WO2009081692A1 - Agent d'alignement de cristal liquide et procédé de formation de film d'alignement de cristal liquide - Google Patents

Agent d'alignement de cristal liquide et procédé de formation de film d'alignement de cristal liquide Download PDF

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Publication number
WO2009081692A1
WO2009081692A1 PCT/JP2008/071759 JP2008071759W WO2009081692A1 WO 2009081692 A1 WO2009081692 A1 WO 2009081692A1 JP 2008071759 W JP2008071759 W JP 2008071759W WO 2009081692 A1 WO2009081692 A1 WO 2009081692A1
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Prior art keywords
liquid crystal
group
acid
formula
carbon atoms
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PCT/JP2008/071759
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English (en)
Japanese (ja)
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Toshiyuki Akiike
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Jsr Corporation
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Priority to KR1020107011515A priority Critical patent/KR101534887B1/ko
Priority to CN200880122740.5A priority patent/CN101910928B/zh
Priority to JP2009547004A priority patent/JP4544439B2/ja
Publication of WO2009081692A1 publication Critical patent/WO2009081692A1/fr

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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
    • G02F1/133788—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation by light irradiation, e.g. linearly polarised light photo-polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133719—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films with coupling agent molecules, e.g. silane

Definitions

  • the present invention relates to a liquid crystal aligning agent and a method for forming a liquid crystal aligning film.
  • a nematic fine type liquid crystal having positive dielectric anisotropy is made into a sandwich structure with a substrate with a transparent electrode having a liquid crystal alignment film, and the major axis of the liquid crystal molecules is between the substrates as required.
  • Liquid crystal such as TN (Tw isted Nematic) type, STN (Super Twisted Nematic) type, I PS (In Plane Switching) type, etc.
  • Liquid crystal display elements having cells are known (see Japanese Patent Application Laid-Open Nos. 56-91277 and 1-120528).
  • liquid crystal alignment film In such a liquid crystal cell, it is necessary to provide a liquid crystal alignment film on the substrate surface in order to align liquid crystal molecules in a predetermined direction with respect to the substrate surface.
  • This liquid crystal alignment film is usually formed by a method (rubbing method) in which the organic film surface formed on the substrate surface is rubbed in one direction with a cloth material such as rayon.
  • rubbing method a method in which the organic film surface formed on the substrate surface is rubbed in one direction with a cloth material such as rayon.
  • dust and static electricity are likely to be generated in the process, and there is a problem that dust adheres to the alignment film surface and causes display defects.
  • TFT Thin Film Transistor
  • the TFT element circuit breaks down due to the generated static electricity, resulting in a decrease in yield.
  • liquid crystal display elements with higher definition in the future will have unevenness on the substrate surface as the pixel density increases, making uniform rubbing difficult.
  • polarized light is applied to photosensitive thin films such as polyvinyl cinnamate, polyimide, and azobenzene derivatives formed on the substrate surface.
  • photosensitive thin films such as polyvinyl cinnamate, polyimide, and azobenzene derivatives formed on the substrate surface.
  • a photo-alignment method that imparts liquid crystal alignment ability by irradiating non-polarized radiation is known. According to this method, uniform liquid crystal alignment can be realized without generating static electricity or dust (Japanese Patent Laid-Open No. 6-287453, Japanese Patent Laid-Open No. 10-251646, Japanese Patent Laid-Open No. 11-2815, JP11-152475, JP2000-144136, JP2000-319510, JP2000-281724, JP9-1297313, JP2003-307736, JP (See 2004-163646 and 2002-250924).
  • the liquid crystal alignment film tilts the liquid crystal molecules at a predetermined angle with respect to the substrate surface. It must have pre-tilt angle characteristics.
  • the pretilt angle characteristic is usually imparted by irradiation with radiation whose incident direction to the substrate surface is inclined from the substrate normal.
  • a vertical (homeotope pick) alignment mode in which liquid crystal molecules having negative dielectric anisotropy are aligned perpendicularly to a substrate is also known.
  • this operation mode when a voltage is applied between the substrates and the liquid crystal molecules tilt in the direction parallel to the substrate, the liquid crystal molecular force S tilts from the normal direction of the substrate toward one direction in the substrate plane.
  • a method of providing protrusions on the substrate surface a method of providing stripes on the transparent electrode, and using a rubbing alignment film, liquid crystal molecules are slightly directed from the substrate normal direction to one direction in the substrate surface.
  • a method of tilting pre-J
  • the photo-alignment method is known to be useful as a method for controlling the tilt direction of liquid crystal molecules in a vertical alignment mode liquid crystal cell. That is, it is known that the tilt direction of liquid crystal molecules during voltage application can be uniformly controlled by using a vertical alignment film imparted with alignment regulating ability and pretilt angle expression by a photo-alignment method (Japanese Patent Laid-Open No. 2003-307736). JP, 2004-163646, JP 20 02-250924, JP 2004-83810, JP 9-21 1468 and JP 2003-1144.37).
  • the liquid crystal alignment film produced by the photo-alignment method can be effectively applied to various liquid crystal display elements.
  • the conventional photo-alignment film has a problem that a large amount of radiation is required to obtain a large pretilt angle.
  • a liquid crystal alignment ability is imparted to a thin film containing an azobenzene derivative by the photo-alignment method
  • radiation whose optical axis is tilted from the substrate normal is 10,000 JZm 2 or more. It has been reported that it must be irradiated (see JP 2002-250924 A and JP 2004-83810 A and J. oft he S ID 11/3, 2003, p 579).
  • the liquid crystal alignment film produced by the photo-alignment method has a light-sensitive site in the side chain of the polymer as the main component.
  • the photosensitivity of the side chain There is concern that the part may not be able to wipe out the possibility of thermal decomposition during heating in the liquid crystal panel manufacturing process, causing problems that contaminate the substrate and panel manufacturing lines.
  • a liquid crystal alignment film having good liquid crystal alignment ability, excellent electrical characteristics and high heat resistance can be formed by a photo-alignment method with a small amount of radiation irradiation, and there is a problem of thermal decomposition during post baking.
  • a liquid crystal aligning agent that does not cause the problem has not been known so far. Disclosure of the invention
  • the present invention has been made in view of the above circumstances, and its purpose is excellent in storage stability and has a good liquid crystal alignment ability even with a small exposure amount by irradiation with polarized or non-polarized radiation without rubbing treatment.
  • the above object of the present invention is as follows.
  • R 1 is a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms
  • R 11 R IV and R v are each independently a hydrogen atom, a methyl group, a cyan group or a fluorine group.
  • R 111 is a monovalent organic group having 1 to 40 carbon atoms
  • R 1 is other than a hydrogen atom
  • R 111 is a carboxyl group.
  • X 1 is a monovalent organic group having an epoxy group
  • Y 1 is a hydroxyl group, an alkoxyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or carbon.
  • the number 6 to 20 arele base.
  • liquid crystal aligning agent containing a radiation-sensitive polyorganosiloxane obtained by reacting the above.
  • the liquid crystal aligning agent of the present invention comprises a compound represented by the above formula (1) (hereinafter referred to as “cinnamic acid derivative (1)”),
  • the cinnamic acid derivative (1) used in the present invention is a compound represented by the above formula (1).
  • R 11 , R IV and R v are each preferably a hydrogen atom.
  • Cinnamic acid derivative (1) is represented by the following formula (2)
  • R VI is a single bond, an ether bond, a thioether bond, an ester bond, a thioester bond or R VI 1 is an amide bond, and R VI 1 is an alkyl group having 1 to 30 carbon atoms which may be substituted with a fluorine atom or an alicyclic group having 3 to 40 carbon atoms which may be substituted with a fluorine atom.
  • R VI 11 has 1 to 30 is an alicyclic group having 3 to 40 carbon atoms which may be substituted with 30 alkyl groups or fluorine atoms.
  • R VI in the above formula (2) is an oxygen atom or an ester bond (wherein the oxygen atom is bonded to the group R v 11 ).
  • R VI 1 includes an alkyl group having 1 to 20 carbon atoms which may be substituted with a fluorine atom, a cholesteryl group, a cholesteryl group, a cyclohexyl group or an alkyl group having 1 to 10 carbon atoms. A cyclohexyl group is preferred.
  • Examples of the compound represented by the above formula (2) include, for example, the following formulas (2-1) to (2-10)
  • Preferred R VI 11 in the above formula (3) is an alkyl group having 1 to 20 carbon atoms, a group C d F 2d + 1 C e H 2e- (where d is an integer of 1 to 3, e is 0 And an alkyl hexyl group having 1 to 10 carbon atoms of a cholesterol group, a cholestenyl group, a cyclohexyl group, or an alkyl group.
  • This alkyl hexyl group includes 4-butylcyclohexyl group or 4-amyl hexyl group.
  • a xyl group is preferred.
  • Such a cinnamic acid derivative (1) can be synthesized by a conventional method of organic chemistry.
  • the compound represented by each of the above formulas (2-1) to (2-5) can be obtained by reacting, for example, a compound RVI1 OH corresponding to a desired compound with trimellitic anhydride octaride.
  • the synthesis of the intermediate ester compound is preferably carried out in a suitable solvent in the presence of a basic compound.
  • the solvent that can be used here include tetrahydrofuran, and examples of the basic compound include triethylamine. Can be mentioned respectively.
  • the reaction between the ester compound and the 4-aminocinnamic acid is, for example, a method in which both are refluxed in acetic acid, both in toluene or xylene with an appropriate catalyst (for example, an acid catalyst such as sulfuric acid or a base catalyst such as triethylamine).
  • an appropriate catalyst for example, an acid catalyst such as sulfuric acid or a base catalyst such as triethylamine.
  • a compound represented by each of the above formulas (2-6) and (2-7) can be obtained by dehydrating and ring-closing 5-hydroxyphthalic acid in, for example, jetylbenzene to form an acid anhydride.
  • an imide compound as a first intermediate is synthesized, and then the imide compound and a compound corresponding to the desired compound R VI 1 — X (where X is It is a halogen atom and can be synthesized by reacting.
  • This reaction is preferably carried out in a suitable solvent in the presence of a basic compound.
  • the solvent that can be used here include amide compounds such as N, N-dimethylacetamide, and examples of the basic compound include potassium carbonate.
  • the compound represented by each of the above formulas (2-8) to (2-10) can be obtained by, for example, reacting the compound R VI 1— ⁇ H corresponding to the desired compound with 4-fluoro-o-xylene. Then, the ether compound as the first intermediate was synthesized, and then the ether compound was oxidized and further dehydrated by heating to synthesize the acid anhydride as the second intermediate.
  • the synthesis of the first intermediate ether compound is preferably carried out in a suitable solvent in the presence of a basic compound. Examples of the solvent that can be used here include tetrahydrofuran, and examples of the basic compound include tert-butoxypotassium.
  • the synthesis of the acid anhydride from this ether compound and the reaction of the dianhydride with 4-aminocinnamic acid were carried out according to the methods in the synthesis of the compounds represented by the above formulas (2-6) and (2-7), respectively. Can be done.
  • the compound represented by the above formula (3) includes 4 12 trocinnamic acid obtained by treating 4 12 trocinnamic acid with, for example, octarogenated thionyl, and a compound R VI corresponding to the desired compound.
  • the body can be synthesized by reacting with trimellitic anhydride.
  • the synthesis of the first intermediate ester compound is preferably carried out in the presence of a basic compound such as triethylamine.
  • the reduction reaction of the nitro group of the ester compound can be preferably carried out by a combination of zinc and ammonium chloride or an appropriate reduction system such as tin chloride.
  • the reaction between the second intermediate and trimellitic anhydride is carried out between the ester compound and 4-aminocinnamic acid in the synthesis of the compounds represented by the above formulas (2-1) to (2-5). It can be done according to the reaction.
  • the polyorganosiloxane having an epoxy group used in the present invention is selected from the group consisting of a polyorganosiloxane having a repeating unit represented by the above formula (S-1), a hydrolyzate thereof and a condensate of the hydrolyzate. At least one type.
  • X 1 in the above polyorganosiloxane having an epoxy group is represented by the following formula (X 1 — 1) or (X 1 — 2)
  • the group represented by is preferable.
  • Examples of the alkoxy group having 1 to 10 carbon atoms of Y 1 include, for example, a methoxyl group and an ethoxy group; and examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and n_ Butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-lauryl group, n-detenzole group, n-tritesylile, n- Tetradene group, n-pentadenfre group, n-hexadecyl group, n-heptadecyl group, n-year-old ktadecyl group, n-nonadecyl group, n-eicosyl group, etc .;
  • the polyorganosiloxane having an epoxy group preferably has a polystyrene-reduced weight average molecular weight of 500 to 100, 000, as measured by gel permeation chromatography (GPC). More preferably, it is 0 0 to 1 0, 0 0 0, and more preferably 1, 0 0 0 to 5, 0 0 0.
  • Such polyorganosiloxane having an epoxy group is preferably a silane compound having an epoxy group or a mixture of a silane compound having an epoxy group and another silane compound, preferably an appropriate organic solvent, water and catalyst. It can be synthesized by hydrolysis or hydrolysis / condensation in the presence of.
  • silane compound having an epoxy group examples include 3-glycidyloxip Poxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxy hexyl) ethyltriethoxysilane, and the like.
  • silane compounds examples include tetrachlorosilane, teramethoxy silane, teraoxysilane, tera- ⁇ -propoxysilane, teller i-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, Trichlorosilane, trimethoxysilane, triethoxysilane, tri-n-propoxysilane, tri-i-propoxysilane, tri-n-buoxysilane, tri-sec_butoxysilane, fluorotrichlorosilane, fluorotrimethoxysilane, fluorotriethoxy Silane, Fluorotri n-propoxysilane, Fluorotriline i —Propoxy silane, Fluorotri n-butoxy silane, Fluoro sec sec-Boxy silane, Methyltrichlorosilane, Methyltrimethoxysilane ,
  • the epoxy group-containing polyorganosiloxane used in the present invention preferably has an epoxy equivalent of 100 to 10,000 gZ mol, more preferably 150 to 1,000 g / mol. . Therefore, when synthesizing a polyorganosiloxane having an epoxy group, the proportion of the silane compound having an epoxy group and another silane compound is used so that the obtained polyorganosiloxane epoxy equivalent falls within the above range. It is preferable to adjust and set to.
  • organic solvent examples include hydrocarbons, ketones, esters, ethers, alcohols, and the like.
  • hydrocarbon examples include toluene and xylene
  • ketone examples include methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, jetyl ketone, and cyclohexanone;
  • ester examples include ethyl acetate, n-butyl acetate, i-amyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, and ethyl lactate;
  • Examples of the ether include ethylene glycol dimethyl ether, ethylene dallicol cetyl ether, tetrahydrofuran, dioxane, and the like.
  • Examples of the alcohol include 1 hexanol, 4 1 methyl 1 2-pentanol, ethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether / reether, propylene glycol mono ⁇ / remono n-propyl ether, etc. And, respectively. Of these, water-insoluble ones are preferred.
  • organic solvents can be used alone or in admixture of two or more.
  • the amount of the organic solvent used is preferably 10 to: L 0, 0,000 parts by weight, more preferably 5 0 to: L, 0,000 parts by weight with respect to 100 parts by weight of the total silane compounds. .
  • the amount of water used in producing the polyorganosiloxane having an epoxy group is preferably 0.5 to 100 times mol, more preferably 1 to 30 times mol, based on all silane compounds.
  • Examples of the catalyst that can be used include acids, alkali metal compounds, organic bases, titanium compounds, and zirconium compounds.
  • alkali metal compound examples include sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, and potassium ethoxide.
  • organic base examples include primary and secondary organic amines such as edylamine, jetylamine, piperazine, piperidine, pyrrolidine, and pyrrole;
  • Examples include quaternary organic amines such as tetramethylammonium hydroxide.
  • quaternary organic amines such as tetramethylammonium hydroxide.
  • tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, and quaternary organic amines such as tetramethylammonium hydroxide. S is preferred.
  • an alkali metal compound or an organic base is preferable as a catalyst for producing a polyorganosiloxane having an epoxy group.
  • an alkali metal compound or organic salt group is preferable.
  • the desired polyorganosiloxane can be obtained at a high hydrolysis and condensation rate without causing side reactions such as ring opening of the epoxy group. It is preferable because it is excellent in production stability.
  • the liquid crystal aligning agent of the present invention containing a reaction product of a polyorganosiloxane having an epoxy group synthesized using an alkali metal compound or an organic base as a catalyst and a cinnamic acid derivative (1) has storage stability. It is convenient because it is extremely excellent.
  • an organic base is particularly preferable.
  • the amount of organic base used varies depending on the type of organic base, reaction conditions such as temperature, and should be set appropriately. For example, it is preferably 0.1 to 3 moles per mole of all silane compounds. More preferably, it is 0.05-1 mol.
  • a silane compound having an epoxy group and other silane compounds as required are dissolved in an organic solvent, and this solution is mixed with an organic base and water, and heated by, for example, an oil bath. It is preferable to carry out by doing.
  • the heating temperature is preferably 130 ° C or lower, more preferably 40 to 100 ° C, preferably 0.5 to 12 hours, more preferably 1 to 8 hours. desirable.
  • the mixed solution may be stirred or refluxed.
  • the organic solvent layer separated from the reaction solution is preferably washed with water.
  • washing with water containing a small amount of salt for example, an aqueous solution of about 0.2% by weight ammonium nitrate is preferred because the washing operation becomes easy. Washing is carried out until the aqueous layer after washing becomes neutral, and then the organic solvent layer is dried with a suitable desiccant such as anhydrous sulfuric acid and molecular sieves as necessary, and then the solvent is removed.
  • a suitable desiccant such as anhydrous sulfuric acid and molecular sieves as necessary, and then the solvent is removed.
  • a target polyorganosiloxane having an epoxy group can be obtained.
  • polyorganosiloxane having an epoxy group may be used.
  • examples of such commercially available products include DMS-E01, DMS-E12, DMS-E21, EMS-32 (manufactured by Chisso Corporation). ⁇ Radiation sensitive polyorganosiloxane>
  • the radiation-sensitive polyorganosiloxane used in the present invention is synthesized by reacting the polyorganosiloxane having an epoxy group as described above with a cinnamic acid derivative (1), preferably in the presence of a catalyst.
  • a cinnamic acid derivative (1) preferably in the presence of a catalyst.
  • (1) is preferably used in an amount of 0.001 to 1.5 mol, more preferably 0.01 to 1 mol, and even more preferably 0.05 to 0.9 mol with respect to 1 mol of the epoxy group of the polyorganosiloxane. Is done.
  • an organic base or a compound known as a so-called curing accelerator that promotes a reaction between an epoxy compound and an acid anhydride can be used.
  • the organic base include primary to secondary organic amines such as edylamine, jetylamine, piperazine, piperidine, pyrrolidine, and pyrrole;
  • Tertiary organic amines such as triedilamine, tri-n-propylamine, tri-n-ptylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene;
  • Examples include quaternary organic amines such as tetramethylammonium hydroxide.
  • quaternary organic amines such as tetramethylammonium hydroxide.
  • tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, and 4-dimethylaminopyridine; quaternary amines such as tetramethylammonium hydroxide Organic amines are preferred.
  • curing accelerator examples include tertiary amines such as benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, cyclohexyldimethylamine, and triethanolamine;
  • Organophosphorus compounds such as diphenylphosphine, triphenylphosphine, triphenyl phosphite;
  • Benzyltriphenylphosphonium chloride tetra_n-butylphosphonium bromide, methyltriphenylphosphonium amide, ethyltriphenylphosphonium amide, n-butyltriphenylphosphonium Mubromide, tetraphenylphosphonium amide, ethyltriphenylphosphine musdeide, ethyltriphenylphosphonium cetate, tetra-n-butylphosphonium-o, o-jetylphospho Mouth dithionate, tetra-n-butyl phosphonium benzotriazolate, tetra-n_butylphosphonium tetrafluoroborate, tetra-n-butyl phosphonium tetraphenyl porate, tetraphenylphosphonium Mutetrahue Quaternary Fosufoniumu salt, such as Ruporeto;
  • Organometallic compounds such as zinc octylate, tin octylate, aluminum acetylethylacetone complexes;
  • Quaternary ammonium salts such as tetraethyl ammonium bromide, tetra n-butyl ammonium bromide, tetraethyl ammonium chloride, tetra n-butyl ammonium chloride;
  • Boron compounds such as boron trifluoride and triphenyl borate
  • Metal halides such as zinc chloride and stannic chloride
  • Amine addition accelerators such as adducts of dicyandiamide amine and epoxy resin High melting point dispersion type latent curing accelerator such as
  • Microphone-mouth type latent curing accelerator with a polymer coated surface of a curing accelerator such as the imidazole compound, organophosphorus compound or quaternary phosphonium salt; amine salt type latent curing agent accelerator;
  • Examples include latent curing accelerators such as high temperature dissociation type thermal cationic polymerization type latent curing accelerators such as Lewis acid salts and Bronsted acid salts.
  • Quaternary ammonium salts such as ptylammonium bromide, tetraethylammonium chloride, and tetra-n-butylammonum chloride.
  • the catalyst is preferably 100 parts by weight or less, more preferably from 0.001 to 100 parts by weight, and even more preferably from 0 to 100 parts by weight of the polyorganosiloxane having an epoxy group. Used in an amount of 1 to 20 parts by weight.
  • the reaction temperature is preferably 0 to 200 ° C., more preferably 50 to 150 ° C.
  • the reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours.
  • the synthetic reaction of the radiation-sensitive polyorganosiloxane can be carried out in the presence of an organic solvent, if necessary.
  • organic solvents include hydrocarbon compounds, ether compounds, ester compounds, ketone compounds, amide compounds, alcohol compounds, and the like.
  • ether compounds, ester compounds, and ketone compounds are preferred from the viewpoints of solubility of raw materials and products and ease of purification of the products.
  • the amount of the solvent is such that the solid content concentration (the ratio of the total weight of components other than the solvent in the reaction solution to the total weight of the solution) is preferably 0.1% by weight or more, more preferably 5 to 50% by weight. Used in.
  • the radiation-sensitive polyorganosiloxane of the present invention introduces a structure derived from cinnamic acid derivative (1) by ring-opening addition of epoxy to polyorganosiloxane having an epoxy group.
  • This production method is simple and is a very suitable method in that the rate of introduction of structures derived from cinnamic acid derivatives can be increased.
  • R IX — Z (In the formula (4), R IX is an alkyl group having 4 to 20 carbon atoms which may be substituted with fluorine, or a monovalent organic group having 3 to 40 carbon atoms including an alicyclic group. Z is a monovalent group selected from the group consisting of a carboxyl group, a hydroxyl group, —SH, one NCO, one NHR, one CH ⁇ CH 2 and one SO 2 C 1)
  • R IX in the formula (4) may be an alkylphenyl group having an alkyl group which may be substituted with fluorine (however, the alkyl group has 8 to 20 carbon atoms) or may be substituted with fluorine.
  • An alkoxyphenyl group having an alkoxyl group (however, this alkoxyl group has 8 to 20 carbon atoms) is preferred.
  • Z is preferably a strong lpoxyl group.
  • the compound represented by each of these is more preferable.
  • the compound represented by the above formula (4) can be introduced into the photosensitive polyorganosiloxane by reacting with a polyorganosiloxane having an epoxy group under the same reaction conditions as the cinnamic acid derivative (1).
  • the compound represented by the above formula (4) is preferably 50 mol% or less, more preferably 33 mol% based on the sum of the cinnamic acid derivative (1) and the compound represented by the above formula (4). It can be used in the following proportions.
  • the usage rate of the compound represented by the above formula (4) exceeds the usage rate of the cinnamic acid derivative (1), an abnormal domain is generated when the obtained liquid crystal display element is turned on (voltage applied state). There may be a problem that occurs. ⁇ Other ingredients>
  • the liquid crystal aligning agent of the present invention contains the radiation sensitive polyorganosiloxane as described above.
  • the liquid crystal aligning agent of the present invention may further contain other components as long as the effects of the present invention are not impaired.
  • other components include polymers other than radiation-sensitive polyorganosiloxane (hereinafter referred to as “other polymers”), curing agents, curing catalysts, curing accelerators, and at least one in the molecule.
  • a compound having an epoxy group hereinafter referred to as “epoxy compound”
  • epoxy compound a functional silane compound
  • surfactant and the like can be mentioned.
  • Said other polymer can be used in order to improve the solution characteristic of the liquid crystal aligning agent of this invention, and the electrical property of the liquid crystal aligning film obtained.
  • other polymer for example, at least one polymer selected from the group consisting of polyamic acid and polyimide, the following formula (S-2):
  • X 2 is a hydroxyl group, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms; Y 2 Is a hydroxyl group or an alkoxyl group having 1 to 10 carbon atoms.
  • a polysiloxane represented by the formula: Derivatives, polyacetals, polystyrene derivatives, poly (styrene monophenylmaleimide) derivatives, poly (meth) acrylates, and the like.
  • the polyamic acid can be obtained by reacting tetra force sulfonic acid dianhydride and diamine.
  • Examples of tetra-force sulfonic dianhydrides that can be used in the synthesis of polyamic acid include butanetetracarboxylic dianhydride, 1, 2, 3, 4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl- 1, 2, 3, 4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutantetracarboxylic dianhydride, 1,3-dichloro 1,2,3 , 4-cyclobutanetracarboxylic dianhydride, 1, 2, 3, 4-tetramethyl— 1, 2, 3, 4-cyclobutanetetracarboxylic dianhydride, 1, 2, 3, 4-cyclopentane Tetracarboxylic dianhydride, 1, 2, 4, 5-cyclohexanetetracarboxylic dianhydride, 3, 3, 4, 4, 4-dicyclohexyltetracarboxylic dianhydride, 2, 3, 5— Tricarboxyc dpentylace
  • 1 ⁇ ⁇ 13 ⁇ 4 3 are each a divalent organic group having an aromatic ring, and R 2 and R 4 are each a hydrogen atom or A plurality of R 2 and R 4 may be the same or different.
  • Aliphatic tetracarboxylic dianhydrides and alicycles such as compounds represented by Formula tetracarboxylic dianhydride;
  • aromatic tetracarboxylic dianhydride such as a compound represented by each of the above can be mentioned.
  • the aromatic tetracarboxylic dianhydride has one benzene ring or
  • tetracarboxylic dianhydrides may be used alone or in combination of two or more.
  • diamines used in the synthesis of the polyamic acid include p-phenylene diamine, m-phenylene diamine, 4, 4, diaminodiphenylmethane, 4, 4, diaminodiphenylethane, 4, 4 ′.
  • R 5 is a monovalent organic group having a ring structure containing a nitrogen atom selected from the group consisting of pyridine, pyrimidine, triazine, piperidine and piperazine, and X 3 is Indicates a divalent organic group.
  • R 6 is a divalent organic group having a ring structure containing pyridine, pyrimidine, triazine, a nitrogen atom selected from the group consisting of piperidine Contact Yobipipe Rajin, X 4
  • X 4 Each represents a divalent organic group, and a plurality of X 4 may be the same or different.
  • a diamine having two primary amino groups and a nitrogen atom other than the primary amino group in the molecule such as a compound represented by:
  • R 7 is a divalent organic group selected from the group consisting of —O—, 1 COO—, 1 OC0—, 1 NHCO_, —CONH—, and 1 CO—
  • 8 is a teroid skeleton, a trifluoromethylphenyl group, a trifluoromethoxyphenyl group, a monovalent organic group having a fluorophenyl group or an alkyl group having 6 to 30 carbon atoms.
  • each R 9 is a hydrocarbon group having carbon numbers:! To 12, and a plurality of R 9 may be the same or different, and p is each 1 to 3 is an integer, and q is an integer of 1 to 20.)
  • Diaminoorganosiloxanes such as compounds represented by:
  • the benzene ring of the compound represented by each of the above aromatic diamines, the above formulas (D—I) to (D—III) and (D-1) to (D-5) has one or more carbon atoms. It may be substituted with an alkyl group of 1 to 4 (preferably a methyl group). These diamines can be used alone or in combination of two or more.
  • 1,3-bis (3-aminopropyl) -tetramethyldisiloxane force S is preferable.
  • the proportion of tetracarboxylic dianhydride and diamine used in the polyamic acid synthesis reaction is such that the acid anhydride group of tetracarboxylic dianhydride is 0.2 to 1 equivalent to 1 equivalent of amino group contained in diamine. A ratio of 2 equivalents is preferable, and a ratio of 0.3 to 1.2 equivalents is more preferable.
  • the polyamic acid synthesis reaction is preferably performed in an organic solvent, preferably at a temperature of 20 to 150 ° C, more preferably at a temperature of 0 to 100 ° C, preferably 1 to 48 hours. More preferably, it is performed for 2 to 10 hours.
  • the organic solvent is not particularly limited as long as it can dissolve the synthesized polyamic acid.
  • N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethyl Aprotic polar solvents such as formamide, N, N-dimethylimidazolidinone, dimethyl sulfoxide, aptilolactone, tetramethylurea, hexamethylphosphortriamide; m-cresol, xylenol, phenol, halogen Examples thereof include phenol solvents such as phenol.
  • the amount of organic solvent used (a) is such that the total amount of tetracarboxylic dianhydride and diamine (b) is 0.1 to 30% by weight with respect to the total amount of the reaction solution (a + b). Preferably it is.
  • the usage-amount (a) of the said organic solvent means the usage-amount of the total of an organic solvent and a poor solvent.
  • organic solvent alcohol, ketone, ester, ether, octagenated hydrocarbon, hydrocarbon, etc., which are generally believed to be poor solvents for polyamic acid, are used in combination as long as the polyamic acid to be produced does not precipitate. be able to.
  • such poor solvents include, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol mono Methyl ether, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate Chill, methyl methyl propionate, ethyl propionate, ethyl oxalate, jetyl malonate, jetyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol mono n-propyl ether, ethylene glycol mono i-propyl Ether, Ethylene glycol n_butyl
  • the use ratio can be appropriately set within the range in which the produced polyamic acid does not precipitate. It is 0% by weight or less, more preferably 20% by weight or less.
  • reaction solution obtained by dissolving polyamic acid is obtained.
  • This reaction solution may be used as it is for the preparation of the liquid crystal aligning agent, may be used for the preparation of the liquid crystal aligning agent after isolating the polyamic acid contained in the reaction solution, or the isolated polyamic acid may be purified.
  • Polyamic acid is isolated by pouring the reaction solution into a large amount of poor solvent to obtain a precipitate, and drying the precipitate under reduced pressure, or by distilling the reaction solution under reduced pressure using an evaporator. Can be performed.
  • the polyamic acid can be purified by a method in which the polyamic acid is dissolved again in an organic solvent and then precipitated in a poor solvent, or a method in which the step of evaporating under reduced pressure in an evaporator is performed once or several times.
  • the polyimide can be synthesized by dehydrating and ring-closing a polyamic acid obtained by reacting tetracarboxylic dianhydride and diamine.
  • Examples of the tetracarboxylic dianhydride used for the synthesis of the polyimide include the same compounds as the tetra-force sulfonic acid dianhydride used for the synthesis of the polyamic acid described above.
  • tetracarboxylic dianhydride used for the synthesis of the polyimide in the present invention, it is preferable to use a tetracarboxylic dianhydride including an alicyclic tetracarboxylic dianhydride.
  • Particularly preferred alicyclic tetracarboxylic dianhydrides include 2, 3, 5 _trioxyloxycyclopentylacetic acid dianhydride, 1, 3, 3 a, 4, 5, 9 b-hexahydro-mono 5- ( Tetrahydro-2,5-dioxo-3-furanyl) —naphtho [1, 2—c] furan 1,3-dione, 1, 3, 3 a, 4, 5, 9b —hexahydro—8-methyl-5- (tetrahydro 1 2,5-dioxo 3-furanyl) 1 naphtho [1, 2— c] furan 1, 3-dione, 3-oxabicyclo [3.2.1] octane 1, 2, 4-dione _6—spiro 1 '-(Tetrahydrofuran-1,2,5'-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -1-3-methyl-3-cyclohexene-1
  • an alicyclic tetracarboxylic dianhydride and other tetracarboxylic dianhydrides may be used in combination.
  • the ratio of the alicyclic tetracarboxylic dianhydride in the total tetra force sulfonic dianhydride is preferably 10 mol% or more, more preferably 50 mol% or more.
  • Examples of the diamine used for the synthesis of the polyimide include the same compounds as the diamine used for the synthesis of the polyamic acid described above.
  • a diamine containing a diamine represented by the above formula (D-III) Preferred examples thereof include dodecanoxy 2,4-diaminobenzene, pen decanoxy 2,4-diaminobenzene, hexadecanoxy-1,2,4-diaminobenzene, among the compounds represented by the above formula (D-III), Decanoxy-2,4-diaminobenzene, dodecanoxy-1,2,5-diaminobenzene, Pen Decanoxy 2,5-diaminobenzene, Hexadecanoxy-2,5-diaminobenzene, Octanodecanoxy _ 2,5-diaminobenzene And compounds represented by the formulas (D-8) to (D-16).
  • the diamine represented by the above formula (D-III) may be used in combination with other diamines.
  • the other diamines preferred are p-phenylenediamine, 4, 4, diaminodiphenylbenzene, 4, 4, diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2, 2, 1-dimethyl-4,4, -diaminobiphenyl, 2,2, -ditrifluoromethyl-4,4'-diaminobiphenyl, 2,7-diaminofluorene, 4,4, -diaminodiphenyl ether, 2 , 2-bis [4- (4-aminophenoxy) phenyl] propane, 9, 9-bis (4-aminophenyl) fluorene, 2,2bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2, 2-bis (4-aminophenyl) he
  • the diamine represented by the above formula (D-III) is preferably 0.5% by weight or more based on the total diamine. Particularly preferably, 1% by weight or more is used.
  • the polyimide dehydration cyclization reaction that can be used in the present invention includes (i) a method in which polyamic acid is heated, or (ii) polyamic acid is dissolved in an organic solvent, and a dehydrating agent and a dehydration ring closure catalyst are added to the solution. However, it can be carried out by a heating method if necessary.
  • the reaction temperature in the method of heating the polyamic acid of U) is preferably 50 to 20 ° C., more preferably 60 to 170 ° C. If the reaction temperature is less than 50 ° C, the dehydration ring-closing reaction does not proceed sufficiently, and if the reaction temperature exceeds 200 ° C, the molecular weight of the resulting polyimide may decrease.
  • the reaction time in the method of heating the polyamic acid is preferably 0.5 to 48 hours, more preferably 2 to 20 hours.
  • an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride is used as the dehydrating agent. It can.
  • the amount of the dehydrating agent used is preferably a force S of 0.01 to 20 moles per mole of the amic acid structure.
  • tertiary amines such as pyridine, collidine, lutidine, and triethylamine can be used. However, it is not limited to these.
  • the amount of the dehydration ring-closing catalyst used is preferably from 0.01 to 10 mol per 1 mol of the dehydrating agent used.
  • the organic solvent used for the dehydration ring-closing reaction include the organic solvents exemplified as those used for the synthesis of polyamic acid.
  • the reaction temperature of the dehydration cyclization reaction is preferably 0 to 180 ° C, more preferably 10 to 1550 ° C, and the reaction time is preferably 0.5 to 24 hours. More preferably, it is 1 to 10 hours.
  • the polyimide obtained by the above method (i) may be used for the preparation of the liquid crystal aligning agent as it is, or may be used for the preparation of the liquid crystal aligning agent after purification.
  • a reaction solution containing polyimide is obtained.
  • This reaction solution may be used as it is for the preparation of the liquid crystal aligning agent, or may be used for the preparation of the liquid crystal aligning agent after removing the dehydrating agent and the dehydrating ring-closing catalyst from the reaction solution.
  • it may be used for preparing a liquid crystal aligning agent, or may be used for preparing a liquid crystal aligning agent after purifying the isolated polyimide.
  • a method such as solvent replacement can be applied.
  • the isolation and purification of the polyimide can be performed by performing the same operations as described above as the method for isolating and purifying the polyamic acid.
  • the polyimide that can be used in the present invention may be one in which all of the amic acid structure has been dehydrated, and the partial force of the amic acid structure s dehydration and ring closure, and the imide ring structure and the amic acid structure and force S may coexist.
  • the imidation ratio in the polyimide that can be used in the present invention is preferably 80% or more, and more preferably 85% or more.
  • the “imidation rate” is a percentage of the number of imide rings to the total number of amic acid structures and the number of imide rings in the polymer. At this time, a part of the imide ring may be an isoimide ring.
  • Imidization rate was dissolved polyimide in a suitable deuterated solvent (e.g. deuterated dimethyl sulfoxide), the results of measurement of 1 .eta. NMR at room temperature using tetramethylsilane as a reference substance, the following equation (i) Can be requested.
  • Imidization rate (%) (1 ⁇ 1 ⁇ 2 ⁇ ⁇ ) X 1 0 0 (i).
  • a 1 is the peak area derived from protons of NH groups appearing around 10 ppm in chemical shift
  • a 2 is the peak area derived from other protons
  • ⁇ is the precursor of polyimide. This is the ratio of the number of other protons to one proton in the base (polyamic acid).
  • the polyamic acid and the polyimide may be of a terminal modified type with a controlled molecular weight.
  • Such a terminal-modified type can be synthesized by adding a molecular weight regulator to the reaction system when synthesizing the polyamic acid.
  • the molecular weight regulator include an anhydride, a monoamine compound, a monoisocyanate compound, and the like.
  • the acid monoanhydride for example, maleic anhydride, anhydrous fuuric acid, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride And n-hexadecyl succinic anhydride.
  • Monoamine compounds include, for example, aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-year-old cutylamine, n-nonylamine, n-decylylamine, n-undecylamine. , N-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecyl J-reamine, n-hexadecylamine, n-heptodecylamine, n-aged decadecamine, n-eicosylamine, and the like.
  • Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.
  • the molecular weight regulator is preferably 20 parts by weight or less, more preferably 5 parts by weight or less, with respect to 100 parts by weight of the total of tetracarboxylic dianhydride and diamine used when synthesizing the polyamic acid. Used.
  • the polyamic acid or polyimide obtained as described above should have a solution viscosity of 20 to 800 mPa's when a 10% by weight solution is used. It is more preferable that it has a solution viscosity of 0 to 500 mPa's.
  • the solution viscosity (mPa ⁇ s) of the above polymer is an E-type rotational viscometer for a polymer solution having a concentration of 10% by weight using a good solvent of the polymer (for example, N-methyl-2-pyrrolidone). This is the value measured at 25 ° C using. [Other polysiloxanes]
  • the polysiloxane having a repeating unit represented by the above formula (S-2), at least one selected from the group consisting of a hydrolyzate thereof and a condensate of the hydrolyzate (other polysiloxanes) includes the above formula.
  • X 2 is preferably a polyorganosiloxane in which X 2 is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms.
  • Such other polysiloxane is, for example, at least one silane compound selected from the group consisting of an alkoxysilane compound and an octarogenated silane compound (hereinafter also referred to as “raw silane compound”), preferably an appropriate organic solvent. It can be synthesized by hydrolysis or hydrolysis / condensation in the presence of water and a catalyst.
  • raw material silane compounds that can be used here include tetramethoxysilane, tetraethoxysilane, tetra-n_propoxysilane, tetra-iso-hydroxysilane, tetra-n-hydroxysilane, tailor sec-hydroxysilane, tetra-tert- Butoxysilane, Tetrachlorosilane; Methyltrimethoxysilane, Methyltriethoxysilane, Methyltri-n-Propoxysilane, Methyltri-iso-Propoxysilane, Methyltri-n-Butoxysilane, Methyl _sec-Butoxysilane, Methyltri-tert-Butoxysilane , Methyl triethoxysilane, ethyl n _propoxy silane, ethyl tri-iso-propoxy silane, ethyl n-butoxy si
  • tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, Dimethyldimethoxysilane, dimethyljetoxysilane, trimethylmethoxysilane, or trimethylethoxysilane is preferred.
  • organic solvents examples include alcohol compounds, ketone compounds, amide compounds, ester compounds, and other aprotic compounds. These can be used alone or in combination of two or more.
  • Examples of the alcohol compound include methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i 1-pen-butanol, 2-methylbutanol, sec 1-pen-butanol, t-penbutanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec —Hep Yunol, Hep Yunol 1, n—Ok Yunol, 21—Ethyl Hexanol, sec —Ok Yunol, n—Nonyl Alcohol, 2,6-Dimethyl Hep Yunol—4, n—Dekanol , Sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl
  • ketone compound examples include acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, jetyl ketone, methyl i-butyl ketone, methyl n-pentyl ketone, ethyl n-butyl ketone, methyl n-hexyl ketone, G-i-Butylketone, Trimethylnonanone, Diclonal Hexanone, 2 Monohexanone, Methylcyclohexanone, 2,4_Penpentenedione, acetonylacetone, acetophenone, fenchon and other monoketone compounds ;
  • amide compound examples include formamide, N-methylformamide, N, N-dimethylformamide, N_ethylformamide, N, N-jetylformamide, acetoamide, N-methylacetamide, and N, N-dimethylacetamide.
  • These amide compounds may be used alone or in combination of two or more.
  • ester compound examples include jetyl carbonate, ethylene carbonate, propylene carbonate, jetyl carbonate, methyl acetate, ethyl acetate, aptilolactone, valerolactone, n-propyl acetate, i-propyl acetate, and n-butyl acetate.
  • Examples of the other aprotic compounds include acetonitrile, dimethyl sulfoxide, N, N, N ′, N′-tetraethylsulfamide, hexamethylphosphoric triamide, N-methylmorpholone, N-methylpyrrole, N-ethylpyrrole, N-methyl- ⁇ 3-pyrroline, N-methylbiperidine, N-ethylpiperidine, N, N-dimethylbiperazine, N-methylimidazole, N-methyl-4-piperidone, N ⁇ Methyl-2-piperidone, N-methyl-1-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyltetrahydro-2 (1 H) —Pyrimidinone.
  • polyhydric alcohol compounds include polyhydric alcohol compounds, partial ethers or ester compounds of polyhydric alcohol compounds are particularly preferred.
  • the amount of water used in the synthesis of other polysiloxanes is preferably 0.5 to 100 moles with respect to 1 mole of the total amount of alkoxyl groups and octalogen atoms in the raw material silane compound. More preferably, it is 1 to 30 mol, and further preferably 1 to 1.5 mol.
  • the metal chelate compound examples include triethoxy mono (acetyl acetonate) titanium, ri-n-propoxy mono (acetyl cetate) titanium, and i-propoxy mono (acetyl cetonate).
  • Titanium Tri-n-Butoxy.Mono (Acetylacetana) Titanium, Tree sec-Butoxy-Mono (Acetylasetonate) Titanium, Tri-t-Butoxy 'Mono (Acetylase Toner) Titanium, Jet Xi-bis (Acetyl asetonate) Titanium, gin propoxy bis (Acetyl asetonate) Titanium, zi i-propoxy bis (Acetyl asetonate) Titanium, di-n-butoxy 'Bis (acetylacetate) Titanium, G sec-Butoxy bis (Acetylasetonate) Titanium, Di-t-butoxy bis (Acetyl) Settonate) Titanium, Monoethoxy Tris (
  • Examples thereof include aluminum chelate compounds such as tris (acetyl acetate) aluminum and tris (ethyl acetate 1) aluminum.
  • the organic acid include acetic acid, propionic acid, butanoic acid, pentanoic acid, and Xanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallic acid, butyric acid, meritic acid, arachidonic acid, shikimic acid, 2-ethylhexan Acid, oleic acid, stearic acid, linoleic acid, linoleic acid, salicylic acid, benzoic acid, P-aminobenzoic acid, P-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, dichloroace
  • Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.
  • organic base examples include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, and monomethylethanolamine.
  • Triethanolamine diazabicycloocrane, diazabicyclononane, diazabicycloundecene, tetramethylammonium hydride mouthpiece, and the like.
  • alkali metal compound examples include sodium hydroxide, sodium 7 oxidation power, barium hydroxide, and 7K calcium carbonate.
  • These catalysts may be used alone or in combination of two or more.
  • a metal chelate compound, an organic acid or an inorganic acid is preferable, and a titanium clear compound or an organic acid is more preferable.
  • the amount of the catalyst used is preferably 0.001 to 10 parts by weight, more preferably 0.01 to 1 part by weight, based on 100 parts by weight of the raw material silane compound.
  • Water added during the synthesis of other polysiloxanes can be added intermittently or continuously in the raw material silane compound or in a solution of the silane compound dissolved in an organic solvent.
  • the catalyst may be added in advance to a raw material silane compound or a solution in which the silane compound is dissolved in an organic solvent, or may be dissolved or dispersed in the added water.
  • the reaction temperature in the synthesis of other polysiloxane is preferably 0 to 10 ° C., more preferably 15 to 80 ° C.
  • the reaction time is preferably 0.5 to 24 hours, more preferably 1 to 8 hours.
  • the content of the other polymer is as follows: Radiation sensitive polyorganosiloxane 100 It is preferable that it is 10 0,000 parts by weight or less with respect to parts by weight. The more preferable content of the other polymer varies depending on the type of the other polymer.
  • liquid crystal aligning agent of the present invention contains at least one polymer selected from the group consisting of radiation-sensitive polyorganosiloxane, polyamic acid and polyimide
  • the total amount of polyamic acid and polyimide with respect to 100 parts by weight of radiation-sensitive polyorganosiloxane is 10 to 5 parts by weight, and further 200 parts by weight to 200 parts by weight. Force S is preferred.
  • the liquid crystal aligning agent of the present invention contains a radiation-sensitive polyorganosiloxane and another polysiloxane
  • the more preferred use ratio of both is the cinnamic acid-containing polysiloxane of the present invention 100 parts by weight.
  • the amount of other polysiloxanes relative to is from 100 to 2,000 parts by weight.
  • the type of the other polymer is at least selected from the group consisting of polyamic acid and polyimide.
  • One polymer or another polysiloxane is preferred.
  • the curing agent and the curing catalyst can be contained in the liquid crystal aligning agent of the present invention for the purpose of strengthening the crosslinking reaction of the radiation-sensitive polyorganosiloxane
  • the accelerator can be contained in the liquid crystal aligning agent of the present invention for the purpose of accelerating the curing reaction controlled by the curing agent.
  • a curing agent generally used for curing a curable compound having an epoxy group or a curable composition containing a compound having an epoxy group can be used.
  • examples thereof include polyvalent carboxylic acid anhydrides and polyvalent carboxylic acids.
  • polyvalent carboxylic acid anhydride examples include anhydrides of hexanetricarboxylic acid and other polyvalent carboxylic acid anhydrides.
  • cyclohexane carboxylic anhydrides include, for example, cyclohexane-1,3,4,1tricarboxylic acid-3,4monoanhydride, cyclohexane-1,3,5-tricarboxylic acid 1,3,5-anhydride, cyclohexane-1,2,3-tricarboxylic acid 1,2,3 monoanhydride, etc.
  • Other polyhydric carboxylic acid anhydrides include, for example, 4 -Methyltetrahydrophthalic anhydride, methyl nadic anhydride, dodecenyl succinic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, formula (5)
  • r is an integer of 1 to 20
  • Examples of the curing catalyst include an antimony hexafluoride compound and a phosphorous hexafluoride compound. And aluminum triacetyl cetate can be used. These catalysts can catalyze the cationic polymerization of epoxy groups by heating.
  • Examples of the curing accelerator include imidazole compounds;
  • Organometallic compounds such as zinc octylate, tin octylate, aluminum acetylethylacetone complexes;
  • Boron compounds such as boron trifluoride and triphenyl borate; metal halides such as zinc chloride and stannic chloride,
  • High melting point dispersion type latent curing accelerators such as dicyandiamide and amine addition accelerators such as adducts of amine and epoxy resin;
  • Microphone mouth type latent curing accelerator with a polymer coated surface such as quaternary phosphonium salt
  • Examples include high temperature dissociation type thermal cationic polymerization type latent hardening accelerators such as Lewis acid salts and Blensted acid salts. ⁇ Epoxy compound>
  • the said epoxy compound can be used from a viewpoint of improving the adhesiveness with respect to the substrate surface of the liquid crystal aligning agent of this invention.
  • epoxy compound examples include ethylene dalycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene dalycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1 , 6 monohexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2 dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanehexane, N, N ,, ', N'-tetraglycidyl m-xylenediamine, 1,3-bis (N, N-diglycidylamino Methyl) cyclohexane, N, ⁇ , ⁇ ', N' —tetraglycidyl 1,4 ′ —d
  • Examples of the functional silane compounds include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyl trimethoxysilane, 2-aminopropyltriethoxysilane, ⁇ — ( 2-aminoethyl) —3-Aminopropyltrimethoxysilane, ⁇ — (2-aminoethyl) -3-7 Minopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane , ⁇ ⁇ ⁇ -Ethoxycarbonyl 3-aminoaminotrimethoxysilane, ⁇ -ethoxycarbonyl 3-aminopromine, ⁇ ⁇ -trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl mono-1,4,7-triazadecane , 1 0-trie
  • surfactant examples include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, silicone surfactants, polyalkylene oxide surfactants, and fluorine-containing surfactants. it can.
  • the content is preferably 10 parts by weight or less, more preferably 1 part by weight with respect to 100 parts by weight of the entire liquid crystal aligning agent. Less than parts by weight.
  • the liquid crystal aligning agent of the present invention contains a radiation-sensitive polyorganosiloxane as an essential component, and additionally contains other components as necessary.
  • each component is an organic solvent. It is prepared as a dissolved solution composition.
  • the organic solvent that can be used to prepare the liquid crystal aligning agent of the present invention include those that dissolve the radiation-sensitive polyorganosiloxane and other optional components and do not react with them. .
  • the organic solvent that can be preferably used in the liquid crystal aligning agent of the present invention varies depending on the type of other polymer that is optionally added.
  • the liquid crystal aligning agent of the present invention contains at least one polymer selected from the group consisting of radiation-sensitive polyorganosiloxane, boric acid and polyimide
  • synthesis of polyamic acid The solvent illustrated as what is used for reaction can be mentioned.
  • the poor solvents exemplified as those that can be used together in the synthesis reaction of polyamic acid can be appropriately selected and used together.
  • Particularly preferred organic solvents that can be used in this case include N-methyl-2-pyrrolidone, alpha-pyrolactone, r-ptylolactam, N, N-dimethylformamide, N, N-dimethylacetoa.
  • the liquid crystal aligning agent of the present invention contains only a radiation-sensitive polyorganosiloxane as a polymer, or contains a radiation-sensitive polyorganosiloxane and another polysiloxane.
  • preferable organic solvents include: 1-Ethoxy-2-propanol, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monoacetate, dipropylene glycol methyl ether, dipropylene diamine.
  • n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate and the like can be mentioned.
  • the solid content concentration in the liquid crystal aligning agent of the present invention (the ratio of the components other than the solvent in the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) is selected in consideration of viscosity, volatility, and the like. .
  • a preferable solid content concentration is in the range of 1 to 10% by weight. That is, the liquid crystal aligning agent of the present invention is applied to the substrate surface to form a coating film that becomes a liquid crystal aligning film. If the solid content concentration is less than 1% by weight, When the solid content concentration exceeds 10% by weight, it is difficult to obtain a good liquid crystal alignment film. In addition, the viscosity of the liquid crystal aligning agent increases, resulting in poor coating properties.
  • the particularly preferable solid concentration range varies depending on the method used when applying the liquid crystal aligning agent to the substrate.
  • a range force S of 1.5 to 4.5% by weight S is particularly preferable.
  • the solid content concentration is in the range of 3 to 9% by weight, and thereby the solution viscosity is in the range of 12 to 5 OmPa ⁇ s.
  • the solid content concentration is in the range of 1 to 5% by weight, and the solution viscosity is in the range of 3 to 15 mPa ⁇ s.
  • the temperature at which the liquid crystal aligning agent of the present invention is prepared is preferably 0 ° C. to 200 ° C., more preferably 20 ° C. to 60 ° C. ⁇ Method for forming liquid crystal alignment film>
  • the liquid crystal aligning agent of this invention can be used conveniently in order to form a liquid crystal aligning film by the photo-alignment method.
  • the liquid crystal alignment film of the present invention is applied on a substrate.
  • a method of forming a coating film by coating and then imparting liquid crystal alignment ability to the coating film by a photo-alignment method can be mentioned.
  • the liquid crystal aligning agent of the present invention is appropriately applied to the transparent conductive film side of the substrate provided with the patterned transparent conductive film, for example, a roll coating method, a spinner method, a printing method, an ink jet method, or the like.
  • the film is applied by a method, for example, heated at a temperature of 40 to 25 ° C. for 0.1 to 120 minutes to form a coating film.
  • the thickness of the coating film is preferably from 0.01 to 1 xm, more preferably from 0.05 to 0.5 m, as the thickness after removal of the solvent.
  • glass such as flow glass, soda glass, transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethylene tersulfone, polycarbonate, poly (alicyclic olefin), etc. are used. be able to.
  • Examples of the transparent conductive film NESA film made of S N_ ⁇ 2, I n 2 ⁇ 3 - or the like can be used IT_ ⁇ film consisting of S N_ ⁇ 2.
  • IT_ ⁇ film consisting of S N_ ⁇ 2.
  • a photo-etching method or a method using a mask when forming the transparent conductive film is used.
  • the coating film is irradiated with linearly polarized light or partially polarized radiation or non-polarized radiation, and in some cases, a heat treatment is preferably performed at a temperature of 150 to 250, preferably for 1 to 120 minutes.
  • a liquid crystal alignment film can be provided by imparting liquid crystal alignment ability.
  • the radiation for example, ultraviolet rays including light having a wavelength of 150 to 80 nm and visible light can be used, and ultraviolet rays including light having a wavelength of 300 to 400 nm are preferable. Ultraviolet rays containing light having a wavelength of 300 nm or more and less than 3 65 nm are more preferable.
  • the liquid crystal aligning agent of the present invention does not cause a photoreaction by light in a long wavelength region having a wavelength of 365 nm or longer, the liquid crystal panel can be produced without any trouble in the process. There is also an advantage of long-term stability against backlight light during use.
  • the irradiation can be from a direction perpendicular to the substrate surface or from an oblique direction to provide a pretilt angle, or These may be combined.
  • the direction of irradiation needs to be oblique.
  • the irradiation dose is preferably 1 J / m 2 or more and less than 10 and less than OOOJ Zm 2 , more preferably 10 to 3, 0 00 J / m 2 .
  • a radiation dose of 10 0, 0 00 J Zm 2 or more was required.
  • the liquid crystal aligning agent of the present invention is used, a good liquid crystal alignment is possible even when the radiation irradiation amount in the photo-alignment method is 3, 00 0 J / m 2 or less, and further 1, 0 0 0 J Jm 2 or less. Can contribute to the reduction of the manufacturing cost of liquid crystal display elements. '
  • the liquid crystal display element formed using the liquid crystal aligning agent of this invention can be manufactured as follows, for example.
  • a pair of (two) substrates on which a liquid crystal alignment film is formed as described above is prepared, and these liquid crystal alignment films are made to face each other so that the polarization direction of the irradiated linearly polarized radiation becomes a predetermined angle.
  • a liquid crystal cell is constructed by sealing the peripheral part between them with a sealing agent, injecting and filling liquid crystal, and sealing the liquid crystal injection port. Next, it is desirable to heat the liquid crystal cell to a temperature at which the liquid crystal used takes an isotropic phase, and then cool it to room temperature to remove the flow alignment at the time of injection.
  • a polarizing plate is bonded to both surfaces so that the polarization direction forms a predetermined angle with the orientation axis of the liquid crystal alignment film of the substrate, whereby a liquid crystal display element can be obtained.
  • liquid crystal alignment film When the liquid crystal alignment film is horizontally aligned, the angle formed by the polarization direction of the irradiated linearly polarized radiation and the angle between each substrate and the polarizing plate are adjusted on the two substrates on which the liquid crystal alignment film is formed.
  • a liquid crystal display element having a TN type or S TN type liquid crystal cell can be obtained.
  • the cell when the liquid crystal alignment film is vertically aligned, the cell is configured such that the directions of easy alignment axes of the two substrates on which the liquid crystal alignment film is formed are parallel to each other.
  • the sealing agent for example, an aluminum oxide sphere as a spacer and an epoxy resin containing a curing agent can be used.
  • liquid crystal for example, a nematic liquid crystal, a smectic liquid crystal, or the like can be used.
  • nematic liquid crystal power having positive dielectric anisotropy S is preferable, for example, biphenyl liquid crystal, phenyl cyclohexane liquid crystal, ester liquid crystal, terphenyl liquid crystal Biphenyl cyclohexane liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal, bicyclooctane liquid crystal, and cubane liquid crystal are used.
  • cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonate, and cholesteryl carbonate; such as “C—15”, “CB—15” (made by Merck), etc.
  • Chiral agent ferroelectric liquid crystal such as p-decyloxybenzylidene-p-amino-2-methyl cinnamate may be further added and used.
  • a nematic type liquid crystal having negative dielectric anisotropy is preferable.
  • a dicyanobenzene type liquid crystal, a pyridazine type liquid crystal, a Schiff base type liquid crystal, an azoxy type liquid crystal, a biphenyl type liquid crystal, A phenylcyclohexane liquid crystal or the like is used.
  • a polarizing film As a polarizing plate used outside the liquid crystal cell, a polarizing film called an “H film” in which polyvinyl alcohol is stretched and absorbed while absorbing iodine is sandwiched between cellulose acetate protective films, or the H film itself.
  • the polarizing plate which consists of can be mentioned.
  • the liquid crystal display element of the present invention thus produced is excellent in various properties such as display characteristics and long-term reliability.
  • the weight average molecular weight is a polystyrene equivalent value measured by gel permeation chromatography under the following conditions.
  • Polyorganosiloxane EPS 1-2 and 3 having an epoxy group were obtained as viscous transparent night bodies in the same manner as in Synthesis Example 1 (1) except that the charged raw materials were as shown in Table 1.
  • Table 1 shows the weight average molecular weight Mw and epoxy equivalent of this polyorganosiloxane EPS.
  • the abbreviations of the raw material silane compounds have the following meanings, respectively.
  • ECETS 2 (3,4-epoxy hexyl) ethyltrimethoxysilane
  • PTMS phenyltrimethoxysilane
  • a 50 OmL eggplant flask equipped with a thermometer and a dropping funnel was charged with 4, 4, 5, 5, 5-pentenfluoropenol alcohol 18 g, triethylamine 11.1 g and tetrahydrofuran 5 OmL, and ice-cooled.
  • a solution consisting of 21 g of trimellitic anhydride chloride and 20 OmL of tetrahydrofuran charged in the dropping funnel was added dropwise over 30 minutes, and the mixture was further stirred for 2 hours to carry out the reaction.
  • a 1,000 OmL eggplant flask equipped with a thermometer and a dropping funnel was charged with 39 g of cholesterol, 11.1 g of triethylamine and 20 OmL of toluene, and cooled with ice.
  • a solution composed of 21 g of trimellitic anhydride chloride and 20 OmL of tetrahydrofuran charged in the dropping funnel was added dropwise over 30 minutes, and the reaction was performed with stirring for 2 hours.
  • reaction mixture was extracted by adding ethyl acetate, and the extract was washed successively with dilute hydrochloric acid and water, then dried over magnesium sulfate, concentrated, and recrystallized with ethyl acetate to give compound (2 — 6— 1A) was obtained in an amount of 14 g.
  • a 300 mL eggplant flask equipped with a dropping port was charged with 12 g of the compound (2-6-1A) obtained above and 7 OmL of N, N-dimethylacetamide and stirred at room temperature for 1 hour.
  • 4, 4, 4-trifluoro-1, 1 g and N, N-dimethylacetamide 3 OmL were added dropwise over 30 minutes, and the reaction was allowed to proceed at room temperature for 8 hours.
  • the reaction mixture was extracted with ethyl acetate, and the extract was washed three times with water, then dried over magnesium sulfate, concentrated, purified on a silica column, and recrystallized with ethanol. 12 g of crystals of the compound (2-6-1) were obtained.
  • Pyromellitic dianhydride as a tetracarboxylic dianhydride 109 g (0.50 molar equivalent) and 1, 2, 3, 4-cyclobutanetetracarboxylic dianhydride 98 gg ((00 .. 5500 equivalents of momol)) 44, 44--didiaamiminonodifuheinilrue 1ttellulu as well as dijamimin and 220000 gg ((11. Equivalent amount of 00 momol)) was dissolved and dissolved in NN——Metetyllulu 22——Pipirololyridone 22 ,, 229900 gg and reacted at 4400 ° CC for 33 hours.
  • the solution viscosity of the polypolyamimite succinate solution here was 113355 mm PP aa... Ss. . Synthesis example PPAA-33
  • Tetetrala Power Lulupoponate Non-anhydride 11, 22, 22, 33, 44——Siclochlorobutabutane Tetetotralacar Carbobo 2200 Nini Anhydrate Anhydrous 119966 gg ((11..00 equimolar equivalent amount)) and didiaminmin 44, 44,, ——diadiaminino diphne fujie rulue 1 teralulu 220000 gg ((11 .. 00 Equivalent amount of momol)) was dissolved in NN——Memethyryl Loan 22——Pypyrrololylidone, 22, 224466 gg, and reacted at 4400 ° CC for 44 hours.
  • 2,3,5_Tricarboxic pentyl acetate dianhydride as tetracarboxylic dianhydride 112g (0.50 mol) and 1, 3, 3 a, 4, 5, 9b—Hexahydro 8— Methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) naphtho [1,2-c] furan 1,3-dione 157 g (0.50 mol), diammine P-phenylene diamamine 96 g (0 89 mole), 25 g (0.10 mol) of bisaminopropylpyrutetramethyldisiloxane and 13 g (0.020 mol) of cholestane 13 g (0.020 mol) and N-octadecylamine as monoamine 8.1 g (0.030 mol) was dissolved in 960 g of N-methyl-2-pyrrolidone and reacted at 60 ° C for 6 hours.
  • N-methyl-2-pyrrolidone 2,700 g was added to the obtained polyamic acid solution, 396 g of pyridine and 306 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 at 4 hours. After the dehydration and ring closure reaction, the solvent in the system was replaced with new N-methyl 2-pyrrolidone, so that a solution containing 9.0% by weight of polyimi F (PI-3) with an imidation ratio of about 89% was obtained. 3,500 g was obtained.
  • PI-3 polyimi F
  • the epoxy obtained in Synthesis Example 1 (1) above was 5.0 g of polyorganosiloxane EPS-1 having a xy group, cinnamic acid derivative (1) compound obtained in Synthesis Example 2 (1) above (2-1-1) 6.7 g (with epoxy group) Equivalent to 1% of 5 Omo with respect to the epoxy group of the polyorganosiloxane, and 0.5 g of tetraptylammonium bromide, and N, N-dimethylacetate so that the solid content concentration becomes 20% by weight. ⁇ amide was added and reacted at 120 ° C for 10 hours. After completion of the reaction, methanol is added to form a precipitate.
  • a solution obtained by dissolving the precipitate in ethyl acetate is washed with water three times, and then the solvent is distilled off to remove the radiation-sensitive polyorganosiloxane S. — 8.4 g of A r IE-1 was obtained as a white powder.
  • the weight average molecular weight Mw of the radiation-sensitive polyorganosiloxane S-ArlE-1 was 28,100.
  • Example A r IE-1 Example A r I was used except that the type of polyorganosiloxane having an epoxy group and the type and amount of cinnamic acid derivative (1) were as shown in Table 2.
  • radiation-sensitive polyorganosiloxane S_Ar IE-2 to S-Ar IE_13 was synthesized.
  • Table 2 shows the weight average molecular weights Mw of these radiation-sensitive polyorganosiloxanes.
  • Ar IE-6 and 7 two cinnamic acid derivatives were used.
  • the solution was filtered through a filter having a pore diameter of 1 m to prepare a liquid crystal aligning agent A—A r I E—1.
  • This liquid crystal aligning agent A—A r I E — 1 was stored at 15 ° C. for 6 months. Viscosity measured with an E-type viscometer was measured before and after storage at 25 ° C. When the change rate of the solution viscosity before and after storage was less than 10%, the storage stability was evaluated as “good” and the change rate of 10% or more was evaluated as “storage failure”. As a result, the liquid crystal alignment agent A—A r IE—1 The storage stability was “good”. Examples Ar I E-15-31 and 33-52
  • Example A r IE-14 the type of radiation-sensitive polyorganosiloxane and the type and amount of other polymers are as shown in Table 3, respectively.
  • liquid crystal alignment agents A—Ar IE—2 to A-18 and A—ArIE—20 to 39 were prepared, respectively.
  • Table 3 T shows the storage stability evaluation results for each liquid crystal aligning agent, which were examined in the same manner as in Example A r I E-14.
  • a solution containing the other polysiloxane PS-1 obtained in the above synthesis example PS-11 was converted to PS-1, and an amount corresponding to 500 parts by weight was taken.
  • Radiation-sensitive polyorganosiloxane obtained with IE-1 S-A r I E-1 was added to obtain a solution having a solid concentration of 4.0% by weight.
  • a liquid crystal aligning agent A—A r IE-19 was prepared by filtering this solution through a filter having a pore size of 1 zm.
  • Table 3 shows the evaluation results of the storage stability of this liquid crystal aligning agent A—A r I E-19 examined in the same manner as in Example A r I E-14.
  • Example A r I E-32 instead of the radiation sensitive polyorganosiloxane S—A r IE—1, the radiation sensitive polyorganosiloxane S—Ar IE—9 obtained in the above Example A r I E-9
  • a liquid crystal aligning agent A_Ar IE-40 was prepared in the same manner as in Example A r IE-32 except that 100 parts by weight of was used, and the storage stability was examined. The evaluation results of storage stability are shown in Table 3.
  • Example A r I E-14 the types and amounts of other polymers were set as shown in Table 3, and the epoxy compounds shown in Table 3 were used in the amounts shown in Table 3. Otherwise, in the same manner as Example Ar IE-14, liquid crystal aligning agent A—A r I E-
  • Table 3 shows the evaluation results of the storage stability of these liquid crystal aligning agents, which were examined in the same manner as in Example Ar I E-14.
  • the liquid crystal aligning agent A—A r IE—1 prepared in the above example Ar I E-14 was applied onto the transparent electrode surface of the glass substrate with a transparent electrode made of an I TO film using a spinner, and 80 ° C. After pre-baking on a hot plate for 1 minute, heating was performed at 180 ° C. for 1 hour to form a coating film having a thickness of 0. By using a Hg_Xe lamp and a Grand Taylor prism on the surface of this coating film, polarized UV light including a 313 nm emission line, 1,000 J / m 2, was irradiated from a direction inclined by 40 ° from the normal of the substrate. A liquid crystal alignment film was formed by imparting performance.
  • An epoxy resin adhesive containing aluminum oxide spheres with a diameter of 5.5 xm is applied by screen printing to the peripheries of the surfaces of the pair of substrates on which the liquid crystal alignment film is formed.
  • the substrates were stacked and pressure-bonded in such a manner that they were heated at 150 ° C for 1 hour to thermally cure the adhesive.
  • a positive nematic liquid crystal (MLC, MLC-6221, containing a chiral agent) was injected and filled into the gap between the substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an epoxy adhesive. Furthermore, in order to remove the flow alignment during liquid crystal injection, this was heated at 150 ° C. for 10 minutes and then slowly cooled to room temperature.
  • the TN alignment type liquid crystal display element is bonded to both the outer surfaces of the substrate by bonding the polarizing plates so that their polarization directions are orthogonal to each other and parallel to the polarization direction of the liquid crystal alignment film.
  • a voltage of 5 V was applied to the liquid crystal display device manufactured as described above for 60 microseconds with a span of 167 milliseconds, and then the voltage holding ratio after 167 milliseconds from the application release was measured.
  • the measuring device used was VHR-1 manufactured by Toyo Corporation.
  • a TN alignment type liquid crystal display device was produced and evaluated in the same manner as in Example Ar IE-58 except that the liquid crystal alignment agents shown in Table 4 were used. The results are shown in Table 4.
  • the liquid crystal aligning agent A—A r IE—16 prepared in the above Example A r I E-29 was applied onto the transparent electrode surface of the glass substrate with a transparent electrode made of IT O film using a spinner, and 80 ° C. After pre-baking for 1 minute on a hot plate, heat the film in an oven with nitrogen replaced at 200 ° C for 1 hour (post-bake) to form a 0.1 urn film did. Next, the surface of the coating film was irradiated with polarized ultraviolet light (1,000 J / m 2) containing a 313 nm emission line from a direction tilted 40 ° from the normal of the substrate using a Hg-Xe lamp and a Grand Taylor prism. A membrane was obtained. The same operation was repeated to create a pair (two) of substrates having a liquid crystal alignment film.
  • polarized ultraviolet light 1,000 J / m 2
  • the polarizing plates are bonded to both the outer surfaces of the substrate so that the polarization directions thereof are orthogonal to each other and make an angle of 45 ° with the projection direction of the optical axis of the liquid crystal alignment film onto the substrate surface.
  • a vertically aligned liquid crystal display device was manufactured.
  • the liquid crystal alignment film was formed and the vertical alignment type liquid crystal display device was manufactured in the same manner as above except that the boss baking temperature in the formation of the liquid crystal alignment film was 250. Regarding the obtained liquid crystal display elements, those with good vertical alignment (showing uniform black display) were marked as “good” and those with light leakage were marked as “bad”. .
  • a vertical alignment type liquid crystal display device was produced and evaluated in the same manner as Example Ar IE-75 except that the liquid crystal alignment agents shown in Table 5 were used. The result was fifth.
  • the liquid crystal aligning agent of the present invention is a liquid crystal aligning agent having excellent liquid crystal aligning properties and electrical characteristics with a small amount of radiation irradiation, compared with a liquid crystal aligning agent conventionally known as a liquid crystal aligning agent to which a photo-alignment method can be applied.
  • a film can be formed. Furthermore, since the liquid crystal alignment film to be formed has high heat resistance, it is possible to manufacture a liquid crystal panel without any problems in the process.
  • liquid crystal display element when this liquid crystal alignment film is applied to a liquid crystal display element, the liquid crystal display element can be manufactured at a lower cost than before, and the obtained liquid crystal display element has excellent performance such as display characteristics and reliability. Become. Therefore, these liquid crystal display elements can be effectively applied to various devices, and can be suitably used for devices such as desk calculators, wristwatches, table clocks, counting display boards, grid processors, personal computers, and liquid crystal televisions. .

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Abstract

L'invention porte sur un agent d'alignement de cristal liquide contenant un polyorganosiloxane sensible au rayonnement et obtenu par réaction d'un composé représenté par la formule (1) avec un polyorganosiloxane spécifique ayant un groupe epoxy. (Dans la formule (1), RI représente un atome d'hydrogène ou un groupe organique monovalent ayant 1-40 atomes de carbone; RII, RIV et RV représentent indépendamment un atome d'hydrogène, un groupe méthyle, un groupe cyano ou un atome de fluor; et si RI est un atome d'hydrogène, RIII représente un groupe organique monovalent ayant 1-40 atomes de carbone, mais si RI est autre qu'un atome d'hydrogène, RIII représente un groupe carboxyle.)
PCT/JP2008/071759 2007-12-26 2008-11-25 Agent d'alignement de cristal liquide et procédé de formation de film d'alignement de cristal liquide WO2009081692A1 (fr)

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CN200880122740.5A CN101910928B (zh) 2007-12-26 2008-11-25 液晶取向剂以及液晶取向膜的形成方法
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JP6048117B2 (ja) * 2012-03-22 2016-12-21 Jsr株式会社 液晶配向剤、液晶配向膜、液晶表示素子及び液晶表示素子の製造方法
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JP4544439B2 (ja) 2010-09-15
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