WO2009069724A1 - Agent d'alignement de cristaux liquides, procédé de formation d'un film d'alignement de cristaux liquides et dispositif d'affichage à cristaux liquides - Google Patents

Agent d'alignement de cristaux liquides, procédé de formation d'un film d'alignement de cristaux liquides et dispositif d'affichage à cristaux liquides Download PDF

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Publication number
WO2009069724A1
WO2009069724A1 PCT/JP2008/071600 JP2008071600W WO2009069724A1 WO 2009069724 A1 WO2009069724 A1 WO 2009069724A1 JP 2008071600 W JP2008071600 W JP 2008071600W WO 2009069724 A1 WO2009069724 A1 WO 2009069724A1
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group
liquid crystal
acid
acetate
aligning agent
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PCT/JP2008/071600
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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 JP2009543859A priority Critical patent/JP4544438B2/ja
Priority to KR1020107009204A priority patent/KR101450942B1/ko
Priority to CN200880117770.7A priority patent/CN101874225B/zh
Publication of WO2009069724A1 publication Critical patent/WO2009069724A1/fr

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • 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
    • 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

Definitions

  • Patent application title Liquid crystal alignment agent, method of forming liquid crystal alignment film, and liquid crystal display device
  • the present invention relates to a liquid crystal alignment agent, a method of forming a liquid crystal alignment film, and a liquid crystal display device.
  • a nematic liquid crystal having a positive dielectric anisotropy is formed into a sandwich structure on 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, if necessary.
  • Liquid crystal cells such as TN (Tw isted nematic), STN (Super Twisted Nematic), and I PS (I n PIN S one S witching), which twist continuously from 0 to 360 ° Liquid crystal display devices having the above-mentioned structure are known (refer to JP-A-56-91277 and JP-A-1-120528).
  • liquid crystal alignment film In such a liquid crystal cell, in order to align liquid crystal molecules in a predetermined direction with respect to the substrate surface, it is necessary to provide a liquid crystal alignment film on the substrate surface.
  • the liquid crystal alignment film is usually formed by rubbing the surface of the organic film formed on the substrate surface with a cloth material such as rayon in one direction (rubbing method).
  • rubbing method a cloth material such as rayon in one direction
  • the liquid crystal alignment film aligns liquid crystal molecules at a predetermined angle with respect to the substrate surface. It is necessary to have pretilt angle characteristics.
  • the pretilt angle is usually given by inclining the incident direction of the radiation to be irradiated onto the substrate surface from the substrate normal.
  • a vertical (homeotropic) alignment mode in which liquid crystal molecules having negative dielectric anisotropy are vertically aligned to the substrate.
  • this operation mode when a voltage is applied between the substrates to tilt the liquid crystal molecules in the direction parallel to the substrate, the liquid crystal molecules are tilted from the normal direction of the substrate toward one direction in the substrate surface.
  • a method of providing a protrusion on the substrate surface a method of providing a stripe on a transparent electrode, and by using a rubbing alignment film, liquid crystal molecules are slightly directed from one direction normal to the substrate to one direction in the substrate surface. Methods such as pretilting are proposed.
  • the photoalignment method is known to be useful as a method of controlling the tilt direction of liquid crystal molecules in a liquid crystal cell of vertical alignment mode. That is, it is known that the tilt direction of liquid crystal molecules can be uniformly controlled at the time of voltage application by using a vertical alignment film provided with alignment control ability and pretilt angle expressivity by the photo alignment method (Japanese Patent Laid-Open No. 2003-307736). JP, 2004-163646, JP, 204-83810, JP, 9-211468, and JP, 2003- 114437).
  • the liquid crystal alignment film produced by the photoalignment method can be effectively applied to various liquid crystal display devices.
  • the conventional photo alignment film has a problem that the radiation dose necessary to obtain a large pretilt angle is large.
  • the radiation whose optical axis is tilted from the substrate normal is 10,000 JZm 2 or more. It has been reported that the light must be irradiated (see Japanese Patent Application Laid-Open Nos. 2002-250924 and 2004-83810 and J. of American S ID 1 1/3, 2003, p. 579). Disclosure of the invention
  • the present invention has been made in view of the above circumstances, and an object thereof is to provide a liquid crystal alignment film having good liquid crystal alignment ability even with a small amount of exposure by irradiation of polarized or non-polarized light without rubbing treatment. It is an object of the present invention to provide a liquid crystal alignment element which gives a liquid crystal alignment layer, a method of manufacturing the liquid crystal alignment film, and a liquid crystal display device excellent in various properties such as display characteristics and reliability. According to the invention, the above object of the invention is first
  • Upsilon 1 is a hydroxyl group, an alkoxyl group, an alkyl group or Ariru group with carbon number from 6 to 20 carbon atoms 1-2 0 1 to 10 carbon atoms.
  • the above object of the present invention is secondly:
  • the above-mentioned liquid crystal aligning agent is applied to form a coating film, and the coating film is irradiated with radiation, which is achieved by the method for forming a liquid crystal alignment film.
  • the liquid crystal aligning agent of the present invention is at least one selected from the group consisting of a polysiloxane having a repeating unit represented by the above formula (1), a hydrolyzate thereof and a condensate of a hydrolyzate (hereinafter referred to as “poly Called “siloxane (1)”),
  • a cinnamic acid derivative having at least one group selected from the group consisting of an alkenyl group and an alkynyl group;
  • the polysiloxane (1) used in the present invention is at least one selected from the group consisting of a polysiloxane having a repeating unit represented by the above formula (1), a hydrolyzate thereof and a condensate of a hydrolyzate thereof. It is a species.
  • alkoxyl group having 1 to 10 carbon atoms of Y 1 in the above formula (1) for example, a methoxyl group, an ethoxyl group, etc .; for example, a methyl group, an ethyl group, an alkyl group having 1 to 20 carbon atoms.
  • aryl groups having 6 to 20 carbon atoms include, for example, phenyl group and the like.
  • the polysiloxane (1) may be linear, ladder-like (ladder), cage-like, cubic-like or random-like, or two or more of these structures may be contained in one molecule. It may be one or a mixture of two or more different polysiloxanes having different structures.
  • the polysiloxane (1) preferably has a weight-average molecular weight in terms of polystyrene as measured by gel permeation chromatography (GP C) of 200 to 150,000, more preferably 200 to 100,000, Furthermore, it is preferable that it is 1, 000-10, 000.
  • GP C gel permeation chromatography
  • polysiloxane (1) particularly preferably used in the present invention, for example, the following formula
  • n 1 and n 2 are each an integer of 3 to 8
  • n 3 and n 5 are each an integer of 1 to 50
  • n 4 and n 6 are each an integer of 0 to 1,000.
  • n 7 is an integer of 5 to 10.
  • the compound etc. which are represented by each of can be mentioned.
  • polysiloxane (1) used by this invention the compound represented by said Formula (1-1) is preferable.
  • the weight of the polysiloxane corresponding to 1 mol of the amount of a single hydrogen bond is preferably 50 to 5,000 gZ mol, more preferably 50 to 500 gZ mol. Is more preferred.
  • the compound can be synthesized according to the method described in na 1 o f Am er ica cin Chem ica Soc i t y, Vol. 92, No. 19, P5586 (1970).
  • polysiloxane (1) in the present invention commercially available ones may be used.
  • a compound represented by the above formula (1-1) is available from TAL MATERIALS I nc.
  • the cinnamic acid derivative having at least one group selected from the group consisting of an alkenyl group and an alkynyl group used in the present invention is, for example, at least one group selected from the group consisting of an alkenyl group and an alkynyl group;
  • R 1 represents an alkyl group having 1 to 40 carbon atoms or a monovalent organic group having 3 to 40 carbon atoms containing an alicyclic group, provided that a part of hydrogen atoms of the alkyl group or All may be substituted with a fluorine atom
  • .R 2 is a single bond, an oxygen atom, -COO-or 100 C
  • R 3 is a divalent aromatic group
  • R 4 is a single bond, an oxygen atom, * -COO, or a divalent heterocyclic ring or a divalent fused cyclic group.
  • R 5 is a single bond, a methylene group or an alkylene group having 2 to 10 carbon atoms
  • R 7 is a fluorine atom or a cyano group
  • X 1 is an oxygen atom or the following formula
  • R 8 is an alkyl group having 1 to 40 carbon atoms or a monovalent organic group having 3 to 40 carbon atoms containing an alicyclic group, provided that a part of hydrogen atoms of the alkyl group or All may be substituted with a fluorine atom
  • R 9 is an oxygen atom, one COO— or one OCO—
  • R 1 () is a divalent aromatic group, a divalent heterocyclic group or a divalent
  • X 2 is an oxygen atom, a phenylene group or the following formula
  • C is a integer of 0 to 3 and d is an integer of 0 to 4;
  • the compound represented by) is preferably S.
  • the alkyl group having 1 to 40 carbon atoms of R 1 in the above formula (2) is, for example, an alkyl group having 1 to 20 carbon atoms, provided that some or all of the hydrogen atoms of this alkyl group are substituted by fluorine atoms. Is also preferable.
  • alkyl group examples include, for example, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-lauryl group, n-dodecyl group 4, n, tridecyl, n, tetradecyl, n, decyl, n, hexadecyl, n, heptadecyl, n, octadecyl, n, nonadecyl, n, eicosyl, 4, 4, 4-Trifluorobutyl group, 4, 4, 5, 5, 5-Pentuol fluoropentyl, 4, 4, 5, 5, 6, 6, 6 1-hepto fluo hexyl group, 3, 3, 4 , 4,5,5,5 heptoyl fluoropentyl group, 2, 2, 2-trifluorochloro group,
  • Examples of the divalent aromatic group for R 3 include, for example, 1,4 phenylene group, 2 fluoro1 1,4 phenethyl group, 3 fluoro-1, 4 4 phenylene group, 2, 3 , 5, 6-tetrafluoro-1, 4-phenylene and the like; and the divalent alicyclic group of R 3 include, for example, a 1, 4-cyclohexylene group and the like; and a divalent of R 3 And the like.
  • Examples of the heterocyclic group of 1 to 4 include, for example, 1, 4-pyridylene group, 2, 5-pyridylene group, 1, 4-furanylene group and the like; and examples of the bivalent fused cyclic group of R 3 include Can be listed respectively.
  • Examples of the compound represented by the above formula (2) include, as cinnamic acid derivatives having an alkenyl group, for example, the following formulas (2-P 1) to (2-P 15) and (2-A1) to (2) -A15)
  • R 1 has the same meaning as in the above formula (2), and i is an integer of 0 to 10.
  • a cinnamic acid derivative having an alkynyl group for example, the following formula (2-P16) to (2-P21)
  • the alkyl group having 1 to 40 carbon atoms of R 8 in the above formula (3) is, for example, an alkyl group having 1 to 20 carbon atoms, provided that some or all of the hydrogen atoms of this alkyl group are substituted by fluorine atoms. Is also preferable.
  • Examples of such an alkyl group include those exemplified as the alkyl group of R 1 in the above-mentioned formula (2).
  • divalent aromatic group, divalent heterocyclic group or divalent fused cyclic group of R 1 Q examples include, for example, a divalent aromatic group of R 3 in the above formula (2), and divalent divalent groups Those exemplified as the heterocyclic group or the divalent fused cyclic group can be mentioned.
  • a 1,4 phenyl group is preferable.
  • Examples of the compound represented by the above formula (3) include, as cinnamic acid derivatives having an alkenyl group, for example, the following formulas (3-P 1) to (3-P 5) and (3-A1) to (3) — A3)
  • R s has the same meaning as in the above formula (3), and h and j are each an integer of 1 to 10)
  • cinnamic acid derivatives having an alkynyl group for example, the following formulas (3-P6) to (3-P8) and (3-A4) and (3-A5)
  • R 8 has the same meaning as in the above formula (3), h and j are Each is an integer of 1 to 10. )
  • the compound represented by the above formula (2) or (3) can be synthesized by a conventional method of organic chemistry.
  • a suitable aqueous alkaline solution such as sodium hydroxide
  • the compound represented by the above-mentioned formula (2-A1) is prepared by reacting a lupoxyl group of a cinnamic acid derivative having an loxyxyl group synthesized in the same manner as described above with thionyl chloride to form an acid salt, It can be obtained by reacting this with hydroxyethyl alcohol in the presence of an appropriate base catalyst such as triethylamine.
  • the compound represented by the above formula (2-P 2) and the compound represented by the above formula (2-A 2) are, as a cinnamic acid derivative having a carboxyl group, an alkyl corresponding to hydroxycinnamic acid and R 1
  • the compound represented by the above formula (2-P4) and the compound represented by the above formula (2-A4) correspond to methyl hydroxybenzoate and R 1 as a cinnamic acid derivative having a hydroxyl group.
  • the compound represented by the above formula (2-P 1) or the above formula (2-A 1) is used except that the compound obtained by the reaction with hydroxycinnamic acid in the presence of a base at a temperature of 0 ° C. to room temperature is used. It can obtain similarly to the synthesis
  • the compound represented by the above formula (2-P5) and the compound represented by the above formula (2-A5) are, as a cinnamic acid derivative having a hydroxyl group, an alkyl corresponding to hydroxybenzoic acid and R 1 Is reacted with an alkyl group having sulfonyl group at a temperature of 0 ° C.
  • the compound represented by the above-mentioned formula (2-P6) and the compound represented by the above-mentioned formula (2-A6) are prepared by adding 4-alkylbenzoic acid as a cinnamic acid derivative having a sulfoxyl group with thionyl chloride
  • the compound is obtained by reacting it with hydroxycinnamic acid at a temperature of 0 ° C. to room temperature in the presence of a suitable base such as carbonic acid, and using the compound described above. 1) It can be obtained in the same manner as the synthesis of the compound represented by 1) or the compound represented by the above formula (2-A 1).
  • the compound represented by the above formula (2-P15) and the compound represented by the above formula (2-A15) can be used as the cinnamic acid derivative having a carboxyl group, methyl 4-hydroxycarboxylate and R 1
  • an alkyl halide having an alkyl group corresponding to an alkyl group in the presence of an appropriate alkyl group such as sodium hydride or metal sodium to give an ether, followed by an aqueous alkaline solution such as sodium hydroxide. It is further hydrolyzed to acid chloride with thionyl chloride, and then this is reacted with hydroxycinnamic acid in the presence of a suitable base such as potassium carbonate at a temperature of 0 ° C.
  • the compound represented by the above-mentioned formula (2-P7) and the compound represented by the above-mentioned formula (2-A7) are alkyl compounds corresponding to R 1 as cinnamic acid derivatives having a hydroxyl group.
  • a suitable base such as potassium carbonate
  • the compound represented by the above formula (2-P8) and the compound represented by the above formula (2-A8) are, as a cinnamic acid derivative having a sulfoxyl group, halogenated alkyl and hydroxy corresponding to R 1
  • the reaction is carried out in the presence of a base such as carbonic acid lithium to form an ether bond, and then a compound obtained by aldol condensation of 4-acetylbenzoic acid in the presence of sodium hydroxide is used, respectively. It can be obtained in the same manner as the synthesis of the compound represented by the above formula (2-P 1) or the compound represented by the above formula (2-A1).
  • the compounds represented by the above formulas (2-A9) to (2-A14) and (2-P9) to (2-P14) can also be obtained by methods analogous thereto.
  • the equation (3- P 1) and a compound represented by the above formula (3- A 1) represented by reduction Gobutsu as cinnamic acid derivative having a force Rupokishiru group, corresponding to the 4-Yodofuenoru and R 1
  • the reaction product is reacted with an alkyl acrylate having an alkyl group (generally called “Heck reaction”) catalyzed by palladium and amine (the reaction is generally called “Heck reaction”).
  • a compound represented by the above-mentioned formula (2-P 1) or a compound represented by the above-mentioned formula (2-A1) is used except for using a compound obtained by cycloaddition of a cyclic acid anhydride. It can be obtained in the same way.
  • the compound represented by the above formula (3-P 2) and the compound represented by the above formula (3 _ A 2) are a cinnamic acid derivative having a sulfoxyl group, and a 4-alkyl group corresponding to R 1
  • a compound represented by the above-mentioned formula (2-P 1) or a compound represented by the above-mentioned formula (2-) is used except that the compound obtained by the aldol condensation of acetophenone and 4-formylbenzoic acid in the presence of sodium hydroxide is used. It can be obtained in the same manner as the synthesis of the compound represented by A1).
  • the compounds represented by the above formulas (3-P 3) and (3-A 3) respectively A compound can also be obtained by the method according to this. [Radiation sensitive polysiloxane]
  • the radiation sensitive polysiloxane contained in the liquid crystal aligning agent of the present invention is preferably a silylated silylate in the presence of a catalyst, preferably in the presence of a catalyst, preferably the polysiloxane (1) and the cinnamic acid derivative as described above. It is a polyorganosiloxane obtained by reacting by reaction.
  • the cinnamic acid derivative is preferably 0.10 to 1.5 moles, more preferably 0.11 to 1 moles, still more preferably 0 moles per 1 mole of the silicon-hydrogen bond possessed by the polysiloxane (1). .05 to 0.9 mol is used.
  • catalysts for hydrosilylation reaction those known as catalysts for hydrosilylation reaction can be used, and for example, compounds or complexes containing platinum, rhodium or palladium can be used.
  • compounds or complexes containing platinum are preferred. Specific examples thereof include hexachloroplatinate (IV) acid hexahydrate, platinum carbonylvinylmethyl complex, platinum-divinyltetramethyldisiloxane complex, platinum-cyclovinylmethyl siloxane complex And platinum-octyl aldehyde / octanoyl complex etc. can be mentioned.
  • the platinum compound or complex may be supported on a suitable carrier such as activated carbon.
  • the amount of the catalyst used is preferably from 0.01 to 10 000 pm pm, more preferably 0 based on the weight of the cinnamic acid derivative used, as the amount of metal atom contained in the compound or complex. l to 100 ppm.
  • the organic solvent which can be used for the hydrosilylation reaction between the polysiloxane (1) and the cinnamic acid derivative aromatic hydrocarbon or ether is preferable.
  • aromatic hydrocarbon or ether is preferable.
  • the solvent has a solid content concentration (the ratio of the weight of components other than the solvent in the reaction solution to the total weight of the solution) force S is preferably 0.1% by weight or more, more preferably 5 to 50% by weight. used. .
  • the reaction temperature is preferably from room temperature to 250 ° C., more preferably from 50 to 18 It is 0.
  • the reaction time is preferably 0.1 to 120 hours, more preferably 1 to 10 hours.
  • the polysiloxane (1) When the polysiloxane (1) is reacted with a cinnamic acid derivative in the synthesis of the radiation sensitive polysiloxane, a part of the cinnamic acid derivative may be replaced by an unsaturated compound having an epoxy group. .
  • a radiation-sensitive polysiloxane crosslinkable group By using a cinnamic acid derivative and an unsaturated compound having an epoxy group in combination, a radiation-sensitive polysiloxane crosslinkable group can be introduced, and the strength of the resulting liquid crystal alignment film can be further improved.
  • the synthesis of the radiation sensitive polysiloxane is preferably carried out by reacting the polysiloxane (1) with a mixture of a cinnamic acid derivative and an unsaturated compound having an epoxy group.
  • Such unsaturated compounds having an epoxy group include, for example, allyl glycidyl ether, 1, 2-epoxy-5-hexene, 1, 2-epoxy-9-decene, glycidyl acrylate, 4-vinyl-1-cyclo Examples include xense 1, 2—epoxide and the like.
  • the proportion of the unsaturated compound having an epoxy group is preferably to the total of the cinnamic acid derivative and the unsaturated compound having an epoxy group. Is less than 50 mol%.
  • the liquid crystal aligning agent of the present invention contains the radiation sensitive polysiloxane 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, in addition to the radiation sensitive polysiloxane as described above.
  • examples of such other components include polymers other than radiation sensitive polysiloxanes (hereinafter referred to as "other polymers"), heat sensitive crosslinking agents, functional silane compounds, surfactants and the like. be able to.
  • Such other polymers can be used to further improve the solution properties of the liquid crystal aligning agent of the present invention and the electrical properties of the resulting liquid crystal alignment film.
  • Such other polymers include, for example, at least one selected from the group consisting of polyamic acids and polyimides. At least one polymer; the following formula (4)
  • X is a hydroxyl group, a halogen atom, a Ariru group of the alkyl group, an alkoxyl group or a carbon number from 6 to 20 from 1 to 6 carbon having 1 to 20 carbon atoms, Upsilon 2 water group or It is a C1-C10 alkoxyl group.
  • At least one member selected from the group consisting of polysiloxanes having a repeating unit represented by the following, a hydrolyzate thereof and a condensate of a hydrolyzate thereof (hereinafter, also referred to as "other polyacetoxane”); polyamic acid Examples include esters, polyesters, polyamides, cellulose derivatives, polyacetals, polystyrene derivatives, poly (styrene-phenylmaleimide) derivatives, poly (meth) acrylates and the like.
  • the polyamic acid can be obtained by reacting tetracarboxylic acid dianhydride with a diamine compound.
  • Examples of the tetracarboxylic acid dianhydride used for the synthesis of the above polyamic acid include butanetetracarboxylic acid dianhydride, 1, 2, 3, 4-cyclophthalene tetracarboxylic acid dianhydride, 1, 2-dimethyl- 1 , 2, 3, 4-Cyclobutane tetracarboxylic acid dianhydride, 1, 3-Dimethyl- 1, 2, 3, 4-cyclobutane tetracarboxylic acid dianhydride, 1, 3-Dichloro-1, 2, 3, 4-cyclobutane Tetracarboxylic acid dianhydride, 1,2,3,4-Tetramethyl-1,2,3,4-Cyclobutyl ester dianhydride, 1,2,3,4-Cyclopentanate tetrabasic rubonic acid dianhydride 1,2,4,5-Cyclohexanetetracarboxylic dianhydride, 3,3 ', 4,4'-dicyclohexyl tetracarboxy
  • aromatic tetracarboxylic acid dianhydrides such as tetracarboxylic acid dianhydride represented by each of the above.
  • butanetetracarboxylic acid dianhydride 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid.
  • Particularly preferred tetracarboxylic acid dianhydrides include 1,2,3,4 cyclopentatetracarboxylic acid dianhydride, 2,3,5 tribasic cyclopentylcyclopentylacetic acid dianhydride, 1,3,3 a, 4,5,9 b-Hexahydro-5-(Tetrahydro 2,5-Dioxo 3 -Furanyl)-Naphtho [1, 2-c] furan 1, 3-Dione, 1, 3, 3 a, 4 5,9 b-Hexahydro-1-methyl-1- (tetrahydro-2-, 5-dioxo 3-furanyl) mononaphtho [1,2-c] furanone 1,3-dione, 3-oxapicyclo [3 2.
  • tetracarboxylic acid dianhydrides can be used alone or in combination of two or more.
  • the diamine compounds used for the synthesis of the above polyamic acid include, for example, p-phenylidenediamine, m-phenylidenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4.
  • Aromatic diamines such as diamine compounds represented by each of
  • Aromatic diamines having a heteroatom such as diaminotetraphenylthiophene; metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, oxamethylenediamine, nonamethylenediamine, 4, 4-Diamino heptamethyridamine, 1, 4-diaminocyclohexane, isophorone diamine, tetrahydrodicyclopentadiene geniendidiamine, hexahydro-4, 7-methanoate Aliphatic diamines and cycloaliphatic diamines such as danilylene methylene diamine, tricyclo [6. 2. 2. 0 2 ' 7 ] — undecylene dimethiamine, 4, 4'- methylene bis (cyclohexylene);
  • diamino organosiloxanes such as diamino hexamethyl disiloxane.
  • p-phenylidenediamine 4,4, diaminodiphenylmethane, 1,5-diaminonaphthalene, 2,7-diaminofluorene, 4,4'-diaminodiphenyl ether, 4 , 4 '-1 (p-phenylensopropylidene) bis-anilin, 2, 2-bis [4- (4 amino-phenyloxy) phenyl] hexafluoropropane, 2, 2- bis (4-amino-phenyl) hexafuro Propane, 2,2-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'-diamino-2,2,1 bis (trifluoromethyl) biphenyl, 4,4 , 1-bis [(4-amino-1-trifluoromethyl) phenyloxy]-okuta fluorobiphenyl, 1-1
  • diamine compounds may be used alone or in combination of two or more.
  • the use ratio of the tetracarboxylic acid dianhydride and the diamine compound to be subjected to the synthesis reaction of the polyamic acid is such that the acid anhydride group of the tetracarboxylic acid dianhydride is equivalent to 1 equivalent of the amino group contained in the diamine compound.
  • a ratio of 0.2 to 2 equivalents is preferable, and The ratio is preferably 0.3 to 1.2 equivalents.
  • the synthesis reaction of the polyamic acid is preferably carried out in an organic solvent under temperature conditions of preferably ⁇ 20 to 150 ° C., more preferably 0 to: L 00.
  • the synthetic reaction time is preferably 0.5 to 24 hours, more preferably 2 to 10 hours.
  • the organic solvent is not particularly limited as long as it can dissolve the polyamic acid to be synthesized.
  • Non-proton polar solvents such as mercapto-lactones, teramethylurea and hexamethylphosphotriamide; phenol solvents such as m-cresol, xylenol, phenol and halogenated phenol can be mentioned.
  • the total amount (b) of the tetracarboxylic acid dianhydride and the diamine compound used in the amount used (a) of the organic solvent is 0.1 to 30% by weight with respect to the total amount (a + b) of the reaction solution. It is preferable that the amount be as follows.
  • the amount of the organic solvent used means the total amount of the organic solvent and the poor solvent used.
  • the organic solvent may be used in combination with an alcohol, ketone, ester, ether, halogenated hydrocarbon, hydrocarbon or the like which is generally believed to be a poor solvent for polyamic acid within the range in which the polyamic acid power S is not precipitated. be able to.
  • poor solvents include, for example, methanol, ethanol, isopropanol, sodium hexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, cetyl lactate, and butyl lactate.
  • the ratio of use thereof can be appropriately set within the range in which the polyamic acid to be purified does not precipitate, but the organic solvent and the poor solvent Preferably it is 80 weight% or less, More preferably, it is 50 weight% or less.
  • reaction solution in which the polyamic acid is dissolved is obtained.
  • the reaction solution may be used as it is for preparation of a liquid crystal alignment agent, or may be used for preparation of a liquid crystal alignment agent after isolating a polyamic acid contained in the reaction solution, or purification of the isolated polyamic acid Then, it may be subjected to the preparation of a liquid crystal aligning agent.
  • 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 evaporating the reaction solution under reduced pressure with an evaporator. It can be carried out.
  • polyamic acid can be purified by dissolving this polyamic acid in an organic solvent again and then precipitating it in a poor solvent, or performing the process of evaporating under reduced pressure with an evaporator once or several times. .
  • the above-mentioned polyimide can be obtained by dehydration ring closure and imidation of the above polyamic acid.
  • all of the amic acid units possessed by the polyamic acid may be subjected to dehydration ring closure, or only a part of the amic acid units may be subjected to dehydration ring closure, and may be a partial imidate in which both the acid acid unit and the imide ring coexist.
  • the imidation ratio of the polyimide is preferably 80% or more, more preferably 85%. It is above.
  • “imidation ratio” is a ratio of the number of imide ring units to the total number of amic acid units and the number of imide ring units in the polymer, as a percentage.
  • a part of the imide ring may be an isoimide ring.
  • the imidization ratio is determined by dissolving the polyimide in an appropriate solvent and measuring 1 H-NMR spectrum at room temperature using tetramethylsilane as a standard substance.
  • a 1 is a proton-induced peak area of the NH group appearing near the chemical shift 1 O p pm
  • a 2 is a peak area derived from other protons
  • ⁇ is a polyimide precursor It is the number ratio of other protons to one proton of ⁇ group in (polyamic acid).
  • the dehydration and ring closure reaction of the polyamic acid can be carried out by either heating the polyamic acid or (ii) dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydrating ring closure catalyst to this solution, if necessary. Heating is performed.
  • the reaction temperature in the method for heating the polyamic acid of the above (i) is preferably 50 to 200 ° C, more preferably 60 to 170 ° C. If the reaction temperature is less than 50 ° C., the dehydration ring closure reaction does not proceed sufficiently, and if the reaction temperature exceeds 200 ° C., the molecular weight of the resulting polyimide may decrease.
  • an acid anhydride such as acetic anhydride, propioanhydride, acid or trifluoroacetic anhydride is used as the dehydrating agent.
  • the amount of the dehydrating agent used is preferably 0.01 to 20 moles relative to 1 mole of the amic acid unit of the polyamic acid.
  • tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used. However, it is not limited to these.
  • the amount of dehydration ring closure catalyst used is preferably 0.01 to 10 moles relative to 1 mole of dehydrating agent used.
  • the organic solvent that can be used include the organic solvents exemplified as those used for the synthesis of polyamic acid.
  • the reaction temperature of the dehydration ring closure reaction is preferably 0 to 180 ° C., more preferably 10 to 150 ° C., and the reaction time is preferably 1 to 48 hours, more preferably 2 It is ⁇ 10 hours.
  • the polyimide obtained in the above method (i) may be used as it is for preparation of a liquid crystal aligning agent, or alternatively, the obtained polyimide may be purified and then used for preparation of a liquid crystal aligning agent.
  • a reaction solution containing a polyimide is obtained as described above. This reaction solution may be used as it is for preparation of a liquid crystal alignment agent, or may be used for preparation of a liquid crystal alignment agent after removing the dehydrating agent and the dehydrating ring closure catalyst from the reaction solution, and the polyimide was isolated.
  • a liquid crystal aligning agent may be subjected to the preparation of a liquid crystal aligning agent, or it may be subjected to the preparation of a liquid crystal aligning agent after purifying the isolated polyimide.
  • a method such as solvent substitution can be applied.
  • the isolation and purification of the polyimide can be carried out by the same procedure as described above for the isolation and purification of polyamic acid.
  • the above-mentioned polyamic acid and polyimide may be of terminal modified type whose molecular weight is adjusted.
  • Such terminal-modified products can be synthesized by adding an appropriate molecular weight modifier such as an acid monoanhydride, a monoamine compound or a monoisocyanate compound to the reaction system when synthesizing a polyamic acid. it can.
  • examples of the acid monoanhydride include maleic anhydride, hydrofluoric acid anhydride, itaconic acid anhydride, n-decylsuccinic acid anhydride, n-dodecylsuccinic acid anhydride, n-tetradecylsuccinic acid An acid anhydride, n-hexadecylsuccinic anhydride and the like can be mentioned.
  • monoamine compounds for example, aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-hydroxy-tyramine, n-nonylamine, n-decylamine, n -Undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecyl decylamine, n-hexadecylamine, Examples include n-heptadecyl decylamine, n-octadecylamine, and n-eicosylamine.
  • the monoisocyanate compound for example, phenyl isocyanate, naphthyl isocyanate and the like can be mentioned.
  • the amount used is preferably 10 parts by weight or less, more preferably 5 parts by weight or less, per 100 parts by weight of diamine. is there.
  • the above polyamic acid is a solution of 10% by weight of N-methyl-2-pyrrolidone, and the solution viscosity measured at 25 ° C. using an E-type rotational viscometer is 20 to 800 mP a's. Is preferable, and 30 to 50 O mP a ⁇ s is more preferable.
  • the above polyimide is a solution of 10% by weight of apeptyrolactone, and the solution viscosity measured at 25 ° C. using an E-type rotational viscometer must be 20 to 800 m Pa ⁇ s Preferably, it is more preferably 30 to 500 mP a's. [Other polysiloxanes]
  • the gel permeation is at least one selected from the group consisting of a polysiloxane having a repeating unit represented by the above formula (4), a hydrolyzate thereof and a condensate of a hydrolyzate thereof.
  • the polystyrene equivalent weight average molecular weight measured by chromatography (GPC) is 500 to 500, preferably 0, preferably 500 to 500, more preferably 0 to 500.
  • GPC polystyrene equivalent weight average molecular weight measured by chromatography
  • at least a portion of X in the above formula (4) is an alkyl group having 1 to 2 carbon atoms
  • at least a portion of Y 2 is an alkoxyl group having 1 to 10 carbon atoms.
  • the other polysiloxane is preferably, for example, an alkoxysilane compound and at least one silane compound (hereinafter, also referred to as a "raw silane compound") selected from the group consisting of halogenated and halogenated silane compounds, preferably. It can be synthesized by hydrolysis or hydrolysis / condensation in an organic solvent in the presence of water and a catalyst.
  • raw material silane compounds that can be used here, for example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tetrachlorosilane Methyltrimethoxysilane, methyltriethoxysilane, methyltri- n- propoxysilane, methyltri- iso-propoxysilane, methyltri- n-butoxysilane, methyltri- sec-butoxysilane, methyltri- tert- butoxysilane, 'methylethlyoxylethoxy Silane, Fetilly n-propoxysilane, Citricly iso-Propoxysilane, Fetilly n-butoxysilane, Fet
  • tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltrihydroxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyl jetoxysilane, trimethylmethoxysilane or trimethylethoxysilane preferable.
  • organic solvent which can be optionally used when synthesizing other polysiloxanes include alcohol compounds, ketone compounds, amide compounds or ester compounds or other aprotic compounds. These can be used alone or in combination of two or more.
  • Examples of the above-mentioned alcohol compounds include methanol, ethanol, n-propanol, i-propanol, n-butyl alcohol, i-butyl alcohol, sec-butyl alcohol, t-butanol, n-pentyl alcohol , 1-Pentanol, 2-Methyl-Butanol, sec-Pentanol, t-Pentanol, 3-Mex-Ist-Butinol, n-Hexanol, 2-Methyl-Pentanol, sec-Hexanol, 2 — Echi Rub-Eunol, sec-Hep-Eunal, Hep-Eunal-3, n-Octanoyl, 2-Ethylhexanol, sec-Oc-Ethanol, n-Nonyl alcohol, 2, 6-Dimethylheptan-ol 4, n-decanol, sec-decyl alcohol, trimethyln
  • Ethylene glycol 1,2-propylene glycol, 1,3-butylene glycol, pentenediol-1,2,4-methylpentanediol-2,4, hexanediol-2,5, heptandiol-1 2, 4, 2-diethylhexane 1, 3, diethylene glycol, dipropylene glycol, triethylene glycol, polyhydric alcohol compounds such as tripropylene glycol;
  • ketone compounds 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, Monoketones such as Thiru n-Hexyl Ketone, Di-peptyl Ketone, Trimethyl Nonanone, Hexagonal Hexanone, 2-Hexanone, Methyl Cyclohexanone, 2, 4-Pentanedione, Acetonyl Acetone, Acetophenone, Fencene, etc. Compound;
  • Acetylacetone 2, 4-hexanedione, 2, 4-heptanedione, 3, 5 monoheptanedione, 2, 4-octanedione, 3, 5-octanedione, 2, 4 nonandione, 3, 5-nonanedione, 5-Methyl-2,4 hexanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1,1,1,5,5,5 Hexafluoro-2,4,1-heptanedione etc.
  • Diketone compounds and the like can be mentioned, respectively. These ketone compounds can be used alone or in combination of two or more.
  • amide compound examples include formamide, N-methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N- jetylformamide, acetoamide, N-methylacetoamide, N, N-dimethylacetoamide, N-Ethylacetamide, N, N-Getylacetoamide, N-Methyl propionamide, N-Methylpyrrolidone, N-Formylmorpholine, N-Formylpiperidine, N-Formylpyrrolidine, N-Acetyl There can be mentioned morpholine, N-acetylpiperidine, N-sertapilic acid lysine and the like. These amide compounds can be used singly or in combination of two or more.
  • ester compounds examples include jetyl carbonate, ethylene carbonate, propylene carbonate, jetyl carbonate, methyl acetate, ethyl acetate, apeptilolactone, avalerolactone, n-propyl acetate, i-propyl acetate, and acetic acid n.
  • Examples of the other aprotic compounds mentioned above include: acetonitrile, dimethyl sulfoxide, N, N,, ′, N′—tetraethylsulfamide, hexamethylphosphoric acid triamide, ⁇ -methylmorpholine, ⁇ -methylvirol, ⁇ — ⁇ ⁇ - ⁇ - ⁇ - ⁇ - ⁇ - ⁇ - ⁇ - ⁇ - ⁇ -pyrroline, ⁇ -methylbiperidine, ⁇ - ⁇ -piperididine, ⁇ , ⁇ ⁇ ⁇ ⁇ -dimethylpiperazine, ⁇ -methylimidazoyl, ⁇ -methyl- 4-piperidone, ⁇ -methyl- 2-pipe Ridone, ⁇ -methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyltetrahydro-2 (1 ⁇ ) -pyrimidinone and the like can be mentioned.
  • polyhydric alcohol compounds and partial ethers or ester compounds of surface alcohol compounds are particularly preferable.
  • the amount of water used in the synthesis of the other polysiloxane is preferably 0.5 to 100 mol, more preferably 0.5 to 100 mol, per 1 mol in total of the alkoxyl group and the halogen atom of the starting silane compound. It is preferably 1 to 30 moles, and more preferably 1 to 1.5 moles.
  • Examples of the above metal chelate compounds include triethoxy and mono (acetylase). Toners) Titanium, ⁇ ry n-propoxy mono (acetyl acetate tort) titanium, ly i propoxy mono (acetyl acetate tonto) titanium, tory n n-butoxy mono (acetyl acetate tonto) ) Titanium, Tory sec-butoxy 'mono (acetyl acetate toner) titanium, lithium mono- (mono-ethyl acetate toner) titanium, Jexi bis (acet ethyl acetate toner) titanium, Di-n-one propoxy bis (acetyl acetate toner) titanium, di-i-propoxy bis (acetyl acetate toner) titanium, di-n-butoxy 'bis (acetyl isocyanate) titanium, di sec- Butoxy Bis (Acetyl Ascetnate) Titanium, Di-t-Bisoxy Bis (Acetyl
  • aluminum chelate compounds such as tritium (acetyl acetate) aluminum and tris (ethyl acetate) aluminum.
  • organic acids include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, decaic acid, maleic acid, maleic acid, methyl malonic acid, adipic acid, sebacic acid, Gallic acid, butyric acid, melittic acid, arachidonic acid, mykimic acid, 2-ethylhexanoic acid, forelic acid, stearic acid, linoleic acid, linoleic acid, salicylic acid, benzoic acid, P-aminobenzoic acid, P-toluenesulfonic acid, Benzene sulfonic acid, monochloroacetic acid, dichloroacetic
  • inorganic acids examples include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid and phosphoric acid.
  • organic base examples include pyridine, pyrrole, piperazin, pyrrolidine, piperidine, picolin, trimethylamine, tolylamine, monoethanol And diethanolamine, dimethylmonoethanolamine, monomethylamine, ethanolamine, diazabiorocamine, diazabicycloanelan, diazabi chrononan, diazabicycloundecene, tetramethylammonium 8iodrooxide, etc. be able to.
  • alkali metal compound examples include sodium hydroxide, 7j potassium oxide, barium hydroxide, calcium hydroxide and the like.
  • These catalysts can be used alone or in combination of two or more.
  • metal chelate compounds organic acids or inorganic acids are preferable, and titanium chelate compounds or organic acids are more preferable.
  • the amount of the catalyst used is preferably 0.01 to 10 parts by weight, and more preferably 0.01 to 1 part by weight, based on 100 parts by weight of the starting silane compound.
  • Water to be added in the synthesis of another polysiloxane can be intermittently or continuously added to the silane compound as a raw material or to a solution in which the silane compound is dissolved in an organic solvent.
  • the catalyst may be added in advance to a silane compound as a raw material or a solution in which the silane compound is dissolved in an organic solvent, or may be dissolved or dispersed in water to be added.
  • the reaction temperature in the synthesis of the other polysiloxane is preferably 0 to 1 o o C, more preferably 15 to 80 o 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. On the other hand, it is preferably 10 parts by weight or less. The more preferable content of the other polymer depends on the type of the other polymer.
  • the liquid crystal aligning agent of the present invention contains at least one polymer selected from the group consisting of radiation-sensitive polysiloxanes and polyamic acids and polyimides
  • the more preferred use ratio of both is radiation-sensitive Total amount of polyamic acid and polyimide relative to 1000 parts by weight of the crosslinkable polysiloxane. It is preferably 5 to 500 parts by weight, and more preferably 200 to 2,000 parts by weight.
  • the liquid crystal aligning agent of the present invention contains a radiation sensitive polysiloxane and another polysiloxane
  • the more preferable usage ratio of the two is more than the other per 100 parts by weight of the radiation sensitive polysiloxane.
  • the amount of the polysiloxane is 100 to 2,000 parts by weight.
  • the type of the other polymer is at least one selected from the group consisting of polyamic acid and polyimide. It is preferable that they are polymers of the following, or other polysiloxanes.
  • the heat-sensitive crosslinking agent can be used to stabilize the pretilt depression angle and to improve the coating strength.
  • polyfunctional epoxy compounds are effective.
  • Evolite 400 E, 3002 above, Kyoeisha Chemical Co., Ltd. product
  • Epicorite 8 2 8, 15 12 Epoxynopolac 1 8 0 S
  • a base catalyst such as 1-benzimidazole 2-methylimidazole may be used in combination for the purpose of efficiently causing a crosslinking reaction.
  • the content ratio thereof is: 100 parts by weight based on the total of the above-mentioned radiation-sensitive polysiloxane and the other optionally used polymer Preferably, it is at most 100 parts by weight, more preferably at most 50 parts by weight.
  • the functional silane compound can be used for the purpose of improving the adhesion of the obtained liquid crystal alignment film to the substrate.
  • Examples of functional silane compounds include, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-7 minopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-amino (2-aminoethyl ) 1-3-aminopropyl trimethoxysilane, N-(2-aminoethyl) 1-3-aminopropylmethyl dimethoxysilane, 3- ureido oral piltrimethoxysilane, 3- ureidopropyltriethoxysilane, N-X 3-hydroxypropyl 3-aminopropyl-trimethoxysilane, N-ethoxycarboxyl-3-aminopropyltriethoxysilane, N-triethoxys
  • liquid crystal aligning agent of the present invention contains a functional silane compound
  • the content ratio thereof is a total of 100 parts by weight of the above-mentioned radiation sensitive polysiloxane and another polymer optionally used. Preferably, it is at most 50 parts by weight, more preferably at most 20 parts by weight.
  • liquid crystal aligning agent of the present invention contains a surfactant, the content ratio thereof is preferably 10 parts by weight or less, more preferably 1 part by weight based on 100 parts by weight of the entire liquid crystal aligning agent. It is below a weight part.
  • the liquid crystal aligning agent of the present invention contains the radiation-sensitive polysiloxane as an essential component and, if necessary, further contains other components, but preferably each component is preferable. It is prepared as a solution-like composition dissolved in an organic solvent.
  • a solvent S which dissolves the radiation sensitive polysiloxane and other components which are optionally used and does not react with them is preferable.
  • the organic solvent which can be preferably used for the liquid crystal aligning agent of the present invention differs depending on the type of other polymer to be added optionally.
  • the liquid crystal aligning agent of the present invention contains at least one polymer selected from the group consisting of radiation sensitive polysiloxanes and polyamic acids and polyimides
  • preferred organic solvents include synthesis of polyamic acids.
  • the organic solvents exemplified above can be mentioned as those used for At this time, the poor solvent exemplified as one used for the synthesis of the polyamic acid of the present invention may be used in combination.
  • organic solvents are N-methyl-2-pyrrolidone, heptyllacton, abutyrolactam, N, N-dimethylformamide, N, N-dimethylacetoamide, diisobutyl ketone, 4-hydroxy-4-methyl-2 -Pentanone, diisopentyl ether, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, isoamyl propionate, isoamyl isobutyrate, methyl methoxy propionate, hydroxyethyl ethoxy propionate, ethylene glycol methyl ether Ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol monopropyl ether, ethylene glycol n-butyl ether (butyl seq), ethylene glycol dimethyl ether Ter, ethylene glycol ether ether ether, ethylene glycol ether dimethyl ether, diethylene glycol ether ether
  • organic solvents can be used alone or in combination of two or more.
  • n-butyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate or sec-pentyl acetate are preferable.
  • Preferred organic solvents used for preparation of the liquid crystal aligning agent of the present invention are obtained by combining one or more of the above-mentioned organic solvents according to the presence or absence of other polymers and the type thereof.
  • Each component contained in the liquid crystal aligning agent does not precipitate at the following preferable solid concentration, and the surface tension of the liquid crystal aligning agent is in the range of 25 to 40 mNm.
  • the solid content concentration of the liquid crystal aligning agent of the present invention that is, the ratio of the weight of all 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, etc. Preferably, it is in the range of 1 to 10% by weight.
  • the liquid crystal aligning agent of the present invention is applied to the surface of a substrate to form a coating film to be a liquid crystal alignment film, but when the solid content concentration is less than 1% by weight, the film thickness of this coating film is too small. In some cases, it is difficult to obtain a good liquid crystal alignment film.
  • the particularly preferable range of the solid content concentration of the liquid crystal aligning agent of the present invention varies depending on the method used when applying the liquid crystal aligning agent to the substrate.
  • the solid concentration is in the range of 1.5 to 4.5% by weight, particularly preferably S.
  • the ink jet method it is particularly preferable to set the solid content concentration in the range of 1 to 5% by weight and thereby to set the solution viscosity in the range of 3 to 15 mPa ⁇ s.
  • the temperature for preparing the liquid crystal aligning agent of the present invention is preferably 0 to 200, more preferably 20 ° C to 60 ° C.
  • the liquid crystal aligning agent of the present invention can be suitably used to form a liquid crystal alignment film by a photoalignment method.
  • a method of forming a liquid crystal alignment film for example, a method of forming a coating film of the liquid crystal alignment film of the present invention on a substrate and then imparting liquid crystal alignment ability to the coating film by photoalignment method can be mentioned.
  • the liquid crystal aligning agent of the present invention is suitably coated by, for example, roll coating method, spinner method, printing method or ink jet method.
  • the coating is applied by a method, for example, and heated at a temperature of 40 to 250 ° C. for 0.1 to 120 minutes to form a coating.
  • the film thickness of the coating film is preferably 0.000 to 1: L m, more preferably 0.50 to 0.5 Atm, as the thickness after solvent removal.
  • the substrate examples include glass such as float glass and soda glass, and polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polyone sulfonate, poly (alicyclic pholene) and the like.
  • a transparent substrate made of plastic can be used.
  • the transparent conductive film it is possible to use a NESA film made of SnO 2 , an ITO film made of In 2 0 3 — Sn 0 2 or the like.
  • a photo-etching method, a method of using a mask when forming the transparent conductive film, or the like is used.
  • a functional silane compound, titanium oxide compound and the like are previously formed on the substrate and the transparent conductive film. It may be applied.
  • the coating film is irradiated with linearly polarized light or partially polarized radiation or non-polarized radiation, and heat treatment is further preferably performed at a temperature of 150 to 250 ° C. for preferably 1 to 120 minutes.
  • heat treatment is further preferably performed at a temperature of 150 to 250 ° C. for preferably 1 to 120 minutes.
  • the liquid crystal alignment ability is imparted to form a liquid crystal alignment film.
  • radiation for example, ultraviolet light and visible light including light of a wavelength of 150 to 800 nm can be used, but ultraviolet light including light of a wavelength of 300 to 400 nm can be used. Is preferred.
  • the radiation used is linearly polarized or partially polarized, the radiation may be performed from the direction perpendicular to the substrate surface, or may be performed from an oblique direction to give a pretilt angle. You may go. In the case of irradiation with non-polarized radiation, the direction of irradiation needs to be oblique.
  • a light source to be used for example, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal octahedral lamp, an argon resonance lamp, a xenon lamp, an excimer laser etc. can be used.
  • the ultraviolet light in the preferred wavelength region can be obtained by means of using the light source in combination with, for example, a filter, a diffraction grating or the like.
  • the radiation dose is preferably 1 J / m 2 or more and 10 0 0 0 J Zm 2 or less, more preferably 10 to 3 and OOOJ Zm 2 .
  • a radiation irradiation amount of 10 0 0 0 J Z m 2 or more is required.
  • the liquid crystal aligning agent of the present invention is used, good liquid crystal alignment properties can be obtained even if the radiation dose in the photoalignment method is 3, 0 0 J Z m 2 or less, and further 1, 0 0 0 J Z m 2 or less. It contributes to the reduction of the manufacturing cost of the night-crystal display device.
  • the “pretilt angle” in the present invention represents the angle of inclination of liquid crystal molecules from the direction parallel to the substrate surface.
  • the liquid crystal display device of the present invention comprises a liquid crystal alignment film formed from the liquid crystal alignment agent of the present invention.
  • the liquid crystal display element of the present invention can be produced, for example, as follows.
  • a pair of (two) substrates provided with the liquid crystal alignment film are prepared, and the liquid crystal alignment films possessed by these are opposed so that the polarization direction of the linearly polarized radiation irradiated becomes a predetermined angle,
  • the periphery of the space is sealed with a sealing agent, liquid crystal is injected and filled, and the liquid crystal inlet is sealed to constitute a liquid crystal cell.
  • the liquid crystal cell be heated to a temperature at which the liquid crystal used takes an isotropic phase, and then cooled to room temperature to remove the flow alignment at the time of injection.
  • polarizing plates are attached to both sides of the liquid crystal display device so that the polarization directions thereof form a predetermined angle with the easy axis of alignment of the liquid crystal alignment film of the substrate.
  • the liquid crystal alignment film is horizontally aligned, adjusting the angle between the polarization direction of the linearly polarized radiation irradiated and the angle between each substrate and the polarizing plate on the two substrates on which the liquid crystal alignment film is formed.
  • a liquid crystal display element having a TN type or an STN type liquid crystal cell can be obtained.
  • 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.
  • a liquid crystal display device having a vertically aligned liquid crystal cell can be obtained by bonding the polarization direction at an angle of 45 ° with the alignment easy axis.
  • 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, nematic liquid crystal, smectic liquid crystal, etc.
  • nematic type liquid crystal having positive dielectric anisotropy is preferable.
  • biphenyl type liquid crystal, phenylcyclohexane type liquid crystal, ester type liquid crystal, terphenyl type liquid crystal, biphenyl type liquid crystal for example, a cyclohexane liquid crystal, a pyrimidine liquid crystal, a dioxane liquid crystal, a bicyclo alcohol liquid crystal, a cubane liquid crystal, or the like is used.
  • cholesteryl chloride cholesteryl nonaate, cholesteryl carbonate, etc.
  • Steric liquid crystals chiral agents such as those sold under the trade names “C1 1 5”, “CB ⁇ 1 5” (all manufactured by Merck); P-desiloxybenzylidene P-amino-2
  • a ferroelectric liquid crystal such as thin film can also be added and used.
  • nematic liquid crystals having negative dielectric anisotropy are preferable.
  • dicyanobenzene liquid crystals, pyridazine liquid crystals, Schiff base night crystals, azoxy liquid crystals, biphenyl liquid crystals Force S such as phenylcyclohexane liquid crystal is used.
  • a polarizing plate used on the outside of the liquid crystal cell a polarizing plate called a “film” obtained by absorbing iodine while stretching and orienting polyvinyl alcohol is sandwiched by a cellulose acetate protective film, or The polarizing plate etc. which consist of a film itself can be mentioned.
  • the liquid crystal display device of the present invention manufactured by force is excellent in various performances such as display characteristics and reliability.
  • the weight average molecular weight in the following examples is a polystyrene conversion value measured by gel permeation chromatography under the following conditions. Column: Higashi-Soichi Co., Ltd. “T S K g e 1 GR C XL I I”
  • reaction mixture is neutralized with hydrochloric acid and extracted with ethyl acetate, and the extract is dried over magnesium sulfate, concentrated, and recrystallized with ethanol to give the compound (2- 90 g of white crystals of P4-1-2 were obtained.
  • Example CH-1 in place of the compound (2- P4-1) 8. 97 g, a mixture of the compound (2- P 4-1) 4.49 g and the allyl glycidyl ether 1.14 g was used The rest was carried out in the same manner as in Example CH-1 to obtain a radiation sensitive polysiloxane S-CH-2.
  • Working Example CH-3 in place of the compound (2- P4-1) 8. 97 g, a mixture of the compound (2- P 4-1) 4.49 g and the allyl glycidyl ether 1.14 g was used The rest was carried out in the same manner as in Example CH-1 to obtain a radiation sensitive polysiloxane S-CH-2.
  • Working Example CH-3 in place of the compound (2- P4-1) 8. 97 g, a mixture of the compound (2- P 4-1) 4.49 g and the allyl glycidyl ether 1.14 g was used The rest was carried out in the same manner as in Example CH-1 to obtain a radiation sensitive polysilox
  • Example CH-1 the compound (3- P5-1) 8.05 g synthesized in the above Synthesis Example P (2) was used instead of the compound (2- P 4-1) 8. 97 g
  • the above Example CH-1 was carried out in the same manner to obtain a radiation sensitive polysiloxane S-CH 13.
  • the solution was filtered through a filter with a pore size of 1 m to prepare a liquid crystal aligning agent A-C H-1.
  • the storage stability of the liquid crystal aligning agent A-CH-1 was evaluated according to the following method and criteria. The storage stability of the liquid crystal aligning agent A-CH-1 was "good”.
  • a coating of a liquid crystal alignment agent was formed on a glass substrate by spin coating with the number of rotations as a variable, and the number of rotations at which the film thickness of the coating after solvent removal was 1,00 OA was examined.
  • liquid crystal aligning agent A-CH-1 was taken and stored at 15 ° C. for 5 weeks.
  • the liquid crystal aligning agent after storage was visually observed, and when precipitation of insoluble matter was observed, it was judged as storage stability “poor”.
  • a coating film is formed on the glass substrate by spin coating at a rotational speed of 1, 000 OA before storage, and the solvent is removed. Film thickness was measured. If the film thickness deviates 10% or more from 1,00 OA, it is judged as storage stability "defective", and if the deviation of the film thickness is less than 10%, the storage stability is "good”. It was judged.
  • the film thickness of the above-mentioned coating film was measured using a stylus-type step thickness meter manufactured by KLA-Tencor.
  • Liquid crystal aligning agent A-CH-2-A-CH- in the same manner as in Example CH-5 except that the types of radiation-sensitive polysiloxane and the types and amounts of other polymers were as described in Table 1. 6 and A—CH—11, A—CH—12 and A—CH— 14 Were prepared respectively.
  • a liquid crystal aligning agent A-CH-8 to A-CH- was carried out in the same manner as in Example CH-11 except that the types and amounts of radiation-sensitive polysiloxane and other polymers were as described in Table 1. 10 and A—CH—13 were prepared respectively.
  • the liquid crystal aligning agent A-CH-1 prepared in the above Example CH 15 is coated on a transparent electrode surface of a glass substrate with a transparent electrode comprising an ITO film using a spinner, and 1 on a 80 hot plate After pre-packing for a minute, the oven is purged with nitrogen.
  • the coating film was formed to a film thickness of 0.1 m by heating at 200 ° C. for 1 hour. Next, using this Hg-Xe lamp and a Granthera prism on this film surface, polarized ultraviolet light 1, 0 0 0 J Zm 2 containing a bright line of 13 13 nm, inclined 40 ° from the substrate normal. It was irradiated from the direction to make a liquid crystal alignment film. The same operation was repeated to create a pair (two sheets) of substrates having a liquid crystal alignment film.
  • the liquid crystal alignment of the pair of substrates is performed.
  • the film surfaces were facing each other, pressure was applied so that the projection direction of the optical axis of ultraviolet light of each substrate on the substrate surface was antiparallel, and the adhesive was thermally cured at 150 ° C. for 1 hour.
  • the liquid crystal injection port was sealed with an epoxy adhesive. Furthermore, in order to remove the flow alignment at the time of liquid crystal injection, this was heated at 150 ° C.
  • the polarization directions of the polarizing plates are orthogonal to each other, and the projection direction of the optical axis of the ultraviolet light of the liquid crystal alignment film on the substrate surface 45.
  • the vertical type liquid crystal display device was manufactured by pasting so as to form an angle of.
  • the liquid crystal display element was evaluated by the following method. The evaluation results are shown in Table 2. Evaluation method for liquid crystal display devices>
  • a voltage of 5 V was applied to the liquid crystal display element manufactured above with an application time of 60 microseconds and a span of 167 milliseconds, and then a voltage retention ratio of 167 milliseconds after release of the application was measured.
  • the measuring device used was “VHR-1” manufactured by Toyo NGO Co., Ltd.
  • Example 33 the light resistance was evaluated as follows, and the evaluation result was “good”.
  • the initial voltage holding ratio was measured under the same conditions as the evaluation of the above voltage holding ratio. Thereafter, the liquid crystal display element was placed at a distance of 5 cm under a 40-watt-type white fluorescent lamp, light was irradiated for 1,000 hours, and then the voltage retention was measured again under the same conditions as described above.
  • the voltage holding ratio was less than ⁇ 2% compared to the initial value, the light resistance was evaluated as “good”, and when it was ⁇ 2% or more, the light resistance was evaluated as “bad”. Comparative example CH-1
  • the solution was filtered through a filter with a pore size of 1 m to prepare a liquid crystal aligning agent R-CH-1.
  • a liquid crystal alignment film was formed in the same manner as in Example CH-19 except that the liquid crystal alignment agent R-CH-1 prepared above was used, and a vertical alignment liquid crystal display element was produced and evaluated. The results are shown in Table 2. Table 2
  • Example CH- 19 A-CH- 1 1,000 Good 89 ° 98 8
  • Example CH- 20 A-CH-2 1,000 Good 89.
  • 98 8 Example CH- 21 A-CH-3 200 Good 89 ° 98 10
  • Example CH-22 A-CH-3 1, 000 Good 89 ° 98 8 Poor example CH- 23 A-CH-3 3, 000 Good 89 ° 98 8
  • Example CH-24 A-CH-4 1,000 Good 89.
  • the liquid crystal aligning agent A-CH-11 prepared in the above Example CH-15 is coated on a transparent electrode surface of a glass substrate with a transparent electrode comprising an ITO film using a spinner, and a hot plate at 80 ° C.
  • the film was prebaked for 1 minute and then heated at 200 ° C. for 1 hour to form a coating having a film thickness of 0.1 zm.
  • the surface of this coating is irradiated with polarized ultraviolet light containing an emission line of 313 nm, 1, 000 JZm 2 from the direction inclined 40 ° from the substrate normal, using an Hg-X e lamp and a Glan-Taylor prism.
  • a liquid crystal alignment film was formed by imparting a liquid crystal alignment ability.
  • An epoxy resin adhesive containing aluminum oxide spheres with a diameter of 5.5 m is applied by screen printing on the periphery of the surface of each of the pair of substrates on which the liquid crystal alignment film is formed, and then the polarized ultraviolet irradiation direction becomes orthogonal.
  • the substrates were overlaid and crimped, and heated at 150 ° C. for 1 hour to thermally cure the adhesive.
  • positive type nematic liquid crystal (MLC-6221, manufactured by Merck, containing a chiral agent) was injected from the liquid crystal injection port into the gap of the substrate and filled, and then the liquid crystal injection port was sealed with an epoxy adhesive. Furthermore, this was heated at 150 ° C.
  • a TN type liquid crystal display device is manufactured by bonding polarizing plates on both outer sides of the substrate so that the polarization directions thereof are orthogonal to each other and in parallel with the polarization direction of the liquid crystal alignment film. did.
  • a TN alignment type liquid crystal display element was manufactured and evaluated in the same manner as in Example CH-34 except that the kind of liquid crystal aligning agent used was as described in Table 3. The results are shown in Table 3.
  • the liquid crystal aligning agent of the present invention is not excellent in storage stability but is compared with the liquid crystal aligning agent for photo alignment known in the prior art. By using a smaller amount of radiation, it is possible to form a liquid crystal alignment film having excellent liquid crystal alignment and electrical properties. Effect of the invention
  • the liquid crystal aligning agent of the present invention is a liquid crystal alignment having excellent liquid crystal alignment and electrical properties at a small radiation dose as compared with liquid crystal aligning agents conventionally known as liquid crystal aligning agents to which the photo alignment method can be applied.
  • a film can be formed. Therefore, 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 in the related art, and moreover, various performances such as display characteristics and reliability can be obtained. Therefore, these liquid crystal display devices can be effectively applied to various devices, and can be suitably used, for example, in devices such as desk calculators, watches, stationary clocks, counting display boards, word processors, personal computers, liquid crystal televisions and the like.

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Abstract

L'invention divulgue un agent d'alignement de cristaux liquides qui contient un polysiloxane sensible au rayonnement, obtenu en faisant réagir au moins une substance sélectionnée dans l'ensemble constitué des polysiloxanes dotés d'une unité répétée représentée par la formule (1), leurs produits d'hydrolyse et les condensats des produits d'hydrolyse, avec un dérivé d'acide cinnamique qui présente au moins un groupe sélectionné dans l'ensemble constitué des groupes alcényle et des groupes alcynyle. (1) (Dans la formule (1), Y1 représente un groupe hydroxyle, un groupe alcoxyle comptant de 1 à 10 atomes de carbone, un groupe alkyle comptant de 1 à 20 atomes de carbone ou un groupe aryle comptant de 6 à 20 atomes de carbone.)
PCT/JP2008/071600 2007-11-27 2008-11-20 Agent d'alignement de cristaux liquides, procédé de formation d'un film d'alignement de cristaux liquides et dispositif d'affichage à cristaux liquides WO2009069724A1 (fr)

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KR1020107009204A KR101450942B1 (ko) 2007-11-27 2008-11-20 액정 배향제, 액정 배향막의 형성 방법 및 액정 표시 소자
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KR20120104987A (ko) * 2009-12-02 2012-09-24 닛산 가가쿠 고교 가부시키 가이샤 액정 배향 처리제 및 그것을 사용한 액정 표시 소자
WO2014017497A1 (fr) * 2012-07-24 2014-01-30 日産化学工業株式会社 L'invention a pour objectif de fournir un procédé pour juger simplement l'état de différenciation, bon ou mauvais, de cellules souches pluripotentes, sans nécessiter le jugement d'un expert qualifié. l'invention a également pour objectif de fournir un procédé permettant l'application d'une détermination automatique des cellules souches pluripotentes ayant débuté une différenciation. ainsi, selon le procédé de l'invention, la bonne ou la mauvaise qualité de cellules souches pluripotentes est évaluée sur la base d'une différence de motifs de coloration des cellules souches pluripotentes.
US20190049796A1 (en) * 2016-02-03 2019-02-14 Sharp Kabushiki Kaisha Oriented film, polymer, and liquid crystal display device
CN111164120A (zh) * 2017-08-03 2020-05-15 日产化学株式会社 固化膜形成用组合物、取向材及相位差材

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WO2013054858A1 (fr) * 2011-10-12 2013-04-18 日産化学工業株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et dispositif d'affichage à cristaux liquides
JP5854205B2 (ja) * 2011-11-21 2016-02-09 Jsr株式会社 液晶配向剤
JP6146100B2 (ja) * 2012-06-21 2017-06-14 Jsr株式会社 液晶配向剤、液晶配向膜、位相差フィルム、液晶表示素子及び位相差フィルムの製造方法

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JP4544438B2 (ja) * 2007-11-27 2010-09-15 Ｊｓｒ株式会社 液晶配向剤、液晶配向膜の形成方法および液晶表示素子
JPWO2009069724A1 (ja) * 2007-11-27 2011-04-14 Jsr株式会社 液晶配向剤、液晶配向膜の形成方法および液晶表示素子
KR20120104987A (ko) * 2009-12-02 2012-09-24 닛산 가가쿠 고교 가부시키 가이샤 액정 배향 처리제 및 그것을 사용한 액정 표시 소자
KR101708962B1 (ko) 2009-12-02 2017-02-21 닛산 가가쿠 고교 가부시키 가이샤 액정 배향 처리제 및 그것을 사용한 액정 표시 소자
WO2014017497A1 (fr) * 2012-07-24 2014-01-30 日産化学工業株式会社 L'invention a pour objectif de fournir un procédé pour juger simplement l'état de différenciation, bon ou mauvais, de cellules souches pluripotentes, sans nécessiter le jugement d'un expert qualifié. l'invention a également pour objectif de fournir un procédé permettant l'application d'une détermination automatique des cellules souches pluripotentes ayant débuté une différenciation. ainsi, selon le procédé de l'invention, la bonne ou la mauvaise qualité de cellules souches pluripotentes est évaluée sur la base d'une différence de motifs de coloration des cellules souches pluripotentes.
CN104937480A (zh) * 2012-07-24 2015-09-23 日产化学工业株式会社 液晶取向膜的制造方法、液晶取向膜、液晶显示元件、聚合物以及液晶取向剂
JPWO2014017497A1 (ja) * 2012-07-24 2016-07-11 日産化学工業株式会社 液晶配向膜の製造方法、液晶配向膜、液晶表示素子、重合体及び液晶配向剤
CN104937480B (zh) * 2012-07-24 2018-01-16 日产化学工业株式会社 液晶取向膜的制造方法、液晶取向膜、液晶显示元件、聚合物以及液晶取向剂
US20190049796A1 (en) * 2016-02-03 2019-02-14 Sharp Kabushiki Kaisha Oriented film, polymer, and liquid crystal display device
US10394083B2 (en) * 2016-02-03 2019-08-27 Sharp Kabushiki Kaisha Oriented film, polymer, and liquid crystal display device
CN111164120A (zh) * 2017-08-03 2020-05-15 日产化学株式会社 固化膜形成用组合物、取向材及相位差材

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