methyl-2-pyrrolidone%, the solution was reacted at 20 ° C for 6 hours. Then the obtained reaction solution was poured into a large excess of acetone to precipitate the reaction product, and the reaction product was separated, washed, and dried to obtain 400.3 g of a polyamino acid polymer. This polymer was dissolved in γ-butyrolactone and filtered through a filter having a pore size of 0.2 / im to obtain a liquid crystal alignment agent (E) having a solid content concentration of 4%. Liquid crystal alignment] When the voltage of the liquid crystal display element is turned on and off, the presence or absence of abnormal regions in the liquid crystal cell is observed with a microscope. When there is no abnormal region, the evaluation is "good". -34- 200537211 The following light irradiation, heat treatment, and [Liquid crystal display element afterimage erasing time] 30 Hz, 3.0V rectangular wave obtained by superimposing 3.0 V DC and 6.0 V AC (peak-to-peak) on the liquid crystal display element at an ambient temperature of 70 ° C 20 After the liquid crystal display element is driven, the voltage is cut off and the time required to remove the afterimage is measured visually. [Voltage residual rate of liquid crystal display element]

A voltage of 5 V was applied to the liquid crystal display element in a time span of 167 milliseconds, and the voltage application time was 60 microseconds. The voltage residual rate after the voltage was released to 1 67 milliseconds was measured. The measurement device was VHR-1 manufactured by Dongyang Technology Co., Ltd., and was performed at 60 ° C. Immediately after the liquid crystal display element was manufactured, the following light irradiation and heat treatment were performed, and then measurement was performed. [Light irradiation] After the liquid crystal display element is manufactured, the entire element is irradiated with light using a metal halide lamp as a light source. Use an optical filter to select a wavelength range of 300-450nm ^, and irradiate with an energy of 2J / cm2. [Heat treatment] After the manufactured liquid crystal display element was placed in an oven at 100 ° C for 3 weeks, it was taken out and slowly cooled to room temperature. Example 1 A liquid crystal alignment agent (A) was coated on a transparent electrode surface of a glass substrate with a transparent electrode of an ITO film by a spin coater, and dried in hot air at 300 ° C for 30 minutes to form a dry average film thickness. It is a coating film of 700 angstroms. -35- 200537211 Fabricate two substrates with liquid crystal alignment films formed as above, apply alumina ball epoxy resin-based adhesive to the peripheral parts of each substrate by screen printing, and pass the two substrates through the gap so that the coating film surfaces face each other. Place it so that the peripheral parts are butted and crimped together to cure the adhesive. Negatively charged nematic liquid crystal was injected into the cell gap where the adhesive was divided on the surface of the substrate and the periphery, and then the injection hole was closed with an epoxy adhesive to obtain a vertically aligned liquid crystal display element. The just-prepared liquid crystal display device obtained as described above was subjected to observation of liquid crystal alignment φ property and measurement of voltage residual ratio. Three liquid crystal display elements manufactured as described above using the liquid crystal alignment agent (A) were prepared, one was illuminated, and then liquid crystal alignment observation and voltage residual ratio measurement were performed, and the other was heat-treated, and then liquid crystal alignment observation and voltage residual ratio were performed. The remaining one was measured for the afterimage erasure time as described. The results are shown in Table 1. Examples 2 to 3 Using the liquid crystal alignment agent obtained in Synthesis Examples 2 to 3, a liquid crystal display device was manufactured in the same manner as in Example 1. Each obtained liquid crystal display device was evaluated for liquid crystal alignment, voltage residual ratio, and afterimage erasure time as shown in Example 1. The results are shown in Table 1. Example 4 A liquid crystal alignment agent (A) was coated on a transparent electrode surface of a glass substrate with a transparent electrode by a spin coater, and dried in hot air at 300 ° C for 30 minutes to form a dry average film thickness of 700. Angstrom's coating. The film was irradiated with an ammonia ion beam from a direction at an angle of 40 degrees to the substrate for 10 seconds by an acceleration voltage of 200 V. -36- 200537211 Then, each of the two ion-beam-treated liquid crystal accommodating substrates, each having a liquid crystal alignment film, was coated with an epoxy-based adhesive to which alumina balls having a diameter of 5.5 mm were added by screen printing. Then, the two liquid crystal alignment film surfaces of the two liquid crystal accommodating substrates are placed opposite to each other, and they are overlapped and pressed perpendicularly to the irradiation direction of the ion beam, so that the adhesive is cured. Next, a nematic liquid crystal (MLC-622 1 manufactured by Meruco) is filled between a pair of substrates through a liquid crystal injection port, and then the liquid crystal injection port is closed with an acrylic light-curing adhesive, and the two outer surfaces of the substrate are filled. The polarizers were bonded so that the polarization direction of the polarized φ sheet and the ion beam irradiation direction of the liquid crystal alignment film of the respective substrates were the same, so that a liquid crystal display element was obtained. Each liquid crystal display element thus prepared was evaluated for liquid crystal alignment, voltage residual ratio, and afterimage erasure time as shown in Example 1. The results are shown in Table 1. Examples 5 to 6 Using the liquid crystal alignment agent obtained in Synthesis Examples 2 to 3, a liquid crystal display device was manufactured in the same manner as in Example 4. Each obtained liquid crystal display device was evaluated for liquid crystal alignment, voltage residual ratio, and afterimage erasure time as shown in Example 1. The results are shown in Table 1. Example 7 A liquid crystal alignment agent (D) was coated on a transparent electrode surface of a glass substrate with a transparent electrode with a ITO film by a spin coater, and dried in hot air at 300 ° C for 30 minutes to form a dry average film thickness. It is a coating film of 7 00 angstroms. Hg-Xe lamp is used to cut 320nm short-wavelength light through a polarized glass (SPLEX-50C-32) made of hard (Pilex) glass (registered trademark), from -37- 200537211 normal direction of the substrate surface This coating film surface was irradiated with linearly polarized light having a main wavelength of 1.065 / cm2, mainly 3 65 nm.

Manufacture two substrates forming a liquid crystal alignment film treated as above, and apply alumina ball epoxy resin-based adhesive by screen printing on the peripheral parts of each substrate, and then overlap the two substrates through the gap to make them overlap. Parallel to the direction of the irradiated ultraviolet polarizing surface, the peripheral parts are butt-bonded and pressed together to cure the adhesive. Nematic liquid crystals (MLC-622 1 manufactured by Melco) are filled into the intercellular space divided by the adhesive on the substrate surface and the peripheral part, and then the injection holes are closed with an epoxy-based adhesive to obtain a liquid crystal. Display element. For each of the thus-produced liquid crystal display elements, the liquid crystal alignment, voltage residual ratio, and afterimage erasing time were evaluated as shown in Example 1. The results are shown in Table 1. Comparative Example 1 The liquid crystal alignment agent (E) obtained in Comparative Synthesis Example 1 was coated on a transparent electrode surface of a glass substrate with a transparent electrode of an ITO film by a spin coater, and dried in hot air at 200 ° C for 20 minutes. A coating film having a dry average film thickness of ^ 600 angstroms was formed. A rubbing machine provided with a roller carrying a cloth made of artificial fiber rubbed the coating film. The rotation speed of the roller was 400 rpm, the table moving speed was 30 mm / sec, and the fluff press-in length was 0.4 mm. For each of the thus-produced liquid crystal display elements, the liquid crystal alignment, voltage residual ratio, and afterimage erasing time were evaluated as shown in Example 1. The results are shown in Table 1. -38- 200537211

Table 1 Example of crystalline orientation ti Voltage residual ratio (%) Afterimage comparison Comparative Example Just-made light-heated place Just-made light-heated place After the post-shooting and post-shooting after the post-shooting (minutes) 1 Good Good Good 98 98 98 4 2 Good Good Good 97 97 97 4 3 Good Good Good 98 97 95 3 Example 4 Good Good 97 97 97 4 5 Good Good Good 98 98 96 5 6 Good Good Good 97 97 96 5 7 Good Good Good 98 98 94 7 Comparative Example 1 Good No orientation No orientation 83 80 76 30 or more

-39-

Claims (1)

200537211 X. Patent application scope: I. A liquid crystal alignment agent, which includes (I) a silicon compound represented by the following formula (1), a reaction product of a silicon compound represented by the following formula (2) and water, and (11) The solvent represented by the formula (3), Si (OR1) 4 ........ (1) wherein R is a hydrogen atom, a fluorine atom, or a monovalent organic group, RSi (OR2) 3 ........ (2) where R is a monovalent organic group, and R2 is a hydrogen atom, a fluorine atom, or a monovalent organic group, 3 Η c I (3) R30 (CH) m (CH2) nOH where R3 is methyl, ethyl, n-propyl, isopropyl, n-butyl or third butyl, and m is 0 or 1, and n is 1, 2 or 3. 2. The liquid crystal alignment agent according to item 1 of the scope of patent application, wherein the sand% compound represented by formula (2) is a group selected from the group consisting of: (A) R in the above formula (2) may be selected from an amine group , A sand compound having 1 to 4 carbon atoms, a vinyl group or a phenyl group substituted with a substituent of glycidoxy and trifluoromethyl, and (B) in the above formula (2), R is selected from (a) a straight-chain alkyl group having 16 or more carbon atoms; (b) a monovalent organic group which may be substituted and having at least one probornyl ring; (0) a monovalent group which may be substituted and have at least one steroid skeleton Organic group; -40-200537211 (d) a monovalent group having an aromatic ring having a substituent selected from a fluorine atom, a trifluoromethyl group or a trifluoromethoxy group and having 8 or more carbon atoms; or (e ) At least one kind of silicon compound having a photosensitive group of a cinnamyl group or a chalcone group. 3. The liquid crystal alignment agent according to item 2 of the patent application range, wherein (b) above may be substituted and have at least one probornorane The ring monovalent organic group is any one of the following formulae (4) to (16) (13) (6) (7) ch3 " CFgCFaCFa H2C-9 ~ ch3 SiH (〇CH2CH3) 2 CF3H3C (16) Each group represented by fcCF2CF2CH2OH. 4. The liquid crystal alignment agent of item 2 of the patent application, wherein (c) may be substituted and the monovalent organic group having at least one steroid skeleton is any one of the following formulae (17) to (26) -4 1- 200537211 h3cH3ch- (ch2) 3CH (ch3) 2 (Π) Η3〇Η3〇η- (〇η2 > 3〇η (〇η3) 2 (18) (19) h3cHsch- (ch2) 3CH (ch3) 2 H3CH3CH- (CHa) 3CH (CH,) 2 (20) H3C 3 CHe (〇Η2) 2〇Η = 0 (ΟΗ3) 2 HaC H3C CH- (CH2) 2CHBC (CH3) a (21) H3CHaC6r (CH2) 3CH = C (CH3) 2 (22) P3) i3c ch3 H3CH3CH- (CH2) 3CHeC (CH3) 2 (24) H3CH3CH * (CH2) 3CH (CH3) 2 (26) 5. The liquid crystal alignment agent according to item 2 of the patent application scope, wherein (d) has a member selected from a fluorine atom, a trifluoromethyl group or a trifluoromethyl group. A monovalent group having an aromatic ring of an oxo substituent and having 8 or more carbon atoms is represented by the following formulae (27) to (30) -42- 200537211 Respective bases. 6. The liquid crystal alignment agent according to item 2 of the application, wherein the compound represented by formula (2) is a combination of a silicon compound (A) and a silicon compound (B). 7. The liquid crystal alignment agent according to item 1 of the scope of patent application, wherein among the compounds represented by the formula (2), the compound in which R is a photosensitive group (e) accounts for 1 to 50 mole%. t 8 · A method for forming a liquid crystal alignment film, comprising a step of applying a liquid crystal alignment agent as described in any one of claims 1 to 7 on a substrate, and heating the coated substrate to make the coating film Cure step. 9 · A method for forming a liquid crystal alignment film with a controlled liquid crystal alignment angle, which is characterized by rubbing the film surface of the liquid crystal alignment film as described in item 8 of the scope of patent application. 10 · —A method for forming a liquid crystal alignment film with a controlled liquid crystal alignment angle, which is characterized by using electromagnetic radiation selected from X-rays and ultraviolet rays, selected from ion beams, -43- 200537211 neutral atomic beams, electron beams, and molecular beams The film surface of the liquid crystal alignment film as described in item 8 of the patent application range is irradiated with the particle beam of the elementary particle beam, or both the electromagnetic radiation and the particle beam. 1 1 · A liquid crystal alignment film manufactured by a method according to any one of claims 8 to 10 of the scope of patent application. 1 2 · A liquid crystal display element, which is characterized by having a liquid crystal alignment film as in item i i of the scope of patent application. -44- 200537211 VII. Designated Representative Map: (1) The designated representative map in this case is: None. (2) Brief description of the component symbols in this representative picture: 8. If there is a chemical formula in this case, please disclose the chemical formula that can best show the characteristics of the invention: ch3 I (3) R30 (CH) m (CH2) nOH