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  • C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
  • C07C217/94—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
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  • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
  • C07C323/31—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
  • C07C323/33—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring
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  • C07D209/80—[b, c]- or [b, d]-condensed
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  • C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
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  • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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  • C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
  • C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
  • C07D241/40—Benzopyrazines
  • C07D241/44—Benzopyrazines with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring
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  • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
  • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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  • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
  • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
  • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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  • 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
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  • 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
  • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
  • C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
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  • 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
  • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
  • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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  • 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
  • C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
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  • 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
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  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2603/00—Systems containing at least three condensed rings
  • C07C2603/02—Ortho- or ortho- and peri-condensed systems
  • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
  • C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
  • C07C2603/24—Anthracenes; Hydrogenated anthracenes
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  • C07C2603/40—Ortho- or ortho- and peri-condensed systems containing four condensed rings
  • C07C2603/42—Ortho- or ortho- and peri-condensed systems containing four condensed rings containing only six-membered rings
  • C07C2603/50—Pyrenes; Hydrogenated pyrenes

Definitions

• the present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display device using the same.
• the liquid crystal alignment film of this polyimide film is prepared by a method of applying a solution of a polyimide precursor polyamic acid or a solvent-soluble polyimide solution to a substrate and subjecting the film obtained by baking to an alignment treatment such as a rubbing treatment. ing.
• This polyamic acid or solvent-soluble polyimide is generally produced by a polycondensation reaction between a tetracarboxylic acid derivative such as tetracarboxylic acid dianhydride and a diamine compound.
• Diamine compounds which are raw materials such as polyamic acid and polyimide, are important because they affect the characteristics of the liquid crystal alignment film obtained therefrom, and thus the characteristics of the liquid crystal display device, and various diamine compounds have been conventionally used. Proposed.
• Patent Document 1 proposes a liquid crystal aligning agent obtained from the following diamine compounds.
• liquid crystal display elements have been improved in performance, area, and power consumption of display devices have been advanced.
• liquid crystal display elements have come to be used in various environments. The characteristics that can be obtained are becoming severe.
• the sensitivity margin means a sensitivity region in which good liquid crystal alignment characteristics can be obtained when polarized ultraviolet rays are irradiated.
• the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a liquid crystal aligning agent capable of obtaining a liquid crystal aligning film having good liquid crystal aligning property and having an increased sensitivity margin. .
• a liquid crystal aligning agent containing a polymer obtained from a novel diamine satisfies the above problems.
• the present invention is based on such findings and has the following gist. From the group consisting of a polyamic acid obtained by reacting a diamine component containing a diamine having a structure represented by the following formula [1] with a tetracarboxylic dianhydride component, and a polyimide obtained by imidizing the polyamic acid.
• a liquid crystal aligning agent comprising at least one polymer selected.
• a 1 and A 2 are each independently a monocyclic group which may have a substituent or a condensed ring group, and A 1 and A 2 are simultaneously a monocyclic group.
• X 1 and X 2 are each independently a single bond, an oxygen atom or a sulfur atom, Q is an alkylene group having 1 or 2 carbon atoms, and m and n are each independently. And is an integer of 1 to 3.
• liquid crystal aligning agent of the present invention a liquid crystal aligning film having good liquid crystal aligning property can be obtained, and a sensitivity margin can be increased.
• the diamine used as a raw material for the liquid crystal aligning agent of the present invention is a diamine having a structure represented by the following formula [1].
• a 1 and A 2 are each independently a monocyclic group which may have a substituent or a condensed ring group, and A 1 and A 2 are simultaneously a monocyclic group. It never happens.
• X 1 and X 2 are each independently a single bond, an oxygen atom or a sulfur atom.
• Q is an alkylene group having 1 or 2 carbon atoms.
• m and n are each independently an integer of 1 to 3.
• a monocyclic group means the remaining atomic group obtained by removing two hydrogen atoms from a monocycle.
• the monocycle include benzene; 5-membered heterocycles such as furan, thiophene, pyrrole, oxazole, thiazole, imidazole, and pyrazole; and 6-membered heterocycles such as pyran, pyrone, pyridine, pyridazine, pyrimidine, and pyrazine.
• the monocycle is preferably benzene or pyridine. When the monocyclic ring is benzene, the monocyclic group is a phenylene group.
• “Fused ring group” means an atomic group remaining after removing two hydrogen atoms from the condensed ring.
• the condensed ring include condensed polycyclic aromatic hydrocarbons such as naphthalene, tetralin, indene, fluorene, anthracene, phenanthrene, and pyrene; benzofuran, thionaphthene, indole, carbazole, coumarin, benzo-pyrone, quinoline, isoquinoline, acridine, Examples include condensed polycyclic heterocycles such as phthalazine, quinazoline, quinoxaline.
• the fused ring is preferably naphthylene, anthracene, pyrene, indole, carbazole, coumarin, benzo-pyrone, quinoline, or isoquinoline.
• the monocyclic group and the condensed ring group may further have a substituent.
• substituents that the monocyclic group and the condensed ring group may have include alkyl having 1 to 4 carbons, alkoxy having 1 to 4 carbons, halogen atom and the like.
• X 1 and X 2 are preferably oxygen atoms.
• Q is preferably alkylene having 2 carbon atoms.
• m and n are preferably 1.
• Specific preferred diamines include, but are not limited to, the followings.
• tetracarboxylic acid dianhydride component a tetracarboxylic dianhydride represented by the following formula [7] (also referred to as a specific tetracarboxylic dianhydride) or a derivative thereof is used as a tetracarboxylic dianhydride component. It is preferably used as a part.
• Z 1 is a tetravalent organic group, and examples thereof include the structures of the following formulas (X1-1) to (X1-19).
• R 3 to R 12 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, 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.
• at least one of R 3 to R 6 is a group other than a hydrogen atom.
• the structure of X 1 is preferably the above formula (X1-1), (X1-3) or (X1-4), and in the formula (X1-1), the following formula (X1-1) At least one selected from the structures represented by -1) to (X1-1-5) is more preferable, and the following formula (X1-1-1) is particularly preferable.
• the tetracarboxylic acid dianhydride represented by the formula [7] or a derivative thereof may be used as a mixture of two or more kinds.
• the use ratio of the tetracarboxylic acid dianhydride represented by the above formula [7] or a derivative thereof is preferably 50 mol% or more based on 1 mol of the tetracarboxylic acid dianhydride component used in the polymer of the present invention, 70 mol% or more is more preferable, and 80 mol% or more is still more preferable. Further, when the tetracarboxylic dianhydride component used in the polymerization of the polymer of the present invention contains the tetracarboxylic dianhydride represented by the above formula [7] or a derivative thereof, suppression of bright spots due to decomposition products It is preferable from the viewpoint of liquid crystal alignment.
• the tetracarboxylic dianhydride component used for the polymerization of the polymer of the present invention may contain a tetracarboxylic dianhydride other than the above formula [7] or a derivative thereof.
• the tetracarboxylic acid dianhydride or derivative thereof other than the above formula [7] may be used alone or in combination of two or more in consideration of the liquid crystal alignment property of the liquid crystal alignment film to be formed, the voltage holding property and the accumulated charge. Can be used.
• the polymer in the present invention means a polyamic acid and / or a polyimide obtained by imidizing the polyamic acid.
• the polyamic acid of the present invention is obtained by the reaction of a diamine component containing a specific diamine and a tetracarboxylic dianhydride component.
• the content ratio of the specific diamine is not limited.
• the content of the specific diamine in the diamine component may be 100%.
• various diamines can be used in combination because they satisfy various properties required for the liquid crystal alignment film, such as a property of increasing the pretilt angle of the liquid crystal and a property of enhancing the vertical alignment property of the liquid crystal.
• the content ratio of the specific diamine in the diamine component used for polymerization is preferably 1 to 50 mol%, particularly preferably 5 to 30 mol%.
• diamine other than the specific diamine used together when the specific diamine is less than 100 mol%, alicyclic diamine, aromatic-aliphatic diamine, aromatic Examples thereof include diamine, heterocyclic diamine, and aliphatic diamine.
• Examples of the alicyclic diamine include 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4′-diaminodicyclohexylmethane, 4,4′-diamino-3,3′-dimethyldicyclohexylamine and isophoronediamine.
• Examples of aromatic diamines include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 3,5-diaminotoluene, 1,4-diamino.
• aromatic-aliphatic diamines include 3-aminobenzylamine, 4-aminobenzylamine, 3-amino-N-methylbenzylamine, 4-amino-N-methylbenzylamine, 3-aminophenethylamine, 4- Aminophenethylamine, 3-amino-N-methylphenethylamine, 4-amino-N-methylphenethylamine, 3- (3-aminopropyl) aniline, 4- (3-aminopropyl) aniline, 3- (3-methylaminopropyl) Aniline, 4- (3-methylaminopropyl) aniline, 3- (4-aminobutyl) aniline, 4- (4-aminobutyl) aniline, 3- (4-methylaminobutyl) aniline, 4- (4-methyl Aminobutyl) aniline, 3- (5-aminopentyl) aniline, 4- (5-aminopentyl Aniline, 3- (5-aminopentyl) aniline, 4-
• heterocyclic diamine examples include 2,6-diaminopyridine, 2,4-diaminopyridine, 2,4-diamino-1,3,5-triazine, 2,7-diaminodibenzofuran and 3,6-diaminocarbazole. , 2,4-diamino-6-isopropyl-1,3,5-triazine, 2,5-bis (4-aminophenyl) -1,3,4-oxadiazole and the like.
• Examples of the aliphatic diamine include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,3-diamino-2,2-dimethylpropane, 1,6-diamino-2,5-dimethylhexane, 1,7- Diamino-2,5-dimethylheptane, 1,7-diamino-4,4-dimethylheptane, 1,7-diamino-3-methylheptane, 1,9-diamino-5-methylnonane, 1,12-diaminododecane, Examples include 1,18-diaminooc
• diamine which has an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocycle, or the macrocyclic substitution body which consists of them in a side chain.
• diamines represented by the following formulas [DA-101] to [DA-130] are exemplified.
• R 6 is an alkyl group or a fluorine-containing alkyl group having 1 to 22 carbon atoms.
• R 7 is an alkyl group, an alkoxy group, having 1 to 22 carbon atoms, It is a fluorine-containing alkyl group or a fluorine-containing alkoxy group.
• R 8 is an alkyl group, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group having 1 to 22 carbon atoms.
• R 9 is a fluorine group, a cyano group, a trifluoromethane group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group, or a hydroxyl group.
• R 10 is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is in the trans form.
• a specific diamine in combination with the above-mentioned [DA-101] to [DA-130] because a more stable pretilt angle can be obtained.
• the diamines of the formulas [DA-110] to [DA-130] are preferred, and the diamines of [DA-110] to [DA-116] are more preferred.
• the preferred content of these diamines is not particularly limited, but is preferably 5 to 50 mol% in the diamine component, and 5 to 30 mol% in terms of printability.
• diamines represented by the following formulas [DA-131] to [DA-138] may be used in combination.
• Diamine is effective in reducing accumulated electrification.
• diaminosiloxane represented by the following formula [DA-139] and the like can also be mentioned as other diamines.
• M is an integer of 1 to 10.
• Y 2 is a divalent organic group having a nitrogen atom bonded to the aromatic group or a nitrogen-containing aromatic heterocycle.
• Examples of Y 2 in the formula (8) include the following formulas (Y2-1) to (Y2-12).
• diamines may be used alone or in combination of two or more depending on properties such as liquid crystal alignment property when the liquid crystal alignment film is formed, voltage holding property and accumulated charge.
• a known method can be used as a method for obtaining the polyamic acid of the present invention by reacting a tetracarboxylic dianhydride component and a diamine component.
• a known method is a method of reacting a tetracarboxylic dianhydride component and a diamine component in an organic solvent.
• the reaction between the tetracarboxylic acid dianhydride component and the diamine proceeds in an organic solvent relatively easily, and no by-product is generated, which is advantageous.
• the organic solvent used for the reaction between the tetracarboxylic dianhydride component and the diamine is not limited as long as it can dissolve the generated polyamic acid. Specific examples are given below. N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, ⁇ -butyrolactone , Isopropyl alcohol, methoxymethyl pentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate
• the organic solvent is preferably dehydrated and dried.
• the tetracarboxylic acid dianhydride component and the diamine component are reacted in an organic solvent, the solution in which the diamine component is dispersed or dissolved in the organic solvent is stirred, and the tetracarboxylic acid dianhydride component as it is, or the organic solvent
• a method of adding by dispersing or dissolving in a solvent, a method of adding a diamine component to a solution in which a tetracarboxylic acid dianhydride component is dispersed or dissolved in an organic solvent, a tetracarboxylic acid dianhydride component and a diamine component are added.
• Examples of the method include alternate addition, and any of these methods may be used.
• the tetracarboxylic dianhydride component or the diamine component is composed of a plurality of types of compounds, they may be reacted in a premixed state, may be individually and sequentially reacted, and are further reacted individually to have a low molecular weight.
• a high molecular weight body may be obtained by mixing and reacting the bodies.
• the temperature at which the tetracarboxylic acid dianhydride component and the diamine component are reacted can be selected from any temperature of -20 to 150 ° C, but is preferably in the range of -5 to 100 ° C.
• the reaction can be carried out at any concentration, but if the concentration is too low, it becomes difficult to obtain a high-molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring is difficult. Therefore, the total concentration of the tetracarboxylic dianhydride component and the diamine component in the reaction solution is preferably 1 to 50% by mass, more preferably 5 to 30% by mass.
• the reaction can be performed at a high concentration in the initial stage, and then an organic solvent can be added.
• the ratio of the total number of moles of the tetracarboxylic dianhydride component to the total number of moles of the diamine component is preferably 0.8 to 1.2, and 0.9 to 1. 1 is more preferable. Similar to the ordinary polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the polyamic acid produced.
• the polyimide of the present invention is a polyimide obtained by dehydrating and ring-closing the above polyamic acid, and is useful as a polymer for obtaining a liquid crystal alignment film.
• the dehydration ring closure rate (imidization rate) of the amic acid group does not necessarily have to be 100%, and can be arbitrarily adjusted according to the application and purpose.
• the method for imidizing the polyamic acid include a thermal imidization method in which a solution of the polyamic acid is heated as it is, and a catalytic imidization method in which a catalyst is added to the solution of the polyamic acid.
• the temperature at which the polyamic acid is subjected to thermal imidization in a solution is 100 to 400 ° C., preferably 120 to 250 ° C., and it is preferable to remove water generated by the imidization reaction outside the system.
• the catalytic imidization of polyamic acid can be carried out by adding a basic catalyst and an acid anhydride to a solution of polyamic acid and stirring the mixture at -20 to 250 ° C, preferably 0 to 180 ° C.
• the amount of the basic catalyst is 0.5 to 30 times, preferably 2 to 20 times the amount of the amic acid group, and the amount of the acid anhydride is 1 to 50 times, preferably 3 to the molar amount of the amic acid group. It is 30 mol times.
• the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Among them, pyridine is preferable because it has a basicity suitable for proceeding the reaction.
• Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic dianhydride, and the use of acetic anhydride is preferable because purification after the reaction is easy.
• the imidization rate by catalytic imidization can be controlled by adjusting the amount of catalyst, reaction temperature, reaction time, and the like.
• the molecular weight of the polymer contained in the liquid crystal aligning agent of the present invention is determined by GPC (Gel Permeation Chromatography) method in consideration of the strength of the obtained coating film, the workability during coating film formation, and the uniformity of the coating film.
• the measured weight average molecular weight is preferably 5,000 to 1,000,000, and more preferably 10,000 to 150,000.
• the liquid crystal aligning agent of the present invention is a coating liquid for forming a liquid crystal aligning film, and is a solution in which a resin component for forming a resin film is dissolved in an organic solvent.
• the resin component contains at least one polymer selected from the above-mentioned polymers of the present invention.
• the content of the resin component in the liquid crystal aligning agent is preferably 1 to 20% by mass, more preferably 3 to 15% by mass, and particularly preferably 3 to 10% by mass. All of the resin components may be the polymer of the present invention, or other polymers may be mixed. At that time, the content of the other polymer in the resin component is 0.5 to 15% by mass, preferably 1 to 10% by mass. Examples of such other polymer include polyamic acid or polyimide obtained by using a diamine compound other than the specific diamine compound as the diamine component to be reacted with the tetracarboxylic dianhydride component.
• the organic solvent used for the liquid crystal aligning agent of the present invention is not particularly limited as long as it is an organic solvent that dissolves the resin component. Specific examples are given below. N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, Dimethyl sulfone, hexamethyl sulfoxide, ⁇ -butyrolactone, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, 1,3 -Dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl is
• the liquid crystal aligning agent of the present invention may contain components other than the above.
• examples thereof include compounds that improve the adhesion between the liquid crystal alignment film and the substrate, such as solvent-rich substances that improve the film thickness uniformity and surface smoothness when the liquid crystal alignment agent is applied.
• Specific examples of the solvent (poor solvent) that improves the uniformity of the film thickness and the surface smoothness include the following.
• Examples of the compound that improves the uniformity of the film thickness and the surface smoothness include a fluorine-based surfactant, a silicone-based surfactant, and a nonion-based surfactant. More specifically, for example, Ftop EF301, EF303, EF352 (manufactured by Tochem Products), Megafac F171, F173, R-30 (manufactured by Dainippon Ink and Chemicals), Fluorard FC430, FC431 (manufactured by Sumitomo 3M) Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.).
• the use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, relative to 100 parts by mass of the resin component contained in the liquid crystal aligning agent.
• the compound that improves the adhesion between the liquid crystal alignment film and the substrate include functional silane-containing compounds and epoxy group-containing compounds shown below.
• phenoplast-based additive for the purpose of preventing the deterioration of the electrical characteristics due to the backlight. Specific phenoplast additives are shown below.
• the liquid crystal aligning agent of the present invention contains a dielectric substance, a conductive substance, and further a film of a liquid crystal alignment film when it is formed into a liquid crystal alignment film for the purpose of changing electrical properties such as dielectric constant and conductivity.
• a crosslinkable compound or the like for the purpose of increasing hardness or compactness may be added.
• the liquid crystal aligning agent of the present invention can be used as a liquid crystal aligning film without applying alignment treatment such as rubbing treatment or light irradiation after being applied on a substrate and baked, or for vertical alignment use.
• the substrate used is not particularly limited as long as it is a highly transparent substrate, and a glass substrate, an acrylic substrate, a plastic substrate such as a polycarbonate substrate, or the like can be used. Further, it is preferable to use a substrate on which an ITO electrode or the like for driving the liquid crystal is formed in terms of simplification of the process.
• an opaque material such as a silicon wafer can be used as long as it is only on one side of the substrate, and in this case, a material such as aluminum that reflects light can be used as the electrode.
• the method for applying the liquid crystal aligning agent is not particularly limited, but industrially, it is generally performed by a method such as screen printing, offset printing, flexographic printing, and inkjet. Other coating methods include dips, roll coaters, slit coaters, spinners and the like, and these may be used depending on the purpose.
• Firing after applying the liquid crystal aligning agent on the substrate is performed at 50 to 300 ° C., preferably 80 to 250 ° C. by a heating means such as a hot plate, and the solvent can be evaporated to form a coating film. If the thickness of the coating film formed after firing is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may decrease, so that the thickness is preferably 5 to 300 nm. It is preferably 10 to 100 nm. When the liquid crystal is horizontally or tilted, the baked coating film is treated by rubbing or irradiation with polarized ultraviolet light.
• the method for aligning a liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention may be a rubbing treatment method, but the liquid crystal aligning agent of the present invention can obtain an alignment treatment with an expanded dose margin as described above. Therefore, the photo-alignment treatment method is preferable.
• radiation having a wavelength of 100 to 800 nm preferably ultraviolet light or visible light
• ultraviolet rays having a wavelength of preferably 100 to 400 nm, more preferably 200 to 400 nm are used.
• the liquid crystal display device of the present invention is a liquid crystal display device in which a liquid crystal alignment film-provided substrate is obtained from the liquid crystal alignment agent of the present invention by the above-mentioned method and then a liquid crystal cell is produced by a known method.
• liquid crystal cell production prepare a pair of substrates on which a liquid crystal alignment film is formed, disperse spacers on the liquid crystal alignment film on one of the substrates, and place the liquid crystal alignment film surface inside.
• examples include a method in which the other substrate is bonded and liquid crystal is injected under reduced pressure for sealing, or a method in which liquid crystal is dropped on the surface of the liquid crystal alignment film on which spacers are dispersed and then the substrate is bonded and sealed.
• the thickness of the spacer is preferably 1 to 30 ⁇ m, more preferably 2 to 10 ⁇ m. ⁇
• NMP N-methyl-2-pyrrolidone
• GBL ⁇ -butyrolactone
• BCS butyl cellosolve
• ethyl acetate (200 g), hexane (100 g) and 1N hydrochloric acid (500 g) were added to the organic layer and added to the separated aqueous layer.
• sodium hydroxide (80 g) was added to make it alkaline.
• the organic layer was separated, washed with saturated aqueous sodium chloride solution, dried over sodium sulfate, filtered, and the filtrate was concentrated to obtain a crude product (154 g).
• Ethyl acetate (462 g) was added to the crude product and the mixture was heated and dissolved at 70 ° C., hexane (770 g) was added, and the mixture was cooled.
• GPC device Shodex (GPC-101), column: Shodex (KD803, KD805 in series), column temperature: 50 ° C, eluent: N, N-dimethylformamide (lithium bromide-water as an additive) 30 mmol / L of hydrate (LiBr.H 2 O), 30 mmol / L of phosphoric acid / anhydrous crystal (o-phosphoric acid), 10 ml / L of tetrahydrofuran (THF), flow rate: 1.0 ml / min
• Calibration curve preparation Standard sample for use TSK standard polyethylene oxide manufactured by Tosoh Corporation (weight average molecular weight (Mw) about 900,000, 150,000, 100,000, 30,000), and polyethylene glycol manufactured by Polymer Laboratory (peak top molecular weight (Mp ) About 12,000, 4,000, 1,000). In order to avoid overlapping of peaks, the measurement was performed using a sample mixed with four kinds of 900,000, 100,000, 12,000 and 1,000
• FFS driving liquid crystal cell In a liquid crystal cell for fringe field switching (FFS) mode, a FOP (Finger on Plate) electrode layer including a surface-shaped common electrode-insulating layer-comb-shaped pixel electrode is formed on the surface.
• FFS fringe field switching
• One glass substrate and a second glass substrate having a columnar spacer having a height of 4 ⁇ m on the front surface and having an ITO film for preventing electrification formed on the back surface were set as a set.
• the pixel electrode has a comb-tooth shape in which a plurality of electrode elements each having a width of 3 ⁇ m and whose central portion is bent at an internal angle of 160 ° are arranged in parallel at intervals of 6 ⁇ m, and one pixel is It has a first region and a second region with a line connecting the bent portions of the plurality of electrode elements as a boundary.
• the liquid crystal alignment film formed on the first glass substrate is subjected to an alignment treatment so that the direction that evenly divides the interior angle of the bent portion of the pixel and the alignment direction of the liquid crystal are orthogonal to each other, and the liquid crystal alignment film that is formed on the second glass substrate is aligned.
• the film is subjected to alignment treatment so that the alignment direction of the liquid crystal on the first substrate and the alignment direction of the liquid crystal on the second substrate coincide with each other when the liquid crystal cell is manufactured.
• a liquid crystal aligning agent filtered with a filter having a pore size of 1.0 ⁇ m was applied to the surface of each of the above-mentioned glass substrates by spin coating, and dried on a hot plate at 80 ° C. for 2 minutes. After that, a predetermined amount of linearly polarized UV light having a wavelength of 254 nm with an extinction ratio of 26: 1 is applied to the surface of the coating film through a polarizing plate, and then baked in a hot air circulating oven at 230 ° C. for 30 minutes to form a liquid crystal film having a thickness of 100 nm. A substrate with an alignment film was obtained.
• a sealant was printed on one of the pair of glass substrates with a liquid crystal alignment film, the other substrate was attached so that the liquid crystal alignment film surfaces faced each other, and the sealant was cured to prepare an empty cell.
• Liquid crystal MLC-3019 manufactured by Merck & Co., Inc.
• the injection port was sealed to obtain an FFS driven liquid crystal cell.
• the obtained liquid crystal cell was heated at 120 ° C. for 1 hour and left overnight, and then the afterimage characteristics were evaluated.
• a liquid crystal cell is installed between two polarizing plates arranged so that their polarization axes are orthogonal to each other, a backlight is turned on, and the liquid crystal cell is arranged so that the transmitted light intensity in the first region of the pixel is minimized.
• the arrangement angle was adjusted, and then the rotation angle required when the liquid crystal cell was rotated so that the transmitted light intensity of the second region of the pixel was minimized was obtained. It can be said that the smaller the value of the rotation angle, the better the afterimage characteristic due to the long-term AC drive.
• the value of the angle ⁇ of the liquid crystal cell was 0.1 ° or less, it was evaluated as “good”.
• A is the component (A)
• B is the component (B)
• C is neither the component (A) nor the component (B)
• PI is polyimide. It means that.
• polyimide resin powder was obtained.
• Example 1 50 ml of 12 g by mass of the polyamic acid solution (A-1-PI) obtained in Synthesis Example 12 and 4.8 g of the 15 mass% of the polyamic acid solution (B-1) obtained in Synthesis Example 10 were used. The mixture was placed in an Erlenmeyer flask, NMP 1.20 g, GBL 6.00 g and BCS 4.00 g were added and mixed at 25 ° C. for 8 hours to obtain a liquid crystal aligning agent (1) (see Table 3 below). No abnormalities such as turbidity and precipitation were observed in this liquid crystal aligning agent, and it was confirmed that the liquid crystal aligning agent was a uniform solution.
• Examples 2 to 16, Comparative Examples 1 and 2> By following the same procedure as in Example 1 except that the polyamic acid solution and the polyimide solution shown in Table 3 below were used instead of the polyimide acid solution (A-1-PI) and the polyamic acid solution (B-1). Thus, liquid crystal aligning agents (2) to (18) were obtained. No abnormalities such as turbidity and precipitation were observed in these liquid crystal aligning agents, and it was confirmed that they were uniform solutions.
• Example 21 [Result of afterimage evaluation by long-term AC drive (when firing is performed before UV irradiation)] ⁇ Example 21> After filtering the liquid crystal aligning agent (1) of Example 1 with a filter having a pore size of 1.0 ⁇ m, a glass substrate having the prepared electrode-attached substrate and a columnar spacer having a height of 4 ⁇ m on which an ITO film is formed on the back surface was applied by spin coating. After drying for 2 minutes on a hot plate at 80 ° C., baking was performed for 30 minutes in a hot air circulation type oven at 230 ° C. to form a coating film having a film thickness of 100 nm.
• This coating film surface was irradiated with linearly polarized ultraviolet light having a wavelength of 254 nm having an extinction ratio of 26: 1 through a polarizing plate and then baked in a hot air circulation oven at 230 ° C. for 30 minutes to obtain a substrate with a liquid crystal alignment film. .
• a set of the above-mentioned two substrates is printed, a sealant is printed on the substrates, and the other substrate is bonded so that the liquid crystal alignment film surfaces face each other and the alignment direction becomes 0 °, and then a seal is formed.
• the agent was cured to prepare an empty cell.
• Liquid crystal MLC-3019 (manufactured by Merck & Co., Inc.) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain an FFS driven liquid crystal cell. After that, the obtained liquid crystal cell was heated at 120 ° C. for 1 hour and left overnight, and afterimage evaluation by long-term AC driving was performed.
• the value of the angle ⁇ of the liquid crystal cell after long-term AC driving is 0.09 ° when the irradiation amount of the ultraviolet rays is 200 mJ / cm 2 , and 0.1 ° when the irradiation amount of 300 mJ / cm 2 is 300 mJ / cm 2 . Since all are 0.1 ° or less, good liquid crystal aligning property was obtained by the liquid crystal aligning agent (1) (see Table 4 below).
• Example 21 except that the liquid crystal aligning agent shown in Table 4 below was used instead of the liquid crystal aligning agent (1) of Example 1 and the ultraviolet irradiation dose was changed to the ultraviolet irradiation dose shown in Table 4 below.
• An FFS-driving liquid crystal cell was produced by the same method as above, and afterimage evaluation by long-term AC driving was performed. Table 4 shows the value of the angle ⁇ of the liquid crystal cell after the long-term AC driving.
• Example 41 [Evaluation result of afterimage by long-term AC drive (when firing is not performed before UV irradiation)] ⁇ Example 41> After filtering with a filter having a pore size of 1.0 ⁇ m using the liquid crystal aligning agent (1) of Example 1, the prepared substrate with an electrode and a columnar spacer having a height of 4 ⁇ m on which an ITO film is formed on the back surface are provided. It was applied to a glass substrate by spin coating. After drying for 2 minutes on a hot plate at 80 ° C, this coating film surface was irradiated with linearly polarized ultraviolet light having a wavelength of 254 nm with an extinction ratio of 26: 1 via a polarizing plate, and then in a hot air circulation oven at 230 ° C.
• a substrate with a liquid crystal alignment film having a film thickness of 100 nm was obtained.
• a set of the above-mentioned two substrates is printed, a sealant is printed on the substrates, and the other substrate is bonded so that the liquid crystal alignment film surfaces face each other and the alignment direction is 0 °, and then a seal is formed.
• the agent was cured to prepare an empty cell.
• Liquid crystal MLC-3019 manufactured by Merck & Co., Inc.
• the value of the angle ⁇ of the liquid crystal cell after long-term AC driving is 0.07 ° when the dose of the ultraviolet rays is 200 mJ / cm 2 , and 0.07 ° when the dose is 300 mJ / cm 2 . Since all are 0.1 ° or less, good liquid crystal aligning property was obtained by the liquid crystal aligning agent (1) (see Table 5 below).
• Example 41 ⁇ Examples 42 to 49, Comparative Examples 41 and 42> Example 41, except that the liquid crystal aligning agent shown in Table 5 below was used in place of the liquid crystal aligning agent (1) of Example 1 and the ultraviolet irradiation dose was changed to the ultraviolet irradiation dose shown in Table 5 below.
• An FFS-driving liquid crystal cell was produced by the same method as above, and afterimage evaluation by long-term AC driving was performed. Table 5 shows the values of the angle ⁇ of the liquid crystal cell after long-term AC driving.
• the angle ⁇ (deg.) Is also an angle ⁇ of 0.1 ° or less, which is a good afterimage characteristic. Therefore, it is possible to improve the display quality of the liquid crystal display device. Excel.
• the liquid crystal aligning agent of the present invention is used in a wide range of fields such as large-sized liquid crystal display devices that require high definition and low cost, and mobile liquid crystal display devices such as smartphones and mobile phones.
• the entire contents of the specification, claims, drawings and abstract of Japanese Patent Application No. 2018-196761 filed on Oct. 18, 2018 are cited herein as disclosure of the specification of the present invention. , Take in.

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