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WO2013039168A1 - Procédé de fabrication d'un film d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides - Google Patents

Procédé de fabrication d'un film d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides Download PDF

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Publication number
WO2013039168A1
WO2013039168A1 PCT/JP2012/073515 JP2012073515W WO2013039168A1 WO 2013039168 A1 WO2013039168 A1 WO 2013039168A1 JP 2012073515 W JP2012073515 W JP 2012073515W WO 2013039168 A1 WO2013039168 A1 WO 2013039168A1
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Prior art keywords
liquid crystal
formula
group
alignment film
crystal alignment
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PCT/JP2012/073515
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English (en)
Japanese (ja)
Inventor
隆夫 堀
直樹 作本
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日産化学工業株式会社
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Priority to KR1020147009609A priority Critical patent/KR101951507B1/ko
Priority to CN201280056047.9A priority patent/CN103946738B/zh
Priority to JP2013533717A priority patent/JP6056759B2/ja
Publication of WO2013039168A1 publication Critical patent/WO2013039168A1/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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • G02F1/133723—Polyimide, polyamide-imide
    • 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

  • the present invention relates to a method for producing a liquid crystal alignment film for a photo-alignment method, a liquid crystal alignment film obtained by this production method, and a liquid crystal display device comprising the obtained liquid crystal alignment film.
  • a liquid crystal alignment film for controlling the alignment state of liquid crystals is usually provided in the element.
  • the most widely used liquid crystal alignment film in the industry is made of a polyamic acid formed on an electrode substrate and / or a polyimide film obtained by imidizing the same with a cloth such as cotton, nylon or polyester. It is manufactured by performing a so-called rubbing process that rubs in the direction.
  • the rubbing treatment of the film surface in the alignment process of the liquid crystal alignment film is an industrially useful method that is simple and excellent in productivity.
  • Patent Document 1 proposes that a polyimide film having an alicyclic structure such as a cyclobutane ring in the main chain is used for the photo-alignment method.
  • the liquid crystal alignment film obtained by the photo-alignment method has a problem that anisotropy with respect to the alignment direction of the polymer liquid crystal alignment film is smaller than that by rubbing. If the anisotropy is small, sufficient liquid crystal orientation cannot be obtained, and when a liquid crystal display element is formed, there is a problem that an afterimage is generated.
  • Patent Literature As a method for increasing the anisotropy of a liquid crystal alignment film obtained by a photo-alignment method, it has been proposed to remove a low molecular weight component generated by cutting the polyimide main chain by light irradiation after light irradiation (Patent Literature). 2).
  • the object of the present invention is to increase the anisotropy of the liquid crystal alignment film obtained by the photo-alignment method, and to suppress the unevenness that occurs during the process, and the method of manufacturing the liquid crystal alignment film And a liquid crystal display element comprising the liquid crystal alignment film obtained by the method for producing the liquid crystal alignment film.
  • the present inventors irradiate a film obtained by applying and baking a polyimide film or a polyimide precursor with polarized radiation, By performing contact treatment such as immersion using a solution containing an organic solvent, the anisotropy of the obtained liquid crystal alignment film can be remarkably improved, and the above-described problem of unevenness occurring in the liquid crystal alignment film can be solved. I found it.
  • the present invention has the following gist. 1. Polarized radiation on an imidized film obtained by applying and baking a liquid crystal aligning agent containing at least one polymer selected from the group consisting of polyimide and a precursor of the polyimide and an organic solvent on a substrate And then at least selected from the group consisting of the following formula (A-1), formula (A-2), formula (A-3), formula (A-4), and formula (A-5) A method for producing a liquid crystal alignment film, wherein the contact treatment is performed with a solution containing one kind of organic solvent.
  • a 1 is a hydrogen atom or an acetyl group
  • a 2 is an alkyl group having 1 to 6 carbon atoms
  • R 2 is a hydrogen atom or a methyl group
  • n is 1 or 2
  • a 3 is an alkyl group having 1 to 4 carbon atoms
  • R 3 and R 4 are each independently a hydrogen atom or
  • a 5 and A 6 each independently represents an alkyl group having 1 to 4 carbon atoms
  • A-5 represents 3 carbon atoms. 6 to 6 alkyl groups or cycloalkyl groups.
  • the organic solvent is 1-methoxy-2-propanol, ethyl lactate, diacetone alcohol, methyl 3-methoxypropionate, or ethyl 3-ethoxypropionate.
  • the polymer contains at least one polymer selected from the group consisting of a polyimide precursor having a structural unit represented by the following formula (3) and an imidized polymer of the polyimide precursor.
  • the manufacturing method of the liquid crystal aligning film in any one of.
  • X 1 is at least one selected from the group consisting of structures represented by the following formulas (X1-1) to (X1-9), and Y 1 is a divalent organic group.
  • R 1 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R 3 , R 4 , R 5 , and R 6 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms. Group, alkenyl group, or phenyl group.
  • 5. From the group consisting of a polyimide precursor in which the polymer contains 60 mol% or more of the structural unit represented by the formula (3) with respect to 1 mol of the whole polymer, and an imidized polymer of the polyimide precursor. 5.
  • Z 1 is a single bond, an ester bond, an amide bond, a thioester bond, or a divalent organic group having 2 to 10 carbon atoms.
  • a contact treatment solution for an alignment film which is selected from the group consisting of Formula (A-1), Formula (A-2), Formula (A-3), Formula (A-4), and Formula (A-5).
  • a contact treatment liquid for a liquid crystal alignment film comprising a solution containing at least one organic solvent.
  • 11. 10 A liquid crystal alignment film obtained by the method for producing a liquid crystal alignment film according to any one of 1 to 9 above. 12 12.
  • a liquid crystal display device comprising the liquid crystal alignment film as described in 11 above.
  • the liquid crystal alignment film according to the production method of the present invention has a high anisotropy and thus has a high liquid crystal alignment regulating force, an excellent afterimage characteristic, and a high-quality liquid crystal display element when used in a liquid crystal display element.
  • the liquid crystal alignment film when the contact treatment is performed with a solution containing at least one organic solvent selected from the group consisting of the compounds represented by the above formulas (A-1) to (A-5) in the present invention, the liquid crystal alignment film
  • the improvement in the anisotropy is greatly improved, and at the same time, the occurrence of unevenness in the obtained liquid crystal alignment film can be remarkably suppressed.
  • ⁇ Polyimide and precursor of the polyimide> at least one polymer selected from the group consisting of a polyimide to which anisotropy is imparted by irradiation with polarized radiation and a precursor of the polyimide (hereinafter also simply referred to as a polymer). ) Is used. If it is the polyimide or polyimide precursor which satisfy
  • a polyimide precursor having a structural unit represented by the following formula (3) is particularly preferable.
  • R 1 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. From the viewpoint of ease of imidization by heating, a hydrogen atom or a methyl group is particularly preferable.
  • X 1 is at least one selected from the group consisting of structures represented by the following formulas (X1-1) to (X1-9).
  • R 3 , R 4 , R 5 , and R 6 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms.
  • An alkenyl group or a phenyl group which may be the same or different.
  • R 3 , R 4 , R 5 , and R 6 are each independently preferably a hydrogen atom, a halogen atom, a methyl group, or an ethyl group, and more preferably a hydrogen atom or a methyl group.
  • X 1 is more preferably at least one selected from the group consisting of structures represented by the following formulas (X1-10) and (X1-11).
  • Y 1 is a divalent organic group, and its structure is not particularly limited. Since the obtained liquid crystal alignment film has high anisotropy, it is preferably at least one selected from the group consisting of structures represented by the following formulas (Y1-1) and (Y1-2).
  • Z 1 is a single bond, an ester bond, an amide bond, a thioester bond, or a divalent organic group having 2 to 10 carbon atoms.
  • the ester bond is represented by —C (O) O— or —OC (O) —.
  • R is an alkyl group, alkenyl group, alkynyl group, aryl group, or a combination thereof having 1 to 10 carbon atoms.
  • alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a hexyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, and a bicyclohexyl group.
  • alkenyl group examples include those in which one or more CH 2 —CH 2 structures present in the above alkyl group are replaced with a CH ⁇ CH structure, and more specifically, vinyl groups, allyl groups, 1- Examples include propenyl group, isopropenyl group, 2-butenyl group, 1,3-butadienyl group, 2-pentenyl group, 2-hexenyl group, cyclopropenyl group, cyclopentenyl group, cyclohexenyl group and the like.
  • Alkynyl groups include those in which one or more CH 2 —CH 2 structures present in the alkyl group are replaced with C ⁇ C structures, and more specifically, ethynyl groups, 1-propynyl groups, 2 -Propynyl group and the like.
  • Examples of the aryl group include a phenyl group.
  • Z 1 is an organic group having 2 to 10 carbon atoms, it can be represented by the structure of the following formula (6).
  • Z 4 , Z 5 , and Z 6 are each independently a single bond, —O—, —S—, —NR 11 —, an ester bond, an amide bond, a thioester bond, a urea bond, It is a carbonate bond or a carbamate bond.
  • R 11 is a hydrogen atom, a methyl group, or a t-butoxycarbonyl group.
  • the ester bond, amide bond, and thioester bond in Z 4 , Z 5 , and Z 6 can have the same structure as the ester bond, amide bond, and thioester bond described above.
  • urea bond a structure represented by —NH—C (O) NH— or —NR—C (O) NR— can be shown.
  • R is an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a combination thereof having 1 to 10 carbon atoms, and these groups are the same examples as the above-mentioned alkyl group, alkenyl group, alkynyl group, and aryl group. Can be mentioned.
  • carbonate bond a structure represented by —O—C (O) —O— can be shown.
  • the carbamate bond is —NH—C (O) —O—, —O—C (O) —NH—, —NR—C (O) —O—, or —O—C (O) —NR—.
  • R is an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a combination thereof having 1 to 10 carbon atoms, and these groups are the same examples as the above-mentioned alkyl group, alkenyl group, alkynyl group, and aryl group. Can be mentioned.
  • R 9 and R 10 in the formula (6) are each independently a structure selected from a single bond, an alkylene group having 1 to 10 carbon atoms, an alkenylene group, an alkynylene group, an arylene group, or a combination thereof. .
  • R 9 and R 10 is a single bond
  • either R 9 or R 10 is an alkylene group, an alkenylene group, an alkynylene group, an arylene group, or a combination thereof having 2 to 10 carbon atoms.
  • As said alkylene group the structure remove
  • a methylene group, 1,1-ethylene group, 1,2-ethylene group, 1,2-propylene group, 1,3-propylene group, 1,4-butylene group, 1,2-butylene group 1,2-pentylene group, 1,2-hexylene group, 2,3-butylene group, 2,4-pentylene group, 1,2-cyclopropylene group, 1,2-cyclobutylene group, 1,3- A cyclobutylene group, a 1,2-cyclopentylene group, a 1,2-cyclohexylene group and the like can be mentioned.
  • the alkenylene group includes a structure in which one hydrogen atom is removed from the alkenyl group. More specifically, 1,1-ethenylene group, 1,2-ethenylene group, 1,2-ethenylenemethylene group, 1-methyl-1,2-ethenylene group, 1,2-ethenylene-1,1- Ethylene group, 1,2-ethenylene-1,2-ethylene group, 1,2-ethenylene-1,2-propylene group, 1,2-ethenylene-1,3-propylene group, 1,2-ethenylene-1, Examples include 4-butylene group and 1,2-ethenylene-1,2-butylene group.
  • the alkynylene group includes a structure in which one hydrogen atom is removed from the alkynyl group.
  • an ethynylene group an ethynylene methylene group, an ethynylene-1,1-ethylene group, an ethynylene-1,2-ethylene group, an ethynylene-1,2-propylene group, an ethynylene-1,3-propylene group
  • Examples include ethynylene-1,4-butylene group, ethynylene-1,2-butylene group and the like.
  • the arylene group includes a structure in which one hydrogen atom is removed from the aryl group. More specific examples include 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group and the like. If the linearity contains a high structural and rigid structure to Y 1, since the liquid crystal alignment film having good liquid crystal alignment property can be obtained, as the structure of Z 1, a single bond, or the following formula (A1-1) The structure of (A15-25) is more preferable.
  • the structure represented by the above formula (4) is particularly preferable as the Y 1 structure.
  • the ratio of the structural unit represented by the above formula (3) is the total of all the polymers. 60 to 100 mol% is preferable with respect to 1 mol of the structural unit. The higher the ratio of the structural unit represented by the above formula (3), the better the liquid crystal alignment film having good liquid crystal alignment, so 80-100 mol% is more preferable, and 90-100 mol% is more preferable.
  • the polymer component of the present invention may be a polyimide precursor containing a structural unit represented by the following formula (7) and the polyimide precursor.
  • R 1 is the same as defined for R 1 in the formula (3).
  • X 3 is a tetravalent organic group, and its structure is not particularly limited. Specific examples include structures of the following formulas (X-9) to (X-42). From the viewpoint of availability of the compound, the structure of X 3 is preferably X-17, X-25, X-26, X-27, X-28, X-32, or X-39. Further, from the viewpoint of alleviation of the accumulated residual charge obtained fast liquid crystal alignment film by a DC voltage, it is preferable to use a tetracarboxylic dianhydride having an aromatic ring structure, the structure of X 3 is, X -26, X-27, X-28, X-32, X-35, or X-37 are more preferred.
  • Y 4 is a divalent organic group, and its structure is not particularly limited. Specific examples of Y 4 include structures of the following formulas (Y-1) to (Y-74).
  • Y 4 in the formula (7) is Y-8, Y-20, Y-21, Y-22, Y-28, Y-29, Y- in order to improve the solubility of the polymer component in the organic solvent. It is preferable to contain a structural unit having a structure of 30, Y-72, Y-73, or Y-74. When the ratio of the structural unit represented by the above formula (7) in the polymer component is high, the ratio of the structural unit represented by the above formula (7) is the total structure in order to reduce the liquid crystal orientation of the liquid crystal alignment film. The amount is preferably 0 to 40 mol%, more preferably 0 to 20 mol%, based on 1 mol of the unit.
  • the polyamic acid ester which is a polyimide precursor used in the present invention can be synthesized by the following methods (1) to (3).
  • the polyamic acid ester can be synthesized by esterifying a polyamic acid obtained from tetracarboxylic dianhydride and diamine. Specifically, the polyamic acid and the esterifying agent are synthesized by reacting them in the presence of an organic solvent at ⁇ 20 to 150 ° C., preferably 0 to 50 ° C., for 30 minutes to 24 hours, preferably 1 to 4 hours. be able to.
  • N N-dimethylformamide dimethyl acetal, N, N-dimethylformamide diethyl acetal, N, N-dimethylformamide dipropyl acetal, N, N-dimethylformamide Dineopentyl butyl acetal, N, N-dimethylformamide di-t-butyl acetal, 1-methyl-3-p-tolyltriazene, 1-ethyl-3-p-tolyltriazene, 1-propyl-3-p -Tolyltriazene, 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride and the like.
  • the addition amount of the esterifying agent is preferably 2 to 6 molar equivalents, more preferably 2 to 4 molar equivalents per 1 mol of the polyamic acid repeating unit.
  • the organic solvent used in the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, ⁇ -butyrolactone, etc. from the solubility of the polymer, and these are used alone or in combination of two or more. May be.
  • the concentration of the polymer in the organic solvent at the time of synthesis is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass from the viewpoint that the polymer hardly precipitates and a high molecular weight product is easily obtained.
  • Polyamic acid ester can be synthesized from tetracarboxylic acid diester dichloride and diamine. Specifically, tetracarboxylic acid diester dichloride and diamine are reacted in the presence of a base and an organic solvent at ⁇ 20 to 150 ° C., preferably 0 to 50 ° C., for 30 minutes to 24 hours, preferably 1 to 4 hours. Can be synthesized.
  • pyridine triethylamine, 4-dimethylaminopyridine and the like can be used, but pyridine is preferable because the reaction proceeds gently.
  • the addition amount of the base is preferably 2 to 4 times mol, preferably 2 to 3 times mol with respect to tetracarboxylic acid diester dichloride, from the viewpoint of easy removal and high molecular weight. More preferred.
  • the organic solvent used in the above reaction is preferably N-methyl-2-pyrrolidone, ⁇ -butyrolactone or the like in view of the solubility of the monomer and polymer, and these may be used alone or in combination.
  • the polymer concentration in the organic solvent at the time of synthesis is preferably 1 to 30% by mass and more preferably 5 to 20% by mass from the viewpoint that the polymer is hardly precipitated and a high molecular weight product is easily obtained.
  • the organic solvent used for the synthesis of the polyamic acid ester is preferably dehydrated as much as possible, and the reaction is preferably performed in a nitrogen atmosphere to prevent contamination of the outside air. .
  • the polyamic acid ester can be synthesized by polycondensation of a tetracarboxylic acid diester and a diamine. Specifically, tetracarboxylic diester and diamine are reacted in the presence of a condensing agent, a base, and an organic solvent at 0 to 150 ° C., preferably 0 to 100 ° C., for 30 minutes to 24 hours, preferably 3 to 15 hours. Can be synthesized.
  • condensing agent examples include triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N′-carbonyldiimidazole, dimethoxy-1,3,5-triazide.
  • Nylmethylmorpholinium O- (benzotriazol-1-yl) -N, N, N ′, N′-tetramethyluronium tetrafluoroborate, O- (benzotriazol-1-yl) -N, N , N ′, N′-tetramethyluronium hexafluorophosphate, (2,3-dihydro-2-thioxo-3-benzoxazolyl) phosphonate diphenyl, and the like.
  • the addition amount of the condensing agent is preferably 2 to 3 times by mole, more preferably 2 to 2.5 times by mole with respect to the tetracarboxylic acid diester.
  • tertiary amines such as pyridine and triethylamine can be used.
  • the addition amount of the base is preferably 2 to 4 times mol, more preferably 2 to 3 times mol with respect to the diamine component, from the viewpoint of easy removal and high molecular weight.
  • the organic solvent include N-methyl-2-pyrrolidone, ⁇ -butyrolactone, N, N-dimethylformamide and the like.
  • the reaction proceeds efficiently by adding Lewis acid as an additive.
  • Lewis acid lithium halides such as lithium chloride and lithium bromide are preferable.
  • the addition amount of the Lewis acid is preferably 0.1 to 5 times mol, more preferably 2 to 3 times mol for the diamine component.
  • a high molecular weight polyamic acid ester is obtained, and thus the synthesis method (1) or (2) is particularly preferable.
  • the polyamic acid ester solution obtained as described above can be polymerized by being poured into a poor solvent while being well stirred. Precipitation is performed several times, and after washing with a poor solvent, a purified polyamic acid ester powder can be obtained at room temperature or by heating and drying.
  • the poor solvent is not particularly limited, and examples thereof include water, methanol, ethanol, 2-propanol, hexane, butyl cellosolve, acetone, toluene and the like, and water, methanol, ethanol, 2-propanol and the like are preferable.
  • the polyamic acid which is a polyimide precursor used in the present invention can be synthesized by the following method. Specifically, tetracarboxylic dianhydride and diamine are reacted in the presence of an organic solvent at ⁇ 20 to 150 ° C., preferably 0 to 50 ° C., for 30 minutes to 24 hours, preferably 1 to 12 hours. Can be synthesized.
  • the organic solvent used in the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, ⁇ -butyrolactone, etc. in view of the solubility of the monomer and polymer. These may be used alone or in combination of two or more. May be used.
  • the concentration of the polymer is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass from the viewpoint that polymer precipitation is difficult to occur and a high molecular weight product is easily obtained.
  • the polyamic acid obtained as described above can be recovered by precipitating the polymer by pouring into the poor solvent while thoroughly stirring the reaction solution. Moreover, the powder of polyamic acid refine
  • the poor solvent is not particularly limited, and examples thereof include water, methanol, ethanol, 2-propanol, hexane, butyl cellosolve, acetone, toluene and the like, and water, methanol, ethanol, 2-propanol and the like are preferable.
  • the polyimide used in the present invention can be produced by imidizing the polyamic acid ester or polyamic acid.
  • chemical imidization in which a basic catalyst is added to the polyamic acid solution obtained by dissolving the polyamic acid ester solution or the polyamic acid ester resin powder in an organic solvent is simple.
  • Chemical imidization is preferable because the imidization reaction proceeds at a relatively low temperature and the molecular weight of the polymer is hardly lowered during the imidization process.
  • Chemical imidation can be performed by stirring the polyamic acid ester to be imidized in an organic solvent in the presence of a basic catalyst.
  • a basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Of these, triethylamine is preferred because it has sufficient basicity to allow the reaction to proceed.
  • the temperature for carrying out the imidization reaction is ⁇ 20 to 140 ° C., preferably 0 to 100 ° C., and the reaction time can be 1 to 100 hours.
  • the amount of the basic catalyst is 0.5 to 30 times mol, preferably 2 to 20 times mol of the amic acid ester group.
  • the imidation ratio of the resulting polymer can be controlled by adjusting the catalyst amount, temperature, and reaction time.
  • the chemical imidation which adds a catalyst to the solution of the said polyamic acid obtained by reaction of a diamine component and tetracarboxylic dianhydride is simple. Chemical imidization is preferable because the imidization reaction proceeds at a relatively low temperature and the molecular weight of the polymer does not easily decrease during the imidization process.
  • Chemical imidation can be performed by stirring a polymer to be imidized in an organic solvent in the presence of a basic catalyst and an acid anhydride.
  • a basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Of these, pyridine is preferred because it has an appropriate basicity for proceeding with the reaction.
  • the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated.
  • the temperature for carrying out the imidization reaction is ⁇ 20 to 140 ° C., preferably 0 to 100 ° C., and the reaction time can be 1 to 100 hours.
  • the amount of the basic catalyst is 0.5 to 30 times mol, preferably 2 to 20 times mol of the polyamic acid group, and the amount of acid anhydride is 1 to 50 times mol, preferably 3 to 30 times mol of the polyamic acid group. Is a mole.
  • the imidation ratio of the resulting polymer can be controlled by adjusting the amount of catalyst, temperature, and reaction time.
  • the liquid crystal aligning agent of the present invention is preferable.
  • the polyimide solution obtained as described above can be polymerized by pouring into a poor solvent while thoroughly stirring. Precipitation is performed several times, and after washing with a poor solvent, a polymer powder purified by drying at normal temperature or by heating can be obtained.
  • the poor solvent examples include, but are not limited to, methanol, 2-propanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and the like. Methanol, ethanol, 2-propanol, Acetone is preferred.
  • the liquid crystal aligning agent used in the present invention has a form of a solution in which a polymer component is dissolved in an organic solvent.
  • the molecular weight of the polymer is preferably 2,000 to 500,000 in terms of weight average molecular weight, more preferably 5,000 to 300,000, and still more preferably 10,000 to 100,000.
  • the number average molecular weight is preferably 1,000 to 250,000, more preferably 2,500 to 150,000, and still more preferably 5,000 to 50,000.
  • the concentration of the polymer of the liquid crystal aligning agent used in the present invention can be appropriately changed depending on the thickness of the coating film to be formed. % From the viewpoint of storage stability of the solution, and preferably 10% by mass or less. A particularly preferred polymer concentration is 2 to 8% by mass.
  • the organic solvent contained in the liquid crystal aligning agent used for this invention will not be specifically limited if a polymer component melt
  • N-dimethylformamide N, N-diethylformamide, N, N-dimethylacetamide
  • N-methyl-2-pyrrolidone N-ethyl-2-pyrrolidone
  • N-methylcaprolactam examples include 2-pyrrolidone, N-vinyl-2-pyrrolidone, dimethyl sulfoxide, dimethyl sulfone, ⁇ -butyrolactone, 1,3-dimethyl-imidazolidinone, 3-methoxy-N, N-dimethylpropanamide and the like. You may use these 1 type or in mixture of 2 or more types. Moreover, even if it is a solvent which cannot melt
  • the liquid crystal aligning agent used for this invention may contain the solvent for improving the coating-film uniformity at the time of apply
  • a solvent a solvent having a surface tension lower than that of the organic solvent is generally used. Specific examples thereof include ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, and 1-butoxy-2-propanol.
  • the purpose is to change the electrical properties such as the dielectric constant and conductivity of the polymer other than the polymer and the liquid crystal aligning film as long as the effects of the present invention are not impaired.
  • an imidization accelerator for the purpose of efficiently imidizing the polyamic acid may be added.
  • the method for producing a liquid crystal alignment film of the present invention comprises a step of applying a liquid crystal aligning agent to a substrate and baking, a step of irradiating the obtained film with polarized radiation, and contacting the irradiated film with a specific solvent. A step of processing.
  • substrate, and baking The liquid crystal aligning agent obtained as mentioned above was apply
  • the substrate to which the liquid crystal aligning agent used in the present invention is applied is not particularly limited as long as it is a highly transparent substrate, and a glass substrate, a silicon nitride substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like can be used. From the viewpoint of simplification of the process, it is preferable to use a substrate on which an ITO electrode or the like for driving liquid crystal is formed.
  • an opaque material such as a silicon wafer can be used as long as only one substrate is used.
  • a material that reflects light such as aluminum can be used.
  • Examples of the method for applying the liquid crystal aligning agent used in the present invention include a spin coating method, a printing method, and an ink jet method.
  • the drying and baking steps after applying the liquid crystal aligning agent can be selected at any temperature and time. Usually, in order to sufficiently remove the organic solvent contained, it is dried at 50 to 120 ° C., preferably 60 to 100 ° C. for 1 to 10 minutes, and then 150 to 300 ° C., preferably 200 to 250 at 5 to 120. It is fired in minutes.
  • the thickness of the coating film after firing is not particularly limited, but if it is too thin, the reliability of the liquid crystal display element may be lowered, and therefore it is 5 to 300 nm, preferably 10 to 200 nm.
  • a step of irradiating the obtained film with polarized radiation The film obtained by the method of (1) above is irradiated with polarized radiation (hereinafter also referred to as photo-alignment treatment), thereby polarizing the film. Anisotropy is imparted in the direction perpendicular to the direction.
  • photo-alignment treatment there is a method in which the surface of the coating film is irradiated with radiation polarized in a certain direction, and in some cases, a heat treatment is further performed at a temperature of 150 to 250 ° C. to impart liquid crystal alignment ability. Can be mentioned.
  • the wavelength of radiation ultraviolet rays and visible rays having a wavelength of 100 to 800 nm can be used.
  • ultraviolet rays having a wavelength of 100 to 400 nm are preferable, and those having a wavelength of 200 to 400 nm are particularly preferable.
  • Dose of the radiation is preferably in the range of 1 ⁇ 10,000mJ / cm 2, and particularly preferably in the range of 100 ⁇ 5,000mJ / cm 2.
  • the process of contact-treating the film irradiated with radiation with a solution containing an organic solvent is then contact-treated with a solution containing a specific organic solvent.
  • the organic solvent used here is selected from the group consisting of the following (A-1), formula (A-2), formula (A-3), formula (A-4), and formula (A-5). At least one organic solvent or organic solvent.
  • a 1 is a hydrogen atom or an acetyl group
  • a 2 is an alkyl group having 1 to 6 carbon atoms
  • R 2 is a hydrogen atom or a methyl group
  • n is 1 or 2 Is an integer.
  • a 3 is an alkyl group having 1 to 4 carbon atoms.
  • R 3 and R 4 are each independently a hydrogen atom or a methyl group.
  • a 5 and A 6 are each independently an alkyl group having 1 to 4 carbon atoms.
  • a 6 is an alkyl group or cycloalkyl group having 3 to 6 carbon atoms.
  • the organic solvents of the above formulas (A-1) to (A-5) are preferably water-soluble having a boiling point of preferably 100 to 180 ° C., more preferably 110 to 160 ° C. If the boiling point is high, it will remain in the film and adversely affect the properties of the liquid crystal alignment film. On the other hand, if the boiling point is low, the film tends to volatilize, which tends to cause unevenness in the film. .
  • the organic solvents represented by the above formulas (A-1) to (A-5) have high anisotropy and are easy to obtain a uniform liquid crystal alignment film.
  • 1-methoxy-2-propanol 1- At least one selected from the group consisting of methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, methyl lactate, diacetone alcohol, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate, and cyclohexyl acetate Species are preferred.
  • at least one selected from the group consisting of 1-methoxy-2-propanol and ethyl lactate is preferable.
  • the solution containing the organic solvent used for the contact treatment may contain other solvents or solvents other than the organic solvents represented by the above formulas (A-1) to (A-5) as long as the effects of the present invention are not impaired.
  • other solvents include, but are not limited to, water, methanol, ethanol, 2-propanol, acetone, and methyl ethyl ketone.
  • water is more preferable from the viewpoints of versatility and safety.
  • the content of the at least one organic solvent selected from the group consisting of the above formulas (A-1) to (A-5) is the amount of the solution used for the contact treatment.
  • the amount is preferably 10 to 100% by mass, more preferably 30 to 100% by mass, and particularly preferably 50 to 100% by mass with respect to the total amount.
  • the contact treatment between the film irradiated with polarized radiation and the solution containing the organic solvent is a treatment such that the film and the liquid are preferably in sufficient contact with each other, such as immersion treatment or spraying treatment.
  • a method of immersing the film in a solution containing an organic solvent preferably 10 seconds to 1 hour, more preferably 1 to 30 minutes is preferable.
  • the contact treatment may be performed at room temperature or preferably at 10 to 80 ° C., more preferably 20 to 50 ° C.
  • a means for enhancing contact such as ultrasonic waves can be applied as necessary.
  • rinsing or rinsing with a low boiling point solvent such as water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, or both are used. May be done.
  • the temperature for drying is preferably from 80 to 250 ° C, more preferably from 80 to 150 ° C.
  • the liquid crystal display element of the present invention is a liquid crystal cell obtained by a known method after obtaining a substrate with a liquid crystal alignment film obtained from the liquid crystal aligning agent obtained by the production method of the present invention, and using the liquid crystal cell. It is a liquid crystal display element.
  • a liquid crystal display element having a passive matrix structure will be described as an example. Note that an active matrix liquid crystal display element in which a switching element such as a TFT (Thin Film Transistor) is provided in each pixel portion constituting the image display may be used.
  • a transparent glass substrate is prepared, a common electrode is provided on one substrate, and a segment electrode is provided on the other substrate.
  • These electrodes can be ITO electrodes, for example, and are patterned so as to display a desired image.
  • an insulating film is provided on each substrate so as to cover the common electrode and the segment electrode.
  • the insulating film can be, for example, a film made of SiO 2 —TiO 2 formed by a sol-gel method.
  • the liquid crystal alignment film of the present invention is formed on each substrate.
  • the other substrate is superposed on one substrate so that the alignment film surfaces face each other, and the periphery is bonded with a sealant.
  • a spacer is usually mixed in the sealing material.
  • a liquid crystal material is injected into the space surrounded by the two substrates and the sealing material through the opening provided in the sealing material. Thereafter, the opening is sealed with an adhesive.
  • a vacuum injection method may be used, or a method utilizing capillary action in the atmosphere may be used.
  • a polarizing plate is installed. Specifically, a pair of polarizing plates is attached to the surfaces of the two substrates opposite to the liquid crystal layer.
  • the molecular weight of the polyamic acid ester was measured by a GPC (room temperature gel permeation chromatography) apparatus, and the number average molecular weight (Mn) and the weight average molecular weight (Mw) were calculated as polyethylene glycol and polyethylene oxide equivalent values.
  • GPC device manufactured by Shodex (GPC-101) Column: manufactured by Shodex (series of KD803 and KD805) Column temperature: 50 ° C Eluent: N, N-dimethylformamide (as additives, lithium bromide-hydrate (LiBr ⁇ H 2 O) is 30 mmol / L (liter), phosphoric acid / anhydrous crystal (o-phosphoric acid) is 30 mmol / L, tetrahydrofuran (THF) is 10 ml / L) Flow rate: 1.0 ml / min Standard sample for preparing a calibration curve: TSK standard polyethylene oxide (weight average molecular weight (Mw) of about 900,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation, and polymer laboratory Polyethylene glycol manufactured by the company (peak top molecular weight (Mp) of about 12,000, 4,000, 1,000). In order to avoid the overlapping of peaks, the measurement was performed by mixing four types of 900,000,
  • the anisotropy of the alignment film was measured as follows. Measurement was performed using an ultraviolet-visible-near infrared spectrophotometer (UV-3100PC) manufactured by Shimadzu Corporation. The degree of anisotropy was measured from the absorbance (value of 235 nm) with respect to the alignment direction of the obtained alignment film and the absorbance with respect to the direction perpendicular to the alignment direction. [Membrane unevenness] For the evaluation of film unevenness, the film-coated substrate after the immersion treatment was visually observed and classified as follows. ⁇ : No unevenness ⁇ : Some unevenness was observed ⁇ : Large unevenness or whitening was observed
  • Example 1 The liquid crystal aligning agent A obtained in Synthesis Example 2 was filtered through a 1.0 ⁇ m filter, spin-coated on a glass substrate, dried on a hot plate at a temperature of 80 ° C. for 3 minutes, and then baked at 230 ° C. for 10 minutes. A polyimide film having a thickness of 100 nm was obtained. The coating surface was irradiated with 254 nm ultraviolet light through a polarizing plate at 1.2 J / cm 2 . Next, the film-coated substrate obtained above was immersed in PGME (boiling point: 120 ° C.) at 25 ° C. for 3 minutes, rinsed with IPA for 1 minute, and dried in an oven at 80 ° C. for 10 minutes.
  • PGME roofing point: 120 ° C.
  • Example 2 In the same manner as in Example 1, using the liquid crystal aligning agent A obtained in Synthesis Example 2, a polyimide substrate coated, dried and baked on a substrate was irradiated with ultraviolet rays to form a substrate with a film PGMEA ( (Boiling point: 146 ° C.) at 25 ° C. for 3 minutes, rinsed with IPA for 1 minute, and dried in an oven at 80 ° C. for 10 minutes to obtain a liquid crystal alignment film.
  • size with respect to the orientation direction of the obtained liquid crystal aligning film was 1.51. Further, when the liquid crystal alignment film was visually observed, no unevenness was observed.
  • Example 4 In the same manner as in Example 1, using the liquid crystal aligning agent A obtained in Synthesis Example 2, a film-coated substrate obtained by irradiating ultraviolet rays onto a polyimide film coated, dried and baked on a substrate was converted into ethyl lactate. After being immersed in (boiling point: 154 ° C.) at 25 ° C. for 3 minutes, it was rinsed with IPA for 1 minute and dried in an oven at 80 ° C. for 10 minutes to obtain a liquid crystal alignment film. The anisotropic magnitude
  • Example 5 In the same manner as in Example 1, using the liquid crystal aligning agent A obtained in Synthesis Example 2, a polyimide substrate coated, dried and baked on a substrate was irradiated with ultraviolet rays, and a substrate with a film was obtained from a butyl cellosolve ( (Boiling point: 169 ° C.) for 10 minutes at 25 ° C., rinsed with IPA for 1 minute, and dried in an oven at 80 ° C. for 10 minutes to obtain a liquid crystal alignment film.
  • size with respect to the orientation direction of the obtained liquid crystal aligning film was 1.69. Further, when the liquid crystal alignment film was visually observed, no unevenness was observed.
  • Example 6> In the same manner as in Example 1, using the liquid crystal aligning agent A obtained in Synthesis Example 2, a polyimide substrate coated, dried and baked on a substrate was irradiated with ultraviolet rays, and a substrate with a film was obtained from PGME ( (Boiling point: 124 ° C.) at 25 ° C. for 3 minutes, rinsed with water for 1 minute, and dried in an oven at 80 ° C. for 10 minutes to obtain a liquid crystal alignment film.
  • size with respect to the orientation direction of the obtained liquid crystal aligning film was 1.82. Further, when the liquid crystal alignment film was visually observed, no unevenness was observed.
  • Example 7 In the same manner as in Example 1, using the liquid crystal aligning agent A obtained in Synthesis Example 2, a film-coated substrate obtained by irradiating ultraviolet rays onto a polyimide film coated, dried and baked on a substrate was converted into ethyl lactate. After being immersed in (boiling point: 154 ° C.) at 25 ° C. for 3 minutes, it was rinsed with water for 1 minute and dried in an oven at 80 ° C. for 10 minutes to obtain a liquid crystal alignment film. The anisotropic magnitude
  • Example 8> In the same manner as in Example 1, the liquid crystal aligning agent A obtained in Synthesis Example 2 was used, and the substrate with a film obtained by irradiating the polyimide film coated, dried and baked on the substrate with ultraviolet rays was converted into diacetone. After being immersed in alcohol (boiling point: 169 ° C.) at 25 ° C. for 3 minutes, rinsed with water for 1 minute and dried in an oven at 80 ° C. for 10 minutes to obtain a liquid crystal alignment film. The anisotropic magnitude
  • Example 9 In the same manner as in Example 1, using the liquid crystal aligning agent A obtained in Synthesis Example 2, a substrate with a film obtained by irradiating ultraviolet rays onto a polyimide film coated, dried and baked on the substrate was converted into MMP ( (Boiling point: 145 ° C.) at 25 ° C. for 3 minutes, rinsed with water for 1 minute, and dried in an oven at 80 ° C. for 10 minutes to obtain a liquid crystal alignment film.
  • size with respect to the orientation direction of the obtained liquid crystal aligning film was 1.77. Further, when the liquid crystal alignment film was visually observed, no unevenness was observed.
  • Example 10 Example 1 was repeated except that 254 nm ultraviolet rays were irradiated at 0.5 J / cm 2 .
  • a polyimide substrate coated, dried and baked on a substrate was irradiated with ultraviolet rays, and a substrate with a film was added to PGME (boiling point: 120 ° C.) at 25 ° C.
  • PGME roofing point: 120 ° C.
  • the substrate was rinsed with IPA for 1 minute and dried in an oven at 80 ° C. for 10 minutes to obtain a liquid crystal alignment film.
  • size with respect to the orientation direction of the obtained liquid crystal aligning film was 1.72. Further, when the liquid crystal alignment film was visually observed, no unevenness was observed.
  • Example 11 Example 1 was repeated except that 254 nm ultraviolet rays were irradiated at 0.5 J / cm 2 .
  • the film-coated substrate was added to ethyl lactate (boiling point: 154 ° C.) at 25 ° C.
  • the substrate was rinsed with IPA for 1 minute and dried in an oven at 80 ° C. for 10 minutes to obtain a liquid crystal alignment film.
  • size with respect to the orientation direction of the obtained liquid crystal aligning film was 2.11. Further, when the liquid crystal alignment film was visually observed, no unevenness was observed.
  • Example 12 Example 1 was repeated except that 254 nm ultraviolet rays were irradiated at 0.5 J / cm 2 .
  • PGME glassing point: 120 ° C.
  • the substrate was rinsed with IPA for 1 minute and dried in an oven at 80 ° C. for 10 minutes to obtain a liquid crystal alignment film.
  • size with respect to the orientation direction of the obtained liquid crystal aligning film was 1.53. Further, when the liquid crystal alignment film was visually observed, no unevenness was observed.
  • Example 13 Example 1 was repeated except that 254 nm ultraviolet rays were irradiated at 0.5 J / cm 2 .
  • the substrate with a film obtained by irradiating the polyimide film coated, dried and baked on the substrate with ultraviolet rays was treated with ethyl lactate (boiling point: 154 ° C.) at 25 After immersing at 3 ° C. for 3 minutes, the substrate was rinsed with IPA for 1 minute and dried in an oven at 80 ° C. for 10 minutes to obtain a liquid crystal alignment film.
  • size with respect to the orientation direction of the obtained liquid crystal aligning film was 1.94. Further, when the liquid crystal alignment film was visually observed, no unevenness was observed.
  • Example 14 Example 1 was repeated except that 254 nm ultraviolet rays were irradiated at 0.5 J / cm 2 .
  • the liquid crystal aligning agent D obtained in Synthesis Example 8 the polyimide substrate coated, dried and baked on the substrate was irradiated with ultraviolet rays, and the substrate with a film was added to PGME (boiling point: 120 ° C.) at 25 ° C. After immersing for 3 minutes, the substrate was rinsed with IPA for 1 minute and dried in an oven at 80 ° C. for 10 minutes to obtain a liquid crystal alignment film.
  • size with respect to the orientation direction of the obtained liquid crystal aligning film was 1.40. Further, when the liquid crystal alignment film was visually observed, no unevenness was observed.
  • Example 15 Example 1 was repeated except that 254 nm ultraviolet rays were irradiated at 0.5 J / cm 2 .
  • the polyimide film coated, dried and baked on the substrate was irradiated with ultraviolet rays, and the film-coated substrate was added to ethyl lactate (boiling point: 154 ° C.) at 25.
  • the substrate was rinsed with IPA for 1 minute and dried in an oven at 80 ° C. for 10 minutes to obtain a liquid crystal alignment film.
  • size with respect to the orientation direction of the obtained liquid crystal aligning film was 1.70. Further, when the liquid crystal alignment film was visually observed, no unevenness was observed.
  • Example 16 Example 1 was repeated except that 254 nm ultraviolet rays were irradiated at 0.5 J / cm 2 .
  • the liquid crystal aligning agent A obtained in Synthesis Example 2 the polyimide substrate coated, dried and baked on the substrate was irradiated with ultraviolet rays, and the substrate with a film was added to PGME (boiling point: 120 ° C.) at 25 ° C. After immersing for 3 minutes, the substrate was rinsed with IPA for 1 minute and dried in an oven at 80 ° C. for 10 minutes to obtain a liquid crystal alignment film.
  • size with respect to the orientation direction of the obtained liquid crystal aligning film was 1.37. Further, when the liquid crystal alignment film was visually observed, no unevenness was observed.
  • Example 17 Example 1 was repeated except that 254 nm ultraviolet rays were irradiated at 0.5 J / cm 2 .
  • a polyimide film coated, dried and baked on a substrate was irradiated with ultraviolet rays, and a film-coated substrate was added to ethyl lactate (boiling point: 154 ° C.) at 25.
  • the substrate was rinsed with IPA for 1 minute and dried in an oven at 80 ° C. for 10 minutes to obtain a liquid crystal alignment film.
  • size with respect to the orientation direction of the obtained liquid crystal aligning film was 1.77. Further, when the liquid crystal alignment film was visually observed, no unevenness was observed.
  • Example 18 Example 1 was repeated except that 254 nm ultraviolet rays were irradiated at 0.5 J / cm 2 .
  • PGME glassing point: 120 ° C.
  • the substrate was rinsed with IPA for 1 minute and dried in an oven at 80 ° C. for 10 minutes to obtain a liquid crystal alignment film.
  • size with respect to the orientation direction of the obtained liquid crystal aligning film was 1.33. Further, when the liquid crystal alignment film was visually observed, no unevenness was observed.
  • Example 19 Example 1 was repeated except that 254 nm ultraviolet rays were irradiated at 0.5 J / cm 2 .
  • the substrate with a film obtained by irradiating the polyimide film coated, dried and baked on the substrate with ultraviolet rays was treated with ethyl lactate (boiling point: 154 ° C.) at 25 ° C. After immersing at 3 ° C. for 3 minutes, the substrate was rinsed with IPA for 1 minute and dried in an oven at 80 ° C. for 10 minutes to obtain a liquid crystal alignment film.
  • size with respect to the orientation direction of the obtained liquid crystal aligning film was 1.2. Further, when the liquid crystal alignment film was visually observed, no unevenness was observed.
  • Example 20> The procedure was the same as Example 1 except that 1.0 J / cm 2 of 254 nm ultraviolet light was irradiated.
  • the substrate with a film obtained by irradiating the polyimide film coated, dried and baked on the substrate with ultraviolet rays was added to PGME (boiling point: 120 ° C.) at 25 ° C.
  • PGME roofing point: 120 ° C.
  • the substrate was rinsed with IPA for 1 minute and dried in an oven at 80 ° C. for 10 minutes to obtain a liquid crystal alignment film.
  • size with respect to the orientation direction of the obtained liquid crystal aligning film was 1.15. Further, when the liquid crystal alignment film was visually observed, no unevenness was observed.
  • Example 21 The procedure was the same as Example 1 except that 1.0 J / cm 2 of 254 nm ultraviolet light was irradiated.
  • a substrate with a film obtained by irradiating the polyimide film coated, dried and baked on the substrate with ultraviolet rays was added to ethyl lactate (boiling point: 154 ° C.) at 25 ° C.
  • IPA ethyl lactate
  • the substrate was rinsed with IPA for 1 minute and dried in an oven at 80 ° C. for 10 minutes to obtain a liquid crystal alignment film.
  • size with respect to the orientation direction of the obtained liquid crystal aligning film was 1.12. Further, when the liquid crystal alignment film was visually observed, no unevenness was observed.
  • Example 22 The procedure was the same as Example 1 except that 1.0 J / cm 2 of 254 nm ultraviolet light was irradiated.
  • the substrate with a film obtained by irradiating the polyimide film coated, dried and baked on the substrate with ultraviolet rays was added to PGME (boiling point: 120 ° C.) at 25 ° C.
  • the substrate was rinsed with IPA for 1 minute and dried in an oven at 80 ° C. for 10 minutes to obtain a liquid crystal alignment film.
  • size with respect to the orientation direction of the obtained liquid crystal aligning film was 1.11. Further, when the liquid crystal alignment film was visually observed, no unevenness was observed.
  • Example 23 The procedure was the same as Example 1 except that 1.0 J / cm 2 of 254 nm ultraviolet light was irradiated.
  • the substrate with a film obtained by irradiating the polyimide film coated, dried and baked on the substrate with ultraviolet rays was treated with ethyl lactate (boiling point: 154 ° C.) at 25 ° C. After immersing at 3 ° C. for 3 minutes, the substrate was rinsed with IPA for 1 minute and dried in an oven at 80 ° C. for 10 minutes to obtain a liquid crystal alignment film.
  • size with respect to the orientation direction of the obtained liquid crystal aligning film was 1.10. Further, when the liquid crystal alignment film was visually observed, no unevenness was observed.
  • IPA (Boiling point: 82.4 ° C.) at 25 ° C. for 3 minutes and then dried in an oven at 80 ° C. for 10 minutes to obtain a liquid crystal alignment film.
  • size with respect to the orientation direction of the obtained liquid crystal aligning film was 1.2. Further, when the alignment film was visually observed, a little unevenness was observed.
  • ⁇ Comparative example 2> In the same manner as in Example 1, using the liquid crystal aligning agent A obtained in Synthesis Example 2, a polyimide film coated, dried and baked on the substrate was irradiated with ultraviolet rays, and the film-coated substrate was treated with water ( (Boiling point: 100 ° C.) for 3 minutes, rinsed with IPA for 1 minute, and dried in an oven at 80 ° C. for 10 minutes to obtain a liquid crystal alignment film.
  • size with respect to the orientation direction of the obtained liquid crystal aligning film was 1.25. Further, when the liquid crystal alignment film was visually observed, some unevenness was observed.
  • Example 1 was repeated except that 254 nm ultraviolet rays were irradiated at 0.5 J / cm 2 .
  • the substrate with the film was made IPA (boiling point: 82.4 ° C.). After being immersed for 3 minutes at 25 ° C., it was dried in an oven at 80 ° C. for 10 minutes to obtain a liquid crystal alignment film.
  • size with respect to the orientation direction of the obtained liquid crystal aligning film was 1.19. Further, when the alignment film was visually observed, a little unevenness was observed.
  • Example 1 was repeated except that 254 nm ultraviolet rays were irradiated at 0.5 J / cm 2 .
  • the substrate with a film obtained by irradiating the polyimide film coated, dried and baked on the substrate with ultraviolet rays was placed in water (boiling point: 100 ° C.) for 3 minutes. After being immersed, the substrate was rinsed with IPA for 1 minute and dried in an oven at 80 ° C. for 10 minutes to obtain a liquid crystal alignment film.
  • size with respect to the orientation direction of the obtained liquid crystal aligning film was 1.17. Further, when the liquid crystal alignment film was visually observed, some unevenness was observed.
  • Example 1 was repeated except that 254 nm ultraviolet rays were irradiated at 0.5 J / cm 2 .
  • Anisotropy with respect to the alignment direction of the liquid crystal alignment film on the film-coated substrate obtained by irradiating the polyimide film coated, dried and baked on the substrate using the liquid crystal alignment agent B obtained in Synthesis Example 4 The magnitude of the property was 1.12. No film unevenness of the liquid crystal alignment film was observed.
  • Example 1 was repeated except that 254 nm ultraviolet rays were irradiated at 0.5 J / cm 2 .
  • the substrate with a film obtained by irradiating the polyimide film coated, dried and baked on the substrate with ultraviolet rays was applied to IPA (boiling point: 82.4 ° C.). After being immersed for 3 minutes at 25 ° C., it was dried in an oven at 80 ° C. for 10 minutes to obtain a liquid crystal alignment film.
  • size with respect to the orientation direction of the obtained liquid crystal aligning film was 1.12. Further, when the alignment film was visually observed, a little unevenness was observed.
  • Example 1 was repeated except that 254 nm ultraviolet rays were irradiated at 0.5 J / cm 2 .
  • the substrate with a film obtained by irradiating the polyimide film coated, dried and baked on the substrate with ultraviolet rays was placed in water (boiling point: 100 ° C.) for 3 minutes. After being immersed, the substrate was rinsed with IPA for 1 minute and dried in an oven at 80 ° C. for 10 minutes to obtain a liquid crystal alignment film.
  • size with respect to the orientation direction of the obtained liquid crystal aligning film was 1.16. Further, when the liquid crystal alignment film was visually observed, some unevenness was observed.
  • Example 1 was repeated except that 254 nm ultraviolet rays were irradiated at 0.5 J / cm 2 .
  • the magnitude of the property was 1.11. No film unevenness of the liquid crystal alignment film was observed.
  • Example 1 was repeated except that 254 nm ultraviolet rays were irradiated at 0.5 J / cm 2 .
  • the substrate with the film was applied to IPA (boiling point: 82.4 ° C.). After being immersed for 3 minutes at 25 ° C., it was dried in an oven at 80 ° C. for 10 minutes to obtain a liquid crystal alignment film.
  • size with respect to the orientation direction of the obtained liquid crystal aligning film was 1.19. Further, when the alignment film was visually observed, a little unevenness was observed.
  • Example 1 was repeated except that 254 nm ultraviolet rays were irradiated at 0.5 J / cm 2 .
  • the substrate with a film obtained by irradiating the polyimide film coated, dried and baked on the substrate with ultraviolet rays was placed in water (boiling point: 100 ° C.) for 3 minutes. After the immersion, the substrate was rinsed with IPA for 1 minute and dried in an oven at 80 ° C. for 10 minutes to obtain a liquid crystal alignment film.
  • size with respect to the orientation direction of the obtained liquid crystal aligning film was 1.19. Further, when the liquid crystal alignment film was visually observed, some unevenness was observed.
  • Example 1 was repeated except that 254 nm ultraviolet rays were irradiated at 0.5 J / cm 2 .
  • the size of was 1.12. No film unevenness of the liquid crystal alignment film was observed.
  • Example 1 was repeated except that 254 nm ultraviolet rays were irradiated at 0.5 J / cm 2 .
  • the substrate with a film obtained by irradiating the polyimide film coated, dried and baked on the substrate with ultraviolet rays was changed to IPA (boiling point: 82.4 ° C.). After being immersed for 3 minutes at 25 ° C., it was dried in an oven at 80 ° C. for 10 minutes to obtain a liquid crystal alignment film.
  • size with respect to the orientation direction of the obtained liquid crystal aligning film was 1.17. Further, when the alignment film was visually observed, a little unevenness was observed.
  • Example 1 was repeated except that 254 nm ultraviolet rays were irradiated at 0.5 J / cm 2 .
  • the substrate with a film obtained by irradiating the polyimide film coated, dried and baked on the substrate with ultraviolet rays was placed in water (boiling point: 100 ° C.) for 3 minutes. After being immersed, the substrate was rinsed with IPA for 1 minute and dried in an oven at 80 ° C. for 10 minutes to obtain a liquid crystal alignment film.
  • size with respect to the orientation direction of the obtained liquid crystal aligning film was 1.17. Further, when the liquid crystal alignment film was visually observed, some unevenness was observed.
  • Example 1 was repeated except that 254 nm ultraviolet rays were irradiated at 0.5 J / cm 2 .
  • Anisotropy with respect to the alignment direction of the liquid crystal alignment film on the substrate with the film obtained by irradiating the polyimide film coated, dried and baked on the substrate using the liquid crystal alignment agent A obtained in Synthesis Example 2 The magnitude of the property was 1.12. No film unevenness of the liquid crystal alignment film was observed.
  • Example 1 was repeated except that 254 nm ultraviolet rays were irradiated at 0.5 J / cm 2 .
  • the substrate with a film obtained by irradiating the polyimide film coated, dried and baked on the substrate with ultraviolet rays was applied to IPA (boiling point: 82.4 ° C.). After being immersed for 3 minutes at 25 ° C., it was dried in an oven at 80 ° C. for 10 minutes to obtain a liquid crystal alignment film.
  • size with respect to the orientation direction of the obtained liquid crystal aligning film was 1.11. Further, when the alignment film was visually observed, a little unevenness was observed.
  • Example 1 was repeated except that 254 nm ultraviolet rays were irradiated at 0.5 J / cm 2 .
  • the substrate with a film obtained by irradiating the polyimide film coated, dried and baked on the substrate with ultraviolet rays was placed in water (boiling point: 100 ° C.) for 3 minutes. After the immersion, the substrate was rinsed with IPA for 1 minute and dried in an oven at 80 ° C. for 10 minutes to obtain a liquid crystal alignment film.
  • size with respect to the orientation direction of the obtained liquid crystal aligning film was 1.11. Further, when the liquid crystal alignment film was visually observed, some unevenness was observed.
  • Example 1 was repeated except that 254 nm ultraviolet rays were irradiated at 0.5 J / cm 2 .
  • Anisotropy with respect to the alignment direction of the liquid crystal alignment film on the substrate with the film obtained by irradiating the polyimide film coated, dried and baked on the substrate using the liquid crystal alignment agent E obtained in Synthesis Example 10 The magnitude of the property was 1.08. No film unevenness of the liquid crystal alignment film was observed.
  • Example 22 The procedure was the same as Example 1 except that 1.0 J / cm 2 of 254 nm ultraviolet light was irradiated.
  • the substrate with a film obtained by irradiating the polyimide film coated, dried and baked on the substrate with ultraviolet rays was applied to IPA (boiling point: 82.4 ° C.). After being immersed for 3 minutes at 25 ° C., it was dried in an oven at 80 ° C. for 10 minutes to obtain a liquid crystal alignment film.
  • size with respect to the orientation direction of the obtained liquid crystal aligning film was 1.04. Further, when the alignment film was visually observed, unevenness was observed.
  • Example 23 The procedure was the same as Example 1 except that 1.0 J / cm 2 of 254 nm ultraviolet light was irradiated.
  • the substrate with a film obtained by irradiating the polyimide film coated, dried and baked on the substrate with ultraviolet rays was placed in water (boiling point: 100 ° C.) for 3 minutes. After being immersed, the substrate was rinsed with IPA for 1 minute and dried in an oven at 80 ° C. for 10 minutes to obtain a liquid crystal alignment film.
  • size with respect to the orientation direction of the obtained liquid crystal aligning film was 1.10. Further, when the liquid crystal alignment film was visually observed, some unevenness was observed.
  • Example 25 The procedure was the same as Example 1 except that 1.0 J / cm 2 of 254 nm ultraviolet light was irradiated.
  • the substrate with a film obtained by irradiating the polyimide film coated, dried and baked on the substrate with ultraviolet rays was applied to IPA (boiling point: 82.4 ° C.). After being immersed for 3 minutes at 25 ° C., it was dried in an oven at 80 ° C. for 10 minutes to obtain a liquid crystal alignment film.
  • size with respect to the orientation direction of the obtained liquid crystal aligning film was 1.09. Further, when the alignment film was visually observed, unevenness was observed.
  • Example 26 The procedure was the same as Example 1 except that 1.0 J / cm 2 of 254 nm ultraviolet light was irradiated.
  • the substrate with a film obtained by irradiating the polyimide film coated, dried and baked on the substrate with ultraviolet rays was placed in water (boiling point: 100 ° C.) for 3 minutes. After being immersed, the substrate was rinsed with IPA for 1 minute and dried in an oven at 80 ° C. for 10 minutes to obtain a liquid crystal alignment film.
  • size with respect to the orientation direction of the obtained liquid crystal aligning film was 1.09. Further, when the liquid crystal alignment film was visually observed, some unevenness was observed.
  • Table 1 summarizes the types of solvents used, the degree of anisotropy of the obtained liquid crystal alignment film, and film unevenness for Examples 1 to 22 and Comparative Examples 1 to 27 described above.
  • the liquid crystal alignment film obtained by the production method of the present invention has high anisotropy, and is widely useful for TN devices, STN devices, TFT liquid crystal devices, and vertical alignment type liquid crystal display devices. Furthermore, by imparting high anisotropy, afterimages derived from liquid crystal orientation, for example, afterimages caused by alternating current drive generated in liquid crystal display elements of the IPS drive method or the FFS drive method can be reduced. This is particularly useful as a liquid crystal alignment film of a liquid crystal display element of an LCD system or FFS driving system or a liquid crystal television.
  • the entire contents of the specification, claims and abstract of Japanese Patent Application No. 2011-202229 filed on September 15, 2011 are incorporated herein as the disclosure of the specification of the present invention. Is.

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Abstract

L'invention concerne un procédé de fabrication d'un film d'alignement de cristaux liquides, par lequel une anisotropie est accrue et l'irrégularité provoquée par le traitement peut être diminuée. Un film obtenu par application d'un agent d'alignement de cristaux liquides contenant au moins un type de polymère choisi dans le groupe consistant en un polyimide et un précurseur du polyimide sur un substrat et cuisson du produit est irradié par un rayonnement polarisé, puis traité par contact avec une solution contenant au moins un type de solvant organique choisi dans le groupe consistant en la formule (A-1), la formule (A-2), la formule (A-3), la formule (A-4), et la formule (A-5). (Dans les formules, A1 représente un atome d'hydrogène ou un groupe acétyle, A2 représente un groupe alkyle en C1-6, R2 représente un atome d'hydrogène ou un groupe méthyle, n représente 1 ou 2, A3 représente un groupe alkyle en C1-4, R3 et R4 représentent un atome d'hydrogène ou un groupe méthyle, A5 et A6 représentent un groupe alkyle en C1-4, et A6 représente un groupe alkyle en C3-6 ou un groupe cycloalkyle).
PCT/JP2012/073515 2011-09-15 2012-09-13 Procédé de fabrication d'un film d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides WO2013039168A1 (fr)

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CN201280056047.9A CN103946738B (zh) 2011-09-15 2012-09-13 液晶取向膜的制造方法、液晶取向膜及液晶显示元件
JP2013533717A JP6056759B2 (ja) 2011-09-15 2012-09-13 液晶配向膜の製造方法、液晶配向膜、及び液晶表示素子

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JPWO2015182762A1 (ja) * 2014-05-30 2017-05-25 日産化学工業株式会社 液晶配向剤、液晶配向膜、及び液晶表示素子

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KR101697336B1 (ko) 2016-03-03 2017-01-17 주식회사 엘지화학 액정 배향막의 제조방법
KR102332258B1 (ko) * 2016-03-22 2021-11-26 닛산 가가쿠 가부시키가이샤 신규 디아민에서 얻어지는 중합체를 함유하는 액정 배향제
JP6777219B2 (ja) 2017-02-28 2020-10-28 Jsr株式会社 液晶配向剤、液晶配向膜及びその製造方法、並びに液晶素子
CN110651221B (zh) * 2017-05-22 2021-10-22 日产化学株式会社 液晶取向剂、液晶取向膜及液晶表示元件
KR102020030B1 (ko) * 2017-08-24 2019-09-10 주식회사 엘지화학 액정 배향제용 중합체, 이를 포함하는 액정 배향제 조성물, 그리고 이를 이용한 액정배향막 및 액정표시소자

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JP2016066044A (ja) * 2014-03-07 2016-04-28 芝浦メカトロニクス株式会社 接液処理装置、接液処理方法、基板処理装置および基板処理方法
WO2015152014A1 (fr) * 2014-03-31 2015-10-08 日産化学工業株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides
JPWO2015152014A1 (ja) * 2014-03-31 2017-04-13 日産化学工業株式会社 液晶配向処理剤、液晶配向膜及び液晶表示素子
JPWO2015182762A1 (ja) * 2014-05-30 2017-05-25 日産化学工業株式会社 液晶配向剤、液晶配向膜、及び液晶表示素子
JPWO2016047774A1 (ja) * 2014-09-26 2017-07-13 日産化学工業株式会社 液晶配向処理剤、液晶配向膜及び液晶表示素子
WO2016047774A1 (fr) * 2014-09-26 2016-03-31 日産化学工業株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides

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