WO2019082975A1 - Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides - Google Patents

Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides

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Publication number
WO2019082975A1
WO2019082975A1 PCT/JP2018/039697 JP2018039697W WO2019082975A1 WO 2019082975 A1 WO2019082975 A1 WO 2019082975A1 JP 2018039697 W JP2018039697 W JP 2018039697W WO 2019082975 A1 WO2019082975 A1 WO 2019082975A1
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WO
WIPO (PCT)
Prior art keywords
liquid crystal
diamine
polyimide
crystal aligning
formula
Prior art date
Application number
PCT/JP2018/039697
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English (en)
Japanese (ja)
Inventor
幸司 巴
大輝 山極
早紀 相馬
新平 新津
Original Assignee
日産化学株式会社
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Filing date
Publication date
Application filed by 日産化学株式会社 filed Critical 日産化学株式会社
Priority to KR1020207012497A priority Critical patent/KR102586312B1/ko
Priority to CN201880069243.7A priority patent/CN111279255B/zh
Priority to JP2019550283A priority patent/JP7276666B2/ja
Publication of WO2019082975A1 publication Critical patent/WO2019082975A1/fr

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    • 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
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/48—Polymers modified by chemical after-treatment
    • 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
    • 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
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • 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
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to a liquid crystal aligning agent, a liquid crystal aligning film, and a liquid crystal display device.
  • the liquid crystal display element is configured by sandwiching a liquid crystal layer by a pair of transparent substrates provided with electrodes. And in a liquid crystal display element, the organic film which consists of organic materials is used as a liquid crystal aligning film so that a liquid crystal may be in a desired orientation state between board
  • the inventors conducted various studies to achieve the above object, and found that the liquid crystal aligning agent having the following constitution is most suitable for achieving the above object, and completed the present invention.
  • a liquid crystal aligning agent containing a polyimide which is a reaction product of a carboxylic acid dianhydride derivative component comprising at least one selected from aliphatic tetracarboxylic acid dianhydrides and alicyclic tetracarboxylic acid dianhydrides and a diamine component.
  • P 1 and P 2 are a phenyl or biphenyl group, and hydrogen on the aromatic ring may be replaced by a methyl group or a fluorine group.
  • Q is a divalent organic group, and n1 and n2 are integers of 0 to 5. However, when at least one of n1 and n2 is 0, Q is an oxygen atom.
  • Preferred specific examples of [A] include diamines of the following formulas [A-1] to [A-6].
  • liquid crystal aligning agent of the present invention it is possible to obtain a liquid crystal alignment film which satisfies various properties required for the liquid crystal alignment film and which gives a low pretilt angle of 1 degree or less.
  • the polyimide contained in the liquid crystal aligning agent of the present invention is a tetracarboxylic acid dianhydride derivative component comprising at least one selected from aliphatic tetracarboxylic acid dianhydride and alicyclic tetracarboxylic acid dianhydride and a specific diamine Is obtained by imidizing a polyimide precursor obtained from a diamine component containing (hereinafter, also referred to as a specific polymer).
  • a specific diamine Is obtained by imidizing a polyimide precursor obtained from a diamine component containing
  • tetracarboxylic acid dihalide compounds tetracarboxylic acid dialkyl esters and tetracarboxylic acid dialkyl esters are used as tetracarboxylic acid derivatives used for producing polyimide precursors Ester dihalides are mentioned.
  • aliphatic and alicyclic tetracarboxylic acid dianhydrides and derivatives thereof those represented by the following formula (4) are preferable.
  • X 1 preferable structures of X 1 include the following formulas (X1-1) to (X1-24).
  • R 3 to R 23 each independently represent 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, It is an alkynyl group having 2 to 6 carbon atoms, a monovalent organic group having 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group.
  • R 3 to R 23 are preferably a hydrogen atom, a halogen atom, a methyl group or an ethyl group, and a hydrogen atom or a methyl group is preferable.
  • Specific examples of the formula (X1-1) include the following formulas (X1-1-1) to (X1-1-6). (X1-1-1) is particularly preferable from the viewpoint of liquid crystal alignment and sensitivity of photoreaction.
  • the diamine component used for manufacture of the polyimide contained in the liquid crystal aligning agent of this invention contains at least 1 sort (s) chosen from the diamine of following formula [A].
  • P 1 and P 2 are a phenyl or biphenyl group, and hydrogen on the aromatic ring may be replaced by a methyl group or a fluorine group.
  • Q is a divalent organic group, and n1 and n2 are integers of 0 to 5. However, when at least one of n1 and n2 is 0, Q is an oxygen atom.
  • Q is preferably an oxygen atom, and in this case, the formula [A] is represented as the following [A ′] .
  • X is a divalent organic group selected from the following structures.
  • Each * represents a bond to an oxygen atom.
  • Preferred specific examples of [A] include diamines of the following formulas [A-1] to [A-6]. These may be used alone or in combination of two or more.
  • the preferred content of the diamine of the above formula [A] is preferably 40% to 80%, more preferably 40% to 70%, still more preferably 40% to 60% of the total diamine components.
  • the diamine component used for manufacture of the polyimide contained in the liquid crystal aligning agent of this invention can use various diamine according to the characteristic of the liquid crystal aligning agent calculated
  • Other diamines are represented by the following formula (5).
  • a 1 and A 2 each independently represent a hydrogen atom, or an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms is there.
  • the structure of Y 1 is not particularly limited. Preferred structures include the following (Y-1) to (Y-177).
  • Me represents a methyl group
  • R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms.
  • D is a thermally leaving group which is preferably desorbed at 150 to 230 ° C., more preferably 180 to 230 ° C. to replace a hydrogen atom.
  • Y including the structure represented by the above formula (6) include (Y-124) and (Y-158) to (Y-163).
  • the polyamic acid which is a polyimide precursor used in the present invention is specified with a tetracarboxylic acid dianhydride derivative component consisting of at least one selected from aliphatic tetracarboxylic acid dianhydride and alicyclic tetracarboxylic acid dianhydride. It is a polyimide precursor obtained from the diamine component containing a diamine, and can be manufactured by the method shown below.
  • an organic tetracarboxylic acid dianhydride derivative component consisting of at least one selected from aliphatic tetracarboxylic acid dianhydrides and alicyclic tetracarboxylic acid dianhydrides and a diamine component containing a specific diamine It can be synthesized by reacting in the presence of a solvent at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C, for 30 minutes to 24 hours, preferably 1 to 12 hours.
  • the organic solvent used for the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone or ⁇ -butyrolactone in view of solubility of monomers and polymers, and one or more of these may be mixed You may use.
  • 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 unlikely to occur and a high molecular weight polymer is easily obtained.
  • the polyamic acid obtained as described above can be recovered by precipitating a polymer by pouring the reaction solution into a poor solvent while well stirring it. Further, precipitation is carried out several times, and after washing with a poor solvent, it is possible to obtain a purified polyamic acid powder by normal temperature or heat drying.
  • the poor solvent is not particularly limited, and water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene and the like can be mentioned.
  • the polyamic acid ester which is one of the polyimide precursors used for this invention can be manufactured by the method of (I), (II) or (III) shown below.
  • a polyamic acid ester can be synthesized by esterifying a polyamic acid obtained from tetracarboxylic acid dianhydride and diamine. Specifically, the polyamic acid and the esterifying agent are reacted in the presence of an organic solvent at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C, for 30 minutes to 24 hours, preferably 1 to 4 hours. It can be synthesized.
  • esterifying agent those which can be easily removed by purification are preferable, and 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 amount of the esterifying agent used is preferably 2 to 6 molar equivalents with respect to 1 mole of the repeating unit of the polyamic acid.
  • the solvent used for the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, or ⁇ -butyrolactone in view of the solubility of the polymer, and these may be used alone or in combination of two or more. Good.
  • the concentration of the polymer in the reaction solution is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass, from the viewpoint that precipitation of the polymer hardly occurs and a polymer can be easily obtained.
  • Polyamic acid ester can be manufactured from tetracarboxylic acid diester dichloride and diamine. Specifically, tetracarboxylic acid diester dichloride and diamine in the presence of a base and an organic solvent at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C, for 30 minutes to 24 hours, preferably 1 to 4 hours It can be synthesized by reaction.
  • pyridine triethylamine, 4-dimethylaminopyridine and the like can be used, but pyridine is preferable because the reaction proceeds mildly.
  • the amount of the base used is preferably 2 to 4 times the molar amount of the tetracarboxylic acid diester dichloride from the viewpoint of easy removal and high molecular weight.
  • the solvent used for the above reaction is preferably N-methyl-2-pyrrolidone or ⁇ -butyrolactone in view of the solubility of monomers and polymers, and these may be used alone or in combination of two or more.
  • the concentration of the polymer in the reaction solution is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass, from the viewpoint that precipitation of the polymer hardly occurs and a polymer can be easily obtained.
  • the solvent used for the synthesis of the polyamic acid ester is preferably dehydrated as much as possible, and it is preferable to prevent the mixing of outside air in a nitrogen atmosphere.
  • Polyamic acid ester can be manufactured by polycondensing tetracarboxylic acid diester and diamine. Specifically, a tetracarboxylic acid diester and a diamine in the presence of a condensing agent, a base and an organic solvent at 0 ° C. to 150 ° C., preferably 0 ° C. to 100 ° C., for 30 minutes to 24 hours, preferably 3 to 15 It can be produced by reacting for time.
  • the condensing agent examples include triphenyl phosphite, dicyclohexyl carbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N′-carbonyldiimidazole, dimethoxy-1,3,5-triadidi Nylmethylmorpholinium, O- (benzotriazol-1-yl) -N, N, N ', N'-tetramethyluronium tetrafluoroborate, O- (benzotriazol-1-yl) -N, N And N ′, N′-tetramethyluronium hexafluorophosphate, diphenyl (2,3-dihydro-2-thioxo-3-benzoxazolyl) phosphonate and the like can be used.
  • the addition amount of the condensing agent is preferably 2 to 3 moles per mol of the tetracarboxylic acid die
  • tertiary amines such as pyridine and triethylamine can be used.
  • the amount of the base used is preferably 2 to 4 moles per mole of the diamine component from the viewpoint of easy removal and high molecular weight.
  • the reaction proceeds efficiently by adding a Lewis acid as an additive.
  • a Lewis acid lithium halides such as lithium chloride and lithium bromide are preferable.
  • the addition amount of the Lewis acid is preferably 0 to 1.0 times the molar amount with respect to the diamine component.
  • the method for producing the above (I) or the above (II) is particularly preferable because a high molecular weight polyamic acid ester can be obtained.
  • the solution of the polyamic acid ester obtained as described above can precipitate the polymer by pouring it into a poor solvent while stirring well. Precipitation is carried out several times, and after washing with a poor solvent, it is possible to obtain a purified polyamic acid ester powder at room temperature or by heating and drying.
  • the poor solvent is not particularly limited, and water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene and the like can be mentioned.
  • the polyimide used in the present invention can be produced by imidizing the above-mentioned polyamic acid or polyamic acid ester.
  • the imidation ratio of the polyimide used in the present invention is preferably 70 to 99% from the viewpoint of the electrical properties.
  • chemical imidization which adds a basic catalyst to the polyamic acid solution obtained by dissolving the said polyamic acid ester solution or 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 molecular weight reduction of the polymer does not easily occur in the imidization process.
  • Chemical imidization can be carried out by stirring the polyamic acid or polyamic acid ester 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 and trioctylamine.
  • pyridine is preferable because it has a suitable basicity to allow the reaction to proceed.
  • acetic anhydride trimellitic anhydride, pyromellitic anhydride and the like can be mentioned, and it is preferable to use acetic anhydride among them because purification after completion of the reaction becomes easy.
  • the temperature at which the imidization reaction is carried out is, for example, ⁇ 20 ° C. to 120 ° C., preferably 0 ° C. to 100 ° C., and the reaction time can be 1 to 100 hours.
  • the amount of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the amic acid group, and the amount of the acid anhydride is 1 to 50 moles, preferably 3 to 30 moles of the amic acid group. It is a double.
  • the imidation ratio of the resulting polymer can be controlled by adjusting the amount of catalyst, temperature and reaction time.
  • the obtained imidized polymer is recovered by the means described below, and redissolved in an organic solvent.
  • the liquid crystal aligning agent of the present invention is used.
  • the solution of the polyimide obtained as mentioned above can precipitate a polymer by inject
  • the poor solvent is not particularly limited, and methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene and the like can be mentioned.
  • the liquid crystal aligning agent of the present invention has a form of a solution in which a polymer containing a specific polymer is dissolved in an organic solvent.
  • the molecular weight of the polyimide precursor and the polyimide described in the present invention is preferably 2,000 to 500,000, more preferably 5,000 to 300,000, and still more preferably 10,000 to 100, in weight average molecular weight. , 000. Also, 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 content of the specific polymer in the liquid crystal aligning agent of the present invention is preferably 2 to 10% by mass, and more preferably 3 to 8% by mass, in the liquid crystal aligning agent.
  • the liquid crystal aligning agent of the present invention may contain, in addition to the specific polymer, a polyamic acid which is a reaction product of an optional tetracarboxylic acid derivative component and an optional diamine component.
  • the proportion is preferably 10 to 900 parts by mass, and more preferably 25 to 700 parts by mass with respect to 100 parts by mass of polyimide.
  • Other polymers may be mixed in all the polymer components in the liquid crystal aligning agent of the present invention.
  • Other polymers include cellulose polymers, acrylic polymers, methacrylic polymers, polystyrenes, polyamides, polysiloxanes, and the like.
  • the content of the other polymer other than that is preferably 0.5 to 15 parts by mass, and more preferably 1 to 10 parts by mass with respect to 100 parts by mass in total of the polyimide and the polyamic acid.
  • the concentration of the polymer of the liquid crystal aligning agent used in the present invention can be appropriately changed by setting the thickness of the coating film to be formed, but from the point of forming a uniform and defect-free coating film, 1 weight % Or more is preferable, and from the viewpoint of storage stability of the solution, 10% by weight or less is preferable.
  • the solvent in the liquid crystal aligning agent of the present invention is a solvent that dissolves a polyimide precursor and a polyimide (also referred to as a good solvent) or a solvent that improves the coating properties and surface smoothness of the liquid crystal alignment film when the liquid crystal aligning agent is applied. (Also referred to as a poor solvent) is preferably used. Specific examples of other solvents are listed below, but are not limited to these examples.
  • the good solvent examples include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-butyl-2-pyrrolidone, ⁇ -butyrolactone, ⁇ -valerolactone, 1,3-dimethylimidazolidinone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, methyl ethyl ketone, cyclohexanone, cyclopentanone, 3-methoxy-N, N-dimethylpropanamide or 4-hydroxy-4-methyl-2-pentanone and the like. be able to.
  • the poor solvent include 1-butoxy-2-propanol, 2-butoxy-1-propanol, 2-propoxyethanol, 2- (2-propoxyethoxy) ethanol, 1-propoxy-2-propanol ethanol, isopropyl alcohol 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isopentyl alcohol, tert-pentyl alcohol, 3 -Methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3 -Heptanol, 1-octano , 2-octanol, 2-ethyl-1-hexanol, cyclohe
  • R 24 and R 25 are each independently a linear or branched alkyl group having 1 to 8 carbon atoms. However, R 24 + R 25 is an integer greater than 3. Further, as the poor solvent, when the solubility of the polyimide precursor and the polyimide contained in the liquid crystal aligning agent in the solvent is high, the solvents represented by the following [D-1] to the formula [D-3] are preferable.
  • D 1 represents an alkyl group having 1 to 3 carbon atoms
  • D 2 represents an alkyl group having 1 to 3 carbon atoms
  • Formula [D-3] among, D 3 is an alkyl group having 1 to 4 carbon atoms.
  • the liquid crystal aligning agent of the present invention is at least one kind of substitution selected from the group consisting of a crosslinkable compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group.
  • a crosslinkable compound having a group or a crosslinkable compound having a polymerizable unsaturated bond may be included.
  • crosslinking compound various known compounds can be used depending on the purpose.
  • the following compounds are preferably used.
  • the content of the crosslinkable compound is preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of all the polymer components. Among these, in order for the crosslinking reaction to proceed and to achieve the desired effect, 0.1 to 100 parts by mass is preferable, and 1 to 50 parts by mass is more preferable.
  • the liquid crystal aligning agent of this invention can contain the compound which improves the uniformity of the film thickness of a liquid crystal aligning film at the time of apply
  • a fluorine-type surfactant As a compound which improves the uniformity of the film thickness of a liquid crystal aligning film, and surface smoothness, a fluorine-type surfactant, a silicone type surfactant, a nonion type surfactant etc. are mentioned.
  • the amount of surfactant used is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 parts by mass, with respect to 100 parts by mass of all polymer components contained in the liquid crystal aligning agent.
  • it contains a silane coupling agent for the purpose of improving the adhesion between the liquid crystal alignment film and the substrate, and an imidization accelerator for the purpose of efficiently advancing the imidization by heating the polyimide precursor when baking the coating film. You may
  • the liquid crystal aligning film of this invention is a film
  • the substrate to which the liquid crystal aligning agent of 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. At that time, it is preferable to use a substrate on which an ITO electrode or the like for driving liquid crystal is formed, from the viewpoint of simplification of the process. Further, in the reflection type liquid crystal display element, an opaque material such as a silicon wafer can be used if it is only on one substrate, and in this case, a material that reflects light such as aluminum can also be used for the electrode.
  • the liquid crystal aligning agent is generally applied by screen printing, offset printing, flexographic printing or ink jet method, and as the other coating methods, dip method, roll coater method, slit coater, etc. Methods, spinner methods or spray methods are known.
  • the solvent can be evaporated by using a heating means such as a hot plate, a thermal circulation type oven or an IR (infrared) type oven to form a liquid crystal alignment film.
  • a heating means such as a hot plate, a thermal circulation type oven or an IR (infrared) type oven to form a liquid crystal alignment film.
  • the drying and baking steps after the application of the liquid crystal aligning agent can be performed at any temperature and time. Usually, in order to sufficiently remove the contained solvent, baking is carried out at 50 to 120 ° C. for 1 to 10 minutes, followed by baking at 150 to 300 ° C. for 5 to 120 minutes.
  • the thickness of the liquid crystal alignment film after firing is preferably 5 to 300 nm, and more preferably 10 to 200 nm, because if it is too thin, the reliability of the liquid crystal display element may decrease.
  • the liquid crystal aligning agent of the present invention can be used as a liquid crystal alignment film without application of alignment treatment in a vertical alignment application or the like after being coated and baked on a substrate and then subjected to alignment treatment by rubbing treatment or photo alignment treatment.
  • a known method or apparatus can be used in alignment treatment such as rubbing treatment or light alignment treatment.
  • a liquid crystal display element having a passive matrix structure is described as an example. It may be a liquid crystal display element of an active matrix structure in which a switching element such as a TFT (Thin Film Transistor) is provided in each pixel portion constituting an image display.
  • TFT Thin Film Transistor
  • 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, for example, ITO electrodes, and are patterned to provide a desired image display.
  • 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 of SiO 2 -TiO 2 formed by a sol-gel method.
  • a liquid crystal alignment film is formed on each substrate, the other substrate is superimposed on one of the substrates so that the liquid crystal alignment film faces each other, and the periphery is bonded with a sealing agent.
  • a spacer in the sealing agent it is usually preferable to mix a spacer in the sealing agent, and to disperse the substrate gap control spacer also in the in-plane portion where the sealing agent is not provided.
  • An opening capable of being filled with liquid crystal from the outside is provided in part of the sealing agent.
  • a liquid crystal material is injected into the space surrounded by the two substrates and the sealing agent through the opening provided in the sealing agent, and then the opening is sealed with an adhesive.
  • the liquid crystal material may be either a positive liquid crystal material or a negative liquid crystal material, preferably a negative liquid crystal material.
  • the polarizing plate is installed. Specifically, a pair of polarizing plates is attached to the surface of the two substrates opposite to the liquid crystal layer.
  • the imidation ratio of the polyimide in the synthesis example was measured as follows. 30 mg of polyimide powder is placed in an NMR (nuclear magnetic resonance) sample tube (NMR sampling tube standard, ⁇ 5 (manufactured by Kusano Scientific Co., Ltd.)), and deuterated dimethyl sulfoxide (DMSO-d6, 0.05 mass% TMS (tetramethylsilane) The mixture (0.53 ml) was added and sonicated to dissolve completely. This solution was subjected to proton NMR measurement at 500 MHz with an NMR measurement device (JNW-ECA 500) (manufactured by Nippon Denshi Datum Co., Ltd.).
  • the imidation ratio is determined using a proton derived from a structure that does not change before and after imidization as a reference proton, and a peak integrated value of this proton and a proton peak derived from the NH group of amic acid appearing around 9.5 ppm to 10.0 ppm It calculated
  • x is the proton peak integrated value derived from the NH group of the amic acid
  • y is the peak integrated value of the reference proton
  • ⁇ is one NH group proton of the amic acid in the case of polyamic acid (imidation ratio is 0%) The ratio of the number of reference protons to.
  • the reaction solution was poured into 2770 g of methanol, and the obtained precipitate was separated by filtration.
  • the precipitate was washed with methanol and then dried under reduced pressure at a temperature of 80 ° C. to obtain a powder of polyimide (imidation ratio: 87%).
  • 40.0 g of the powder of this polyimide is separated in a 500 mL Erlenmeyer flask containing a stirrer, 293 g of NMP is added, and stirred at 70 ° C. for 24 hours for dissolution to obtain a solution SPI-A1 of polyimide.
  • composition example 2 In a 100 mL recovery type flask equipped with a stirrer and a nitrogen inlet tube, 5.62 g (19.2 mmol) of DA-1, 4.18 g (10.5 mmol) of DA-2, and 2.92 g of DA-3 (5. 5 g). 24 mmol) Measured, 54.3 g of NMP was added, and stirred and dissolved while feeding nitrogen. While the diamine solution was stirred under water cooling, 4.50 g (22.7 mmol) of CA-3 was added, 15.5 g of NMP was further added, and the mixture was stirred at 50 ° C. for 1 hour under a nitrogen atmosphere.
  • the reaction solution was poured into 170 g of methanol, and the obtained precipitate was separated by filtration.
  • the precipitate was washed with methanol and then dried under reduced pressure at a temperature of 80 ° C. to obtain a powder of polyimide (imidation ratio: 86%).
  • 4.00 g of the powder of this polyimide is taken into a 500 mL Erlenmeyer flask containing a stirring bar, 29.3 g of NMP is added, and stirred at 70 ° C. for 24 hours to dissolve, and then polyimide solution SPI-A2 I got
  • composition example 3 In a 100 mL recovery type flask equipped with a stirrer and a nitrogen inlet tube, 5.62 g (19.2 mmol) of DA-1, 4.18 g (10.5 mmol) of DA-2, and 2.92 g of DA-3 (5. 5 g). 24 mmol) Measured, 50.9 g of NMP was added, and stirred and dissolved while feeding nitrogen. While stirring this diamine solution under water cooling, 4.50 g (22.7 mmol) of CA-3 was added, and 18.0 g of NMP was further added, and the mixture was stirred at 50 ° C. for 1 hour under a nitrogen atmosphere.
  • the reaction solution was poured into 170 g of methanol, and the obtained precipitate was separated by filtration.
  • the precipitate was washed with methanol and then dried under reduced pressure at a temperature of 80 ° C. to obtain a powder of polyimide (imidation ratio: 86%).
  • 4.00 g of the powder of this polyimide is taken into a 500 mL Erlenmeyer flask containing a stirring bar, 29.3 g of NMP is added, and stirred at 70 ° C. for 24 hours to dissolve, and polyimide solution SPI-A3 I got
  • composition example 4 In a 100 mL recovery type flask equipped with a stirrer and a nitrogen inlet tube, 4.82 g (16.4 mmol) of DA-1, 3.58 g (8.98 mmol) of DA-2, 2.50 g of DA-3 (4. 49 mmol) Measured, 53.3 g of NMP was added, and stirred and dissolved while feeding nitrogen. While the diamine solution was stirred under water cooling, 4.96 g (22.1 mmol) of CA-1 was added, 19.3 g of NMP was further added, and the mixture was stirred at 50 ° C. for 1 hour under a nitrogen atmosphere.
  • the reaction solution was poured into 170 g of methanol, and the obtained precipitate was separated by filtration.
  • the precipitate was washed with methanol and then dried under reduced pressure at a temperature of 80 ° C. to obtain a powder of polyimide (imidation ratio: 84%).
  • 4.00 g of powder of this polyimide is taken into a 500 mL Erlenmeyer flask containing a stirrer, 29.3 g of NMP is added, and stirred at 70 ° C. for 24 hours to dissolve, and then polyimide solution SPI-A4 I got
  • composition example 5 In a 100 mL recovery type flask equipped with a stirrer and a nitrogen inlet tube, 2.89 g (9.88 mmol) of DA-1, 3.94 g (9.89 mmol) of DA-2, and 2.75 g of DA-3 (4. 94 mmol) and 2.01 g (8.22 mmol) of DA-4 were weighed out, 49.5 g of NMP was added, and the solution was stirred and dissolved while feeding nitrogen. While stirring the diamine solution under water cooling, 4.25 g (21.4 mmol) of CA-3 was added, and 14.7 g of NMP was further added, followed by stirring at 50 ° C. for 1 hour under a nitrogen atmosphere.
  • the reaction solution was poured into 160 g of methanol, and the obtained precipitate was separated by filtration.
  • the precipitate was washed with methanol and dried under reduced pressure at a temperature of 80 ° C. to obtain a powder of polyimide (imidation ratio: 82%).
  • 4.00 g of powder of this polyimide is taken into a 500 mL Erlenmeyer flask containing a stirrer, 29.3 g of NMP is added, and stirred at 70 ° C. for 24 hours to dissolve, and polyimide solution SPI-A5 I got
  • the reaction solution was poured into 1040 g of methanol, and the obtained precipitate was separated by filtration.
  • the precipitate was washed with methanol and then dried under reduced pressure at a temperature of 80 ° C. to obtain a powder of polyimide (imidation ratio: 81%).
  • 4.00 g of powder of this polyimide is taken into a 500 mL Erlenmeyer flask containing a stirrer, 29.3 g of NMP is added, and stirred at 70 ° C. for 24 hours to dissolve, and polyimide solution SPI-A6 I got
  • Synthesis Example 8 After 30.0 g of the solution PAA-B1 of the polyamic acid obtained in Synthesis Example 1 was separated, 26.2 g of NMP, 2.44 g of acetic anhydride, and 0.630 g of pyridine were added and stirred at room temperature for 30 minutes. The reaction was allowed to proceed at 40 ° C. for 30 minutes. The reaction solution was poured into 150 g of methanol, and the resulting precipitate was filtered off. The precipitate was washed with methanol and then dried under reduced pressure at a temperature of 80 ° C. to obtain a powder of polyimide (imidation ratio: 40%).
  • Synthesis Example 12 In a 100 mL recovery type flask equipped with a stirrer and a nitrogen inlet tube, 7.09 g (19.3 mmol) of DA-10, 4.18 g (10.5 mmol) of DA-2, and 2.92 g of DA-3 (5. 25 mmol) Measured, 60.5 g of NMP was added, and stirred and dissolved while feeding nitrogen. While stirring this diamine solution under water cooling, 4.51 g (22.8 mmol) of CA-3 was added, and further 15.2 g of NMP was added, and the mixture was stirred at 50 ° C. for 1 hour under a nitrogen atmosphere.
  • Synthesis Example 15 In a 100 mL Erlenmeyer flask containing a stirrer, 30.0 g of the solution of polyamic acid obtained in Synthesis Example 2 is separated, 0.470 g of di-tert-butyl dicarbonate is added, and then reacted at 40 ° C. for 12 hours. The Furthermore, 20.0 g of NMP, 3.85 g of acetic anhydride, and 1.28 g of pyridine were added, and the mixture was stirred at room temperature for 30 minutes and then reacted at 60 ° C. for 4 hours. The reaction solution was poured into 220 g of methanol, and the resulting precipitate was filtered off.
  • Examples 1 to 15 and Comparative Examples 1 to 3 NMP was added to a solution obtained by mixing the solution of polyamic acid obtained in Synthesis Example 1 to 15 and the solution of polyimide in the ratio of polymer 1 and polymer 2 as shown in the following table.
  • GBL, BCS, NMP solution containing 1% by weight of AD-1, and NMP solution containing 10% by weight of AD-2 are added while stirring to obtain the composition shown in the table below, and further stirred at room temperature for 2 hours
  • liquid crystal aligning agents of Examples 1 to 15 and Comparative Examples 1 to 3 were obtained.
  • a substrate with an electrode was prepared.
  • the substrate is a glass substrate with a size of 30 mm ⁇ 40 mm and a thickness of 1.1 mm.
  • An ITO electrode having a film thickness of 35 nm is formed on the substrate, and the electrode has a stripe pattern of 40 mm long and 10 mm wide.
  • the liquid crystal aligning agent was filtered through a filter with a pore diameter of 1.0 ⁇ m, and then applied to the prepared electrode-equipped substrate by spin coating. After drying on a hot plate at 80 ° C. for 2 minutes, baking was carried out in an IR oven at 230 ° C.
  • Two substrates with this liquid crystal alignment film are prepared, and a spacer of 4 ⁇ m is sprayed on the surface of one liquid crystal alignment film, and then a sealing agent is printed thereon, and the rubbing direction of the other substrate is reverse. And, after bonding so that the film surfaces face each other, the sealing agent was cured to produce an empty cell.
  • a liquid crystal MLC-3019 manufactured by Merck & Co., Ltd.
  • a glass substrate with a size of 30 mm ⁇ 35 mm and a thickness of 0.7 mm was prepared.
  • an IZO electrode having a solid pattern is formed, which constitutes a counter electrode as a first layer.
  • a SiN (silicon nitride) film formed by the CVD method is formed as a second layer on the first counter electrode.
  • the film thickness of the second SiN film is 500 nm and functions as an interlayer insulating film.
  • a comb-like pixel electrode formed by patterning an IZO film as a third layer is disposed on the second layer SiN film, and two pixels of a first pixel and a second pixel are formed. ing.
  • the size of each pixel is about 10 mm in height and about 5 mm in width.
  • the first opposing electrode and the third pixel electrode are electrically insulated by the action of the second SiN film.
  • the pixel electrode of the third layer has a comb-like shape configured by arranging a plurality of “ ⁇ ” shaped electrode elements whose central portion is bent as shown in FIG. 3 described in JP-A-2014-77845. It has the shape of The width in the short direction of each electrode element is 3 ⁇ m, and the distance between the electrode elements is 6 ⁇ m. Since the pixel electrode forming each pixel is configured by arranging a plurality of bent " ⁇ " shaped electrode elements in the central portion, the shape of each pixel is not rectangular, and the center is the same as the electrode elements. It has a shape resembling a bold " ⁇ " that bends in parts. And each pixel is divided up and down bordering on the central bending part, and has the 1st field of the upper part of a bending part, and the 2nd field of the lower side.
  • the forming directions of the electrode elements of the pixel electrodes constituting them are different. That is, on the basis of the rubbing direction of the liquid crystal alignment film described later, the electrode element of the pixel electrode is formed at an angle of + 10 ° (clockwise) in the first region of the pixel, and the pixel in the second region of the pixel The electrode elements of the electrodes are formed at an angle of -10 ° (clockwise).
  • the directions of rotational movement (in-plane switching) in the substrate plane of the liquid crystal induced by voltage application between the pixel electrode and the counter electrode are mutually different. It is configured to be in the opposite direction.
  • the liquid crystal aligning agent is filtered with a filter having a pore diameter of 1.0 ⁇ m, and then an ITO film is formed on the back surface as the electrode-attached substrate and the opposite substrate, and a glass substrate having columnar spacers of 4 ⁇ m in height Each was spin-coated.
  • baking was performed at 230 ° C. for 20 minutes to obtain a polyimide film with a film thickness of 60 nm on each substrate.
  • This liquid crystal alignment film is rubbed with a rayon cloth (roller diameter: 120 mm, roller rotation speed: 500 rpm, moving speed: 30 mm / sec, indentation length: 0.3 mm), and then ultrasonic irradiation is performed for 1 minute in pure water. The resultant was washed, air droplets were removed by air blow, and dried at 80 ° C. for 10 minutes to obtain a substrate with a liquid crystal alignment film. Using the two types of substrates with the liquid crystal alignment film, they were combined so that their rubbing directions would be antiparallel, and the periphery was sealed leaving a liquid crystal injection port to produce an empty cell with a cell gap of 3.8 ⁇ m. .
  • Liquid crystal MLC-3019 (manufactured by Merck & Co., Ltd.) was vacuum injected into this empty cell at normal temperature, and then the inlet was sealed to obtain a liquid crystal cell of anti-parallel alignment.
  • the obtained liquid crystal cell constituted an FFS mode liquid crystal display element. Thereafter, the liquid crystal cell was heated at 120 ° C. for 1 hour, allowed to stand at 23 ° C. overnight, and then used for each evaluation described below.
  • Pretilt angle> The pretilt angle in the liquid crystal cell 1 was evaluated using AxoScan Muller matrix polarimeter manufactured by Optometrics.
  • ⁇ Voltage holding ratio> A voltage of 1 V was applied for 60 ⁇ sec at a temperature of 60 ° C. to the liquid crystal cell 1 and the voltage after 50 msec was measured to evaluate how much the voltage could be maintained as a voltage retention rate.
  • this liquid crystal cell After standing overnight at 23 ° C., this liquid crystal cell is placed between two polarizing plates disposed so that the polarization axes are orthogonal to each other, and the backlight is turned on with no voltage applied, and the brightness of the transmitted light
  • the arrangement angle of the liquid crystal cell was adjusted so as to minimize.
  • the rotation angle when the liquid crystal cell is rotated from the angle at which the second region of the first pixel is the darkest to the angle at which the first region is the dark is calculated as the angle ⁇ 1.
  • the angle ⁇ 2 was calculated by comparing with the first region. The average value of these ⁇ 1 and ⁇ 2 was defined as the angle ⁇ of the liquid crystal cell, and the smaller this value, the better the liquid crystal alignment was defined and evaluated.
  • liquid crystal display devices using the liquid crystal aligning agents of Examples 1 to 15 and Comparative Examples 1 to 3 above show the results of the pretilt angle, the voltage holding ratio, and the liquid crystal cell angle ⁇ performed as described above. .
  • the liquid crystal display device using the liquid crystal aligning agent of the embodiment of the present invention has a low pretilt angle, a high voltage holding ratio, and good liquid crystal alignment.
  • liquid crystal aligning agent of the present invention it is possible to obtain a liquid crystal alignment film which satisfies various properties required for the liquid crystal alignment film and which gives a low pretilt angle of 1 degree or less.

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Abstract

La présente invention concerne un agent d'alignement de cristaux liquides qui contient un polyimide qui est un produit de réaction d'un composant diamine et d'un composant dérivé de dianhydride d'acide tétracarboxylique comprenant au moins une espèce choisie parmi un dianhydride d'acide tétracarboxylique aliphatique et un dianhydride d'acide tétracarboxylique alicyclique, le composant diamine contenant au moins une espèce choisie parmi les diamines représentées par la formule [A], et le taux d'imidisation du polyimide étant supérieur ou égal à 70 %. Dans la formule : P1 et P2 sont des groupes phényle ou biphényle, et un atome d'hydrogène sur un cycle aromatique de ceux-ci peut être substitué par un groupe méthyle ou un groupe fluor ; Q est un groupe organique divalent, et n1 et n2 sont des nombres entiers de 0 à 5, Q étant un atome d'oxygène lorsque n1 et/ou n2 sont égaux à 0.
PCT/JP2018/039697 2017-10-26 2018-10-25 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides WO2019082975A1 (fr)

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KR20210125901A (ko) 2020-04-09 2021-10-19 제이에스알 가부시끼가이샤 액정 배향제, 액정 배향막 및 그의 제조 방법, 그리고 액정 소자
KR20220106750A (ko) 2019-11-26 2022-07-29 닛산 가가쿠 가부시키가이샤 액정 배향제, 액정 배향막 및 액정 표시 소자
KR20220109304A (ko) 2021-01-28 2022-08-04 제이에스알 가부시끼가이샤 액정 배향제, 액정 배향막 및 그의 제조 방법, 그리고 액정 소자
KR20230002334A (ko) 2020-04-10 2023-01-05 닛산 가가쿠 가부시키가이샤 액정 배향제, 액정 배향막 및 액정 표시 소자
WO2023074391A1 (fr) * 2021-10-28 2023-05-04 日産化学株式会社 Composition polymère, agent d'alignement de cristaux liquides, film de résine, film d'alignement de cristaux liquides, procédé de production d'élément d'affichage à cristaux liquides et élément d'affichage à cristaux liquides
KR20230109658A (ko) 2020-11-19 2023-07-20 닛산 가가쿠 가부시키가이샤 액정 배향제, 중합체의 제조 방법, 액정 배향막, 액정 표시 소자
KR20240004616A (ko) 2021-05-06 2024-01-11 닛산 가가쿠 가부시키가이샤 액정 배향제, 액정 배향막 및 액정 표시 소자

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WO2020040089A1 (fr) * 2018-08-20 2020-02-27 日産化学株式会社 Agent d'alignement de cristaux liquides et son procédé de production, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides
KR20220106750A (ko) 2019-11-26 2022-07-29 닛산 가가쿠 가부시키가이샤 액정 배향제, 액정 배향막 및 액정 표시 소자
WO2021112095A1 (fr) * 2019-12-06 2021-06-10 日産化学株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, élément d'affichage à cristaux liquides, et procédé de production d'élément d'affichage à cristaux liquides
CN114761866A (zh) * 2019-12-06 2022-07-15 日产化学株式会社 液晶取向剂、液晶取向膜、液晶显示元件以及液晶显示元件的制造方法
KR20210125901A (ko) 2020-04-09 2021-10-19 제이에스알 가부시끼가이샤 액정 배향제, 액정 배향막 및 그의 제조 방법, 그리고 액정 소자
KR20230002334A (ko) 2020-04-10 2023-01-05 닛산 가가쿠 가부시키가이샤 액정 배향제, 액정 배향막 및 액정 표시 소자
KR20230109658A (ko) 2020-11-19 2023-07-20 닛산 가가쿠 가부시키가이샤 액정 배향제, 중합체의 제조 방법, 액정 배향막, 액정 표시 소자
KR20220109304A (ko) 2021-01-28 2022-08-04 제이에스알 가부시끼가이샤 액정 배향제, 액정 배향막 및 그의 제조 방법, 그리고 액정 소자
KR20240004616A (ko) 2021-05-06 2024-01-11 닛산 가가쿠 가부시키가이샤 액정 배향제, 액정 배향막 및 액정 표시 소자
WO2023074391A1 (fr) * 2021-10-28 2023-05-04 日産化学株式会社 Composition polymère, agent d'alignement de cristaux liquides, film de résine, film d'alignement de cristaux liquides, procédé de production d'élément d'affichage à cristaux liquides et élément d'affichage à cristaux liquides

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CN111279255A (zh) 2020-06-12
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JP7276666B2 (ja) 2023-05-18
KR102586312B1 (ko) 2023-10-06
TW201930401A (zh) 2019-08-01

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