Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
  • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
  • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
  • C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
  • C07D251/24—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to three ring carbon atoms
• • 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
  • C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
  • C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
  • C08G73/0644—Poly(1,3,5)triazines
• • 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
  • C08G73/1075—Partially aromatic polyimides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
  • C08K5/3477—Six-membered rings
  • C08K5/3492—Triazines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
  • G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation

Definitions

• the present invention relates to a liquid crystal alignment treatment agent, a liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent, and a liquid crystal display element using the same.
• liquid crystal alignment film of a liquid crystal display element a so-called polyimide-based liquid crystal alignment film, which is obtained by applying and baking a liquid crystal alignment treatment agent mainly composed of a polyimide precursor such as polyamic acid or a soluble polyimide solution, is mainly used. It has been.
• the liquid crystal alignment film is used for the purpose of controlling the alignment state of the liquid crystal.
• the characteristics required of the liquid crystal alignment film are that the alignment of the liquid crystal can be controlled, that the voltage holding ratio (hereinafter also referred to as VHR) is excellent, that the charge accumulated by the DC voltage is quickly relaxed, the amount of ions in the liquid crystal cell There are few things.
• liquid crystal display elements that can withstand long-term use have been demanded.
• the characteristics do not change even if light from the backlight unit or sunlight including ultraviolet rays is irradiated for a long period.
• a liquid crystal alignment film whose display characteristics do not change greatly by backlight light or ultraviolet irradiation.
• Non-Patent Document 1 a process for aligning liquid crystals by irradiating ultraviolet rays has been adopted in recent liquid crystal display element manufacturing processes (see, for example, Non-Patent Document 1).
• a process of irradiating ultraviolet rays has been introduced by a liquid crystal dropping method (ODF), a PSA (Polymer Sustained Alignment) process, and the like.
• ODF liquid crystal dropping method
• PSA Polymer Sustained Alignment
• Patent Documents 1 and 2 As an effort to increase the light resistance of liquid crystal display elements, for example, in Patent Documents 1 and 2, additives such as benzotriazole-based UV absorbers and benzophenone-based UV absorbers are added to the liquid crystal alignment treatment agent to increase the lifetime of the liquid crystal. There are attempts to make it longer. In Patent Document 3, an attempt is made to extend the life of the liquid crystal by further adding an antioxidant to the benzotriazole ultraviolet absorber or the benzophenone ultraviolet absorber.
• Patent Document 4 discloses that the addition of a benzotriazole-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, a dialkyldithiocarbamic acid metal salt, or the like to a liquid crystal alignment treatment agent prevents the resulting alignment film from being decomposed by ultraviolet rays. It is reported that it can be done. Furthermore, Patent Documents 5 and 6 report a method for producing a liquid crystal panel having excellent light resistance by adding a benzotriazole compound or a hindered amine compound to a liquid crystal alignment treatment agent. However, these additives have a problem that the VHR of the liquid crystal alignment film itself is lowered although there is an effect of suppressing the reduction of VHR caused by UV (ultraviolet) irradiation.
• Patent Document 7 a diamine having a triazine skeleton has been proposed.
• Japanese Unexamined Patent Publication No. 56-1116012 Japanese Unexamined Patent Publication No. 57-84429 Japanese Unexamined Patent Publication No. 57-108828 Japanese Unexamined Patent Publication No. 10-148835 Japanese Unexamined Patent Publication No. 2003-215592 Japanese Unexamined Patent Publication No. 2004-53685 Japanese Unexamined Patent Publication No. 2011-128597
• an object of the present invention is to provide a liquid crystal alignment treatment agent that can obtain a liquid crystal alignment film having good rubbing resistance and high light resistance.
• a liquid crystal aligning agent having a compound having a triazine skeleton and a hydroxyl group (hereinafter also referred to as a specific compound). I found what I could achieve. That is, the present invention has the following gist. 1.
• a liquid crystal aligning agent comprising a compound represented by the general formula (1). (Wherein R 1 to R 14 are each independently a hydrogen atom or a divalent organic group, and any one or more of R 1 to R 14 is an alkyl group having 4 or more carbon atoms) An organic group containing 2.
• the content of the compound represented by the formula (1) is 0 with respect to 100 parts by weight of at least one polymer selected from the group consisting of the polyimide precursor and a polyimide obtained by imidizing the polyimide precursor.
• the weight average molecular weight of at least one polymer selected from the group consisting of the polyimide precursor and a polyimide obtained by imidizing the polyimide precursor is 10,000 to 150,000, Liquid crystal aligning agent.
• liquid crystal aligning agent according to any one of 1 to 4 above, wherein the liquid crystal aligning agent contains 92 to 99% by weight of an organic solvent. 6). 6. The liquid crystal aligning agent according to 5 above, wherein the organic solvent contains 5 to 80% by weight of a poor solvent. 7). 7. A liquid crystal alignment film obtained from the liquid crystal alignment treatment agent according to any one of 1 to 6 above. 8). 8. The liquid crystal alignment film as described in 7 above, wherein the film thickness is 10 to 200 ⁇ m. 9. 9. 9. A liquid crystal display device comprising the liquid crystal alignment film according to 7 or 8 above.
• liquid crystal aligning agent capable of obtaining a liquid crystal alignment film having good rubbing resistance and high light resistance.
• each of R 1 to R 14 is independently a hydrogen atom or a monovalent organic group, and any one or more of R 1 to R 14 is an alkyl group having 4 or more carbon atoms. Contains organic groups. By including an alkyl group having 4 or more carbon atoms, there is an effect of increasing the solubility of the specific compound in the organic solvent. Furthermore, the specific compound is effectively gathered on the surface of the fired coating film, and there is an effect that the deterioration of the resin component (liquid crystal alignment film) in the vicinity of the surface that affects the VHR characteristics can be effectively suppressed. Further, it is possible to impart a pretilt expression ability to the liquid crystal alignment film by lengthening the alkyl group.
• the alkyl group may be directly bonded to the phenyl group, but is preferably bonded through a group such as —O—, —NHCO— or —COO— from the viewpoint of solubility.
• the substituent other than the alkyl group is not particularly limited, but a phenyl group is preferable from the viewpoint of heat resistance of the specific compound.
• —OH group, —NH 2 , —COOH, A polar group such as —NHR (R is a monovalent organic group) is preferred, and an alkyl group is particularly preferred from the viewpoint of ease of migration of the specific compound to the membrane surface.
• Preferred specific structural examples include 2- [4,6-bisC2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol, Ciba Japan Tinuvin (R) 400, Tinuvin (R) 405 (generic name: 2- [4-[(2-hydroxy-3- (2′-ethyl) hexyl) oxy] -2-hydroxyphenyl] -4,6- Bis (2,4-dimethylphenyl) -1,3,5-triazine), tinuvin (R) 460 (generic name: 2,4-bis (2-hydroxy-4-butyloxyphenyl) -6- (2, 4-bis-butyloxyphenyl) -1,3,5-triazine), tinuvin (R) 477, tinuvin (R) 479 (generic name: 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] Phenyl)
• the polyimide precursor contained in the liquid crystal alignment treatment agent of the present invention and the polyimide imidized from the polyimide precursor are used.
• the amount is preferably 0.5 to 10 parts by weight, more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of at least one polymer (polymer compound) selected from the group consisting of
• the addition method to the liquid crystal alignment treatment agent is not particularly limited, but a predetermined amount of the specific compound is directly added to the liquid crystal alignment treatment agent and dissolved by stirring, or about 0.5 to 10% by weight of the specific compound is previously added to the organic solvent. It may be dissolved and added to the liquid crystal aligning agent.
• the polyimide precursor contained in the liquid crystal aligning agent of the present invention refers to polyamic acid (also referred to as polyamic acid) and polyamic acid ester.
• a polyamic acid is obtained by reaction of a diamine component and tetracarboxylic dianhydride.
• the polyamic acid ester is obtained by reacting the diamine component and tetracarboxylic acid diester dichloride in the presence of a base, or reacting the tetracarboxylic acid diester and diamine in the presence of a suitable condensing agent or base.
• the polyimide of the present invention can be obtained by dehydrating and ring-closing this polyamic acid or by heating and ring-closing the polyamic acid ester. Any of such polyamic acid, polyamic acid ester, and polyimide is useful as a polymer for obtaining a liquid crystal alignment film.
• the diamine component used is not particularly limited. Specific examples are as follows. Examples of alicyclic diamines include 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4′-diaminodicyclohexylmethane, 4,4′-diamino-3,3′-dimethyldicyclohexylamine, isophorone Examples include diamines.
• aromatic diamines examples include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 3,5-diaminotoluene, 1,4-diamino -2-methoxybenzene, 2,5-diamino-p-xylene, 1,3-diamino-4-chlorobenzene, 3,5-diaminobenzoic acid, 1,4-diamino-2,5-dichlorobenzene, 4,4 '-Diamino-1,2-diphenylethane, 4,4'-diamino-2,2'-dimethylbibenzyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane 4,4′-diamin
• aromatic-aliphatic diamines include 3-aminobenzylamine, 4-aminobenzylamine, 3-amino-N-methylbenzylamine, 4-amino-N-methylbenzylamine, 3-aminophenethylamine, 4-aminobenzylamine, 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-methyl)
• heterocyclic diamines examples include 2,6-diaminopyridine, 2,4-diaminopyridine, 2,4-diamino-1,3,5-triazine, 2,7-diaminodibenzofuran, 3,6-diamino
• examples thereof include carbazole, 2,4-diamino-6-isopropyl-1,3,5-triazine, 2,5-bis (4-aminophenyl) -1,3,4-oxadiazole.
• aliphatic diamines examples 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-methylheptane, 1,12-diamino Examples include dodecane, 1,18-diaminoocta
• diamine compound which has an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, and the macrocyclic substituent which consists of them in a side chain.
• diamines represented by the following formulas [DA1] to [DA26] can be exemplified.
• R 6 represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group.
• S 5 represents —COO—, —OCO—, —CONH—, —NHCO—, —CH 2 —, —O—, —CO—, or —NH—.
• R 6 represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group.
• S 6 represents —O—, —OCH 2 —, —CH 2 O—, —COOCH 2 —, or —CH 2 OCO—
• R 7 represents the number of carbon atoms.
• S 7 represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, — OCH 2 — or —CH 2 —, wherein R 8 is an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group.
• S 8 represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, — OCH 2 —, —CH 2 —, —O— or —NH—, wherein R 9 is a fluorine group, a cyano group, a trifluoromethyl group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group, or It is 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 a trans isomer.
• n is an integer of 1 to 5.
• [DA-27] and [DA-28] can improve the voltage holding ratio (also referred to as VHR) of the liquid crystal display element by using these.
• [DA-29] to [DA-34] It is effective because it is effective in reducing the accumulated charge of the liquid crystal display element.
• diaminosiloxanes represented by the following formula [DA35] can also be exemplified.
• m is an integer of 1 to 10.
• Said diamine compound can also be used 1 type or in mixture of 2 or more types according to characteristics, such as a liquid crystal aligning property at the time of setting it as a liquid crystal aligning film, a voltage holding characteristic, and an accumulation charge.
• the tetracarboxylic dianhydride made to react with a diamine component is not specifically limited. Specific examples are given below. Examples of the tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutane.
• Tetracarboxylic dianhydride 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetra Carboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic Acid dianhydride, 3,4-dicarboxy-1-cyclohexylsuccinic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 1, , 3,4-Butanetetracarboxylic dianhydride, bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride, 3,3 ′, 4,4′-dicyclo
• the liquid crystal alignment is improved and the accumulated charge of the liquid crystal cell is reduced. Since it can reduce, it is preferable.
• Aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic acid Dianhydride, 2,3,3 ′, 4-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,3,3 ′, 4-benzophenonetetra Carboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride And 2,3,6,7-naphthalenetetracarboxylic dianhydride and the like.
• the tetracarboxylic dianhydride
• the tetracarboxylic-acid dialkyl ester made to react with a diamine component is not specifically limited. Specific examples are given below. Specific examples of the aliphatic tetracarboxylic acid diester include 1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2 , 3,4-cyclopentanetetracarboxylic acid dialkyl ester, 2,3,4,5-tetrahydrofurantetracarboxylic acid dialkyl ester, 1,2,4,5-cyclohexanetetracarboxylic acid dialkyl
• aromatic tetracarboxylic acid dialkyl ester examples include pyromellitic acid dialkyl ester, 3,3 ′, 4,4′-biphenyltetracarboxylic acid dialkyl ester, 2,2 ′, 3,3′-biphenyltetracarboxylic acid dialkyl ester, 2,3,3 ′, 4-biphenyltetracarboxylic acid dialkyl ester, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid dialkyl ester, 2,3,3 ′, 4-benzophenone tetracarboxylic acid dialkyl ester, bis (3,4-dicarboxyphenyl) ether dialkyl ester, bis (3,4-dicarboxyphenyl) sulfone dialkyl ester, 1,2,5,6-naphthalenetetracarboxylic acid dialkyl ester, 2,3,6,7- Naphthalenetetracarboxylic acid dialkyl
• a method of adding by dispersing or dissolving a method of adding a diamine component to a solution in which tetracarboxylic dianhydride is dispersed or dissolved in an organic solvent, and alternately adding a tetracarboxylic dianhydride and a diamine component.
• the method etc. are mentioned. Any of these methods may be used.
• the tetracarboxylic dianhydride or diamine component is composed of a plurality of types of compounds, they may be reacted in a premixed state, may be individually reacted sequentially, or may be further reacted individually.
• the body may be mixed and reacted to form a high molecular weight body.
• the polymerization temperature can be selected from -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 is 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 and the diamine component in the reaction solution is preferably 1 to 50% by weight, more preferably 5 to 30% by weight.
• the initial stage of the reaction is carried out at a high concentration, and then an organic solvent can be added.
• the ratio of the total number of moles of tetracarboxylic dianhydride to the total number of moles of the diamine component is preferably 0.8 to 1.2, preferably 0.9 to 1.1. More preferred. Similar to the normal polycondensation reaction, the closer the molar ratio is to 1.0, the higher the molecular weight of the polyamic acid produced.
• the polyimide contained in the liquid crystal aligning agent 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 cyclization rate (imidation rate) of the amic acid group is not necessarily 100%, and can be arbitrarily adjusted according to the application and purpose. .
• Examples of the method for imidizing the polyamic acid include thermal imidization in which the polyamic acid solution is heated as it is, and catalytic imidization in which a catalyst is added to the polyamic acid solution.
• the temperature at which the polyamic acid is thermally imidized in the solution is 100 to 400 ° C., preferably 120 to 250 ° C., and the method is preferably performed while removing water generated by the imidization reaction from the system.
• Catalytic imidation of polyamic acid can be carried out by adding a basic catalyst and an acid anhydride to a polyamic acid solution and stirring at -20 to 250 ° C, preferably 0 to 180 ° C.
• the amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times the amidic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol times the amido group. 30 mole times.
• the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Among them, pyridine is preferable because it has an appropriate basicity for proceeding with the reaction.
• the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is easy.
• the imidization rate by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.
• polyamic acid ester As a method of synthesizing polyamic acid ester, it is a kind of polyimide precursor by reacting tetracarboxylic acid diester dichloride and diamine, or reacting tetracarboxylic acid diester and diamine in the presence of a suitable condensing agent and base. A certain polyamic acid ester can be obtained. Alternatively, it can also be obtained by polymerizing a polyamic acid in advance and esterifying the carboxylic acid in the amic acid using a polymer reaction.
• tetracarboxylic acid diester dichloride and diamine are mixed in the presence of a base and an organic solvent at ⁇ 20 to 150 ° C., preferably 0 to 50 ° C. for 30 minutes to 24 hours, preferably 1 to 4 hours. It can be synthesized by reacting.
• a base pyridine, triethylamine, 4-dimethylaminopyridine and the like can be used, but pyridine is preferable because the reaction proceeds gently.
• the addition amount of the base is preferably 2 to 4 times mol, preferably 2 to 3 times mol with respect to tetracarboxylic acid diester dichloride, from the viewpoint of easy removal and high molecular weight. More preferred.
• examples of the condensing agent include triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N′-carbonyldiimidazole.
• the reaction proceeds efficiently by adding Lewis acid as an additive.
• Lewis acid lithium halides such as lithium chloride and lithium bromide are preferable.
• the addition amount of the Lewis acid is preferably 0.1 to 1.0 times the molar amount relative to the condensing agent, and more preferably 0.3 to 0.8 times the molar amount.
• the solvent used in the above reaction can be a solvent used when polymerizing polyamic acid, but N-methyl-2-pyrrolidone, ⁇ -butyrolactone and the like are preferable from the viewpoint of the solubility of the monomer and polymer, and these are You may use 1 type or in mixture of 2 or more types.
• the concentration at the time of synthesis is preferably 1 to 30% by weight, and more preferably 5 to 20% by weight from the viewpoint that polymer precipitation is unlikely to occur and a high molecular weight product is easily obtained.
• the solvent used for the synthesis of the polyamic acid ester is preferably dehydrated as much as possible, and the reaction is preferably performed in a nitrogen atmosphere while preventing external air from being mixed. .
• the reaction solution may be poured into a poor solvent and precipitated.
• the poor solvent used for precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and water. Of these, methanol is preferable.
• the polymer precipitated in a poor solvent and collected by filtration can be dried at normal temperature or under reduced pressure at room temperature or by heating.
• the molecular weight of the polyamic acid and the polyimide contained in the liquid crystal aligning agent of the present invention is determined by considering the strength of the coating film obtained therefrom, the workability at the time of forming the coating film, and the uniformity of the coating film.
• the weight average molecular weight measured by Permeation Chromatography is preferably 5,000 to 1,000,000, and more preferably 10,000 to 150,000.
• the liquid crystal alignment treatment agent of the present invention is a coating liquid for forming a liquid crystal alignment film, and at least one polymer selected from the group consisting of the polyimide precursor and polyimide described above and the additive of the present invention are organic. It is a solution dissolved in a solvent.
• the solid content concentration in the liquid crystal alignment treatment agent of the present invention can be appropriately changed depending on the thickness of the liquid crystal alignment film to be formed, but is preferably 0.5 to 10% by weight, and preferably 1 to 8% by weight. More preferably. If the solid content concentration is less than 0.5% by weight, it is difficult to form a uniform and defect-free coating film, and if it exceeds 10% by weight, the storage stability of the solution may be deteriorated.
• solid content refers to a component obtained by removing the solvent from the liquid crystal aligning agent, and at least one polymer selected from the group consisting of the polyimide precursor and polyimide described above, the additive of the present invention, and the above description. Means various additives.
• the manufacturing method of the liquid-crystal aligning agent of this invention is not specifically limited. Usually, it manufactures by mixing the solution of the said polyimide precursor, the solution of a polyimide, or the solution of a polyimide, and the solution of a polyimide precursor.
• the polyamic acid reaction solution obtained by polycondensation may be used as it is, or once the polyamic acid is obtained, it is redissolved in an organic solvent to obtain a polyamic acid solution. Can be used.
• the polyamic acid solution may be used after diluted to a desired concentration.
• the reaction solution of soluble polyimide obtained by imidization may be used as it is, or once polyimide powder is obtained, it is redissolved in an organic solvent as a polyimide solution. Can be used.
• the polyimide solution may be used after diluting to a desired concentration.
• the organic solvent used for the liquid-crystal aligning agent of this invention will not be specifically limited if it is an organic solvent in which a resin component is dissolved. Specific examples are given below. N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethyl-2-pyrrolidone, 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 ket
• the content of the organic solvent in the liquid crystal aligning agent is 80 to 99.5% by weight, preferably 90 to 99.5% by weight. From the viewpoint of storage stability of the solution and formation of a uniform coating film, More preferably, it is 92 to 99% by weight.
• the liquid crystal aligning agent of the present invention may contain components other than those described above. Examples include solvents and compounds that improve film thickness uniformity and surface smoothness when a liquid crystal alignment treatment agent is applied, compounds that improve the adhesion between the liquid crystal alignment film and the substrate, and oxidation that improves thermal stability. Inhibitors, light stabilizers that improve light resistance, and the like.
• isopropyl alcohol methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoacetate Isopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipro Lenglycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether
• Examples of compounds that improve film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. More specifically, for example, F-top EF301, EF303, EF352 (manufactured by Tochem Products), MegaFuck F171, F173, R-30 (manufactured by Dainippon Ink), Florard FC430, FC431 (manufactured by Sumitomo 3M) ), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.). The use ratio of these surfactants is preferably 0.01 to 2 parts by weight, more preferably 0.01 to 1 part by weight with respect to 100 parts by weight 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 the following functional silane-containing compounds and epoxy group-containing compounds.
• the compound that improves the thermal stability include the following phenol compounds.
• the liquid crystal aligning agent of the present invention can be preferably formed into a coating film by filtering before applying to the substrate, applying to the substrate, drying and baking.
• the coating film surface is used as a liquid crystal alignment film of the present invention by performing an alignment process such as rubbing or light irradiation.
• the substrate to be used is not particularly limited as long as it is a highly transparent substrate, and a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like can be used.
• an opaque substrate such as a silicon wafer can be used as long as only one substrate is used. In this case, a material that reflects light such as aluminum can be used for the electrode.
• Examples of the method for applying the liquid crystal alignment treatment agent include spin coating, printing, and ink jet methods. From the standpoint of productivity, the flexographic printing method is widely used industrially, and the liquid crystal alignment of the present invention. It is also preferably used in the treatment agent.
• the drying process after applying the liquid crystal alignment treatment agent is not necessarily required, but if the time from application to baking is not constant for each substrate, or if baking is not performed immediately after application, the drying process is performed. Preferably included.
• the drying is not particularly limited as long as the solvent is evaporated to such an extent that the shape of the coating film is not deformed by transporting the substrate or the like.
• a method of drying on a hot plate at 50 to 150 ° C., preferably 80 to 120 ° C., for 0.5 to 30 minutes, preferably 1 to 5 minutes is employed.
• the substrate coated with the liquid crystal aligning agent can be baked at an arbitrary temperature of 100 to 350 ° C., preferably 150 to 300 ° C., more preferably 180 to 250 ° C.
• the polyamic acid contained in the liquid crystal aligning agent changes the conversion rate from polyamic acid to imide by this firing, but the polyamic acid does not necessarily need to be 100% imidized.
• baking is preferably performed at a temperature higher by 10 ° C. or more than the heat treatment temperature required for the manufacturing process of the liquid crystal cell, such as curing of the sealant.
• the thickness of the coating film after baking 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 be lowered, so it is preferably 10 to 200 nm, more preferably 50 to 100 nm.
• An existing rubbing apparatus can be used for rubbing the coating surface formed on the substrate as described above. Examples of the material of the rubbing cloth at this time include cotton, rayon, and nylon.
• the liquid crystal display element of the present invention is a liquid crystal display element obtained by obtaining a substrate with a liquid crystal alignment film from the liquid crystal aligning agent of the present invention by the method described above, and then preparing a liquid crystal cell by a known method.
• a pair of substrates on which a liquid crystal alignment film is formed is preferably an arbitrary rubbing direction of 0 to 270 ° with a spacer of preferably 1 to 30 ⁇ m, more preferably 2 to 10 ⁇ m.
• the angle is set so that the angle is fixed, the periphery is fixed with a sealant, and the liquid crystal is injected and sealed.
• the method for enclosing the liquid crystal is not particularly limited, and examples thereof include a vacuum method of injecting liquid crystal after reducing the pressure inside the produced liquid crystal cell, and a dropping method of sealing after dropping the liquid crystal.
• the liquid crystal display element thus obtained can be reduced in electrical characteristics due to backlight or ultraviolet light irradiation and can be a highly reliable liquid crystal display device.
• GPC device manufactured by Shodex (GPC-101) Column: manufactured by Shodex (series of KD803 and KD805) Column temperature: 50 ° C Eluent: N, N-dimethylformamide (as additives, lithium bromide-hydrate (LiBr ⁇ H 2 O) 30 mmol / L, phosphoric acid / anhydrous crystal (o-phosphoric acid) 30 mmol / L, tetrahydrofuran) (THF) is 10 mL / L) Flow rate: 1.0 mL / minute standard sample for preparing a calibration curve: TSK standard polyethylene oxide (molecular weight: about 900,000, 150,000, 100,000, 30000) manufactured by Tosoh Corporation, and polyethylene glycol (molecular weight: about 12,000, 4000, 1000) manufactured by Polymer Laboratories .
• TSK standard polyethylene oxide molecular weight: about 900,000, 150,000, 100,000, 30000
• polyethylene glycol molecular weight: about
• the imidization ratio of the polyimide was measured by dissolving the polyimide in d6-DMSO (dimethylsulfoxide-d6, TMS (tetramethylsilane) mixed product) and using 400 MHz 1 H NMR (manufactured by Varian). That is, a proton derived from a structure that does not change before and after imidation is determined as a reference proton, and a peak integrated value of this proton and a proton peak integrated value derived from NH group of amic acid appearing in the vicinity of 9.5 to 10.0 ppm was obtained by the following equation.
• Imidization rate (%) (1 ⁇ ⁇ x / y) ⁇ 100
• x is a proton peak integrated value derived from NH group of amic acid
• y is a peak integrated value of reference proton
• ⁇ is one NH group proton of amic acid in the case of polyamic acid (imidation rate is 0%) Is the number ratio of the reference proton to.
• the reaction solution was cooled to about room temperature and then poured into 2000 ml of methanol to recover the precipitated solid.
• the solid was washed several times with methanol and then dried under reduced pressure at 100 ° C. to obtain a white powder of polyimide.
• the number average molecular weight of this polyimide was 12,500, and the weight average molecular weight was 34,100.
• the imidation ratio was 90%.
• 6 g of the obtained powder was dissolved in a mixed solution of 74 g of ⁇ -BL and 20 g of BS by stirring at 50 ° C. for 24 hours to obtain a polymer solution P-2 having a resin component of 6% by weight. .
• the reaction solution was cooled to about room temperature and then poured into 2000 ml of methanol to recover the precipitated solid.
• the solid was washed several times with methanol and then dried under reduced pressure at 100 ° C. to obtain a white powder.
• the number average molecular weight of this polyimide was 10,500, and the weight average molecular weight was 27,600.
• the imidation ratio was 83%.
• 6 g of the obtained powder was dissolved in 94 g of ⁇ -BL by stirring at 50 ° C. for 24 hours to obtain a polymer solution P-5 having a resin component of 6% by weight.
• the reaction solution was cooled to about room temperature and then poured into 1600 ml of methanol to recover the precipitated solid.
• the solid was washed several times with methanol and then dried under reduced pressure at 100 ° C. to obtain a white powder.
• the number average molecular weight of this polyimide was 11,500, and the weight average molecular weight was 38,100.
• the imidation ratio was 58%.
• 6 g of the obtained powder was dissolved in 94 g of ⁇ -BL by stirring at 50 ° C. for 24 hours to obtain a polymer solution P-6 having a resin component of 6% by weight.
• This coating film surface was rubbed with a rubbing apparatus having a roll diameter of 120 mm using a rayon cloth under the conditions of a roll rotation speed of 1000 rpm, a roll traveling speed of 50 mm / sec, and an indentation amount of 0.3 mm to obtain a substrate with a liquid crystal alignment film.
• a rubbing apparatus having a roll diameter of 120 mm using a rayon cloth under the conditions of a roll rotation speed of 1000 rpm, a roll traveling speed of 50 mm / sec, and an indentation amount of 0.3 mm to obtain a substrate with a liquid crystal alignment film.
• a 6 ⁇ m spacer manufactured by JGC Catalysts & Chemicals, AW-II 6.0
• another substrate was laminated so that the liquid crystal alignment film faces each other and the rubbing direction was orthogonal, and then the sealing agent was cured to produce an empty cell.
• Liquid crystal MLC-2003 (C080) (manufactured by Merck) was injected into
• pretilt angle (°) of the twisted nematic liquid crystal cell produced by the method described in ⁇ Preparation of Liquid Crystal Cell> below was measured by “Axo Scan” manufactured by Axo Metrix, using the Mueller matrix method.
• VHR initial voltage holding ratio
• the voltage holding ratio of the twisted nematic liquid crystal cell manufactured by the following method is measured by applying a voltage of 4 V for 60 ⁇ s at a temperature of 60 ° C., measuring the voltage after 16.67 msec, and determining how much the voltage can be held.
• the voltage holding ratio (%) was calculated.
• the voltage holding ratio was measured using a VHR-1 voltage holding ratio measuring device manufactured by Toyo Technica.
• ⁇ UV irradiation> The twisted nematic liquid crystal cell produced by the method described in ⁇ Preparation of Liquid Crystal Cell> below was irradiated with light for 83 seconds using a tabletop UV curing device HCT3B28HEX-1 manufactured by Sen Special Light Source Co., Ltd. At that time, when the illuminance was measured using a luminometer (UV Light MEASUREMODEL UV-M02 manufactured by CRC) and a UV-35 sensor, the illuminance was 60.0 mW / cm 2 .
• VHR voltage holding ratio after UV irradiation>
• the measurement of the voltage holding ratio of the twisted nematic liquid crystal cell processed by the method of ⁇ UV irradiation> described above was performed by applying a voltage of 4 V for 60 ⁇ s at a temperature of 60 ° C., measuring the voltage after 16.67 msec, The voltage holding ratio (%) was calculated as how much was held.
• the voltage holding ratio was measured using a VHR-1 voltage holding ratio measuring device manufactured by Toyo Technica.
• Example 1 Ciba Japan's hydroxyphenyltriazine-based UV absorber Tinuvin (R) 400 was added so that the added amount of the specific compound was 2 parts by weight with respect to 100 parts by weight of the resin of the polymer solution P-1. The mixture was stirred for 1 hour to obtain a liquid crystal aligning agent. Using this liquid crystal aligning agent, the rubbing resistance was evaluated by the following method. As a result, no rubbing residue or scratches were observed. Further, a liquid crystal cell was prepared by the following method, and pre-tilt angle, VHR, and VHR after UV irradiation were measured. As a result, it was found that VHR after UV irradiation was higher than that of a liquid crystal alignment material to which no specific compound was added. . The results are shown in Table 1.
• Example 2 The hydroxyphenyltriazine-based UV absorber Tinuvin (R) 400 manufactured by Ciba Japan Co., Ltd. was added so that the added amount of the specific compound was 5 parts by weight with respect to 100 parts by weight of the resin of the polymer solution P-1. The mixture was stirred for 1 hour to obtain a liquid crystal aligning agent. Using this liquid crystal aligning agent, a liquid crystal cell was prepared in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 1. By adding the specific compound, VHR after UV irradiation was increased and the pretilt angle was also increased.
• Example 3 The hydroxyphenyltriazine-based ultraviolet absorber Tinuvin (R) 400 manufactured by Ciba Japan Co., Ltd. was added so that the added amount of the specific compound was 10 parts by weight with respect to 100 parts by weight of the resin of the polymer solution P-1. The mixture was stirred for 1 hour to obtain a liquid crystal aligning agent. Using this liquid crystal aligning agent, a liquid crystal cell was prepared in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 1. By adding the specific compound, VHR after UV irradiation was increased and the pretilt angle was also increased.
• Example 4 A hydroxyphenyltriazine-based UV absorber Tinuvi (479) manufactured by Ciba Japan Co., Ltd. was added so that the added amount of the specific compound was 2 parts by weight with respect to 100 parts by weight of the resin of the polymer solution P-1. The mixture was stirred for 1 hour to obtain a liquid crystal aligning agent. Using this liquid crystal aligning agent, a liquid crystal cell was prepared in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 1. VHR after UV irradiation became high by adding a specific compound.
• Example 5 A hydroxyphenyltriazine-based UV absorber Tinuvi (479) manufactured by Ciba Japan Co., Ltd. was added so that the amount of the specific compound added was 5 parts by weight with respect to 100 parts by weight of the resin of the polymer solution P-1. The mixture was stirred for 1 hour to obtain a liquid crystal aligning agent. Using this liquid crystal aligning agent, a liquid crystal cell was prepared in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 1. By adding the specific compound, VHR after UV irradiation was increased and the pretilt angle was also increased.
• Example 6 The hydroxyphenyltriazine-based ultraviolet absorber Tinuvin (R) 479 manufactured by Ciba Japan Co., Ltd. was added so that the added amount of the specific compound was 10 parts by weight with respect to 100 parts by weight of the resin of the polymer solution P-1. The mixture was stirred for 1 hour to obtain a liquid crystal aligning agent. Using this liquid crystal aligning agent, a liquid crystal cell was prepared in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 1. By adding the specific compound, VHR after UV irradiation was increased and the pretilt angle was also increased.
• Example 7 The hydroxyphenyltriazine-based UV absorber Tinuvin (R) 1577ED manufactured by Ciba Japan Co., Ltd. was added so that the amount of the specific compound added was 1 part by weight with respect to 100 parts by weight of the resin of the polymer solution P-1. The mixture was stirred for 1 hour to obtain a liquid crystal aligning agent. Using this liquid crystal aligning agent, a liquid crystal cell was prepared in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 1. VHR after UV irradiation became high by adding a specific compound.
• Example 8 The hydroxyphenyl triazine-based ultraviolet absorber Tinuvin (R) 400 manufactured by Ciba Japan Co., Ltd. was added so that the amount of the specific compound added was 5 parts by weight with respect to 100 parts by weight of the resin of the polymer solution P-2. The mixture was stirred for 1 hour to obtain a liquid crystal aligning agent. Using this liquid crystal aligning agent, a liquid crystal cell was prepared in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 1. By adding the specific compound, VHR after UV irradiation was increased and the pretilt angle was also increased.
• Example 9 The hydroxyphenyltriazine-based ultraviolet absorber Tinuvin (R) 479 manufactured by Ciba Japan Co., Ltd. was added so that the added amount of the specific compound was 5 parts by weight with respect to 100 parts by weight of the resin of the polymer solution P-2. The mixture was stirred for 1 hour to obtain a liquid crystal aligning agent. Using this liquid crystal aligning agent, a liquid crystal cell was prepared in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 1. By adding the specific compound, VHR after UV irradiation was increased, but the pretilt angle was also increased.
• R hydroxyphenyltriazine-based ultraviolet absorber Tinuvin
• Example 10 Hydroxyltriazine UV absorber Tinuvin (R) 1577ED manufactured by Ciba Japan Co., Ltd. was added so that the amount of the specific compound added was 1 part by weight with respect to 100 parts by weight of the resin of polymer solution P-2. The mixture was stirred for 1 hour to obtain a liquid crystal aligning agent. Using this liquid crystal aligning agent, a liquid crystal cell was prepared in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 1. VHR after UV irradiation became high by adding a specific compound.
• Example 11 Ciba Japan's hydroxyphenyltriazine-based UV absorber Tinuvin (R) 400 was added so that the amount of the specific compound added was 5 parts by weight per 100 parts by weight of the polymer solution P-4 resin. The mixture was stirred for 1 hour to obtain a liquid crystal aligning agent. Using this liquid crystal aligning agent, a liquid crystal cell was prepared in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 1. VHR after UV irradiation became high by adding a specific compound.
• Example 12 The hydroxyphenyltriazine-based ultraviolet absorber Tinuvin (R) 479 manufactured by Ciba Japan Co., Ltd. was added so that the added amount of the specific compound was 5 parts by weight with respect to 100 parts by weight of the resin of the polymer solution P-4. The mixture was stirred for 1 hour to obtain a liquid crystal aligning agent. Using this liquid crystal aligning agent, a liquid crystal cell was prepared in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 1. VHR after UV irradiation became high by adding a specific compound.
• Example 13 80 g of polymer solution P-1 and 20 g of polymer solution P-5 were mixed and stirred at room temperature for 20 hours.
• Ciba Japan's hydroxyphenyltriazine-based UV absorber Tinuvin (R) 479 is added to 100 parts by weight of the resin of the polymer solution so that the specific compound is added in an amount of 5 parts by weight.
• Stirring to obtain a liquid crystal aligning agent Using this liquid crystal aligning agent, a liquid crystal cell was prepared in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 1. VHR after UV irradiation became high by adding a specific compound.
• Example 14 Hydroxyltriazine UV absorber Tinuvin (R) 1577ED manufactured by Ciba Japan Co., Ltd. was added so that the added amount of the specific compound was 1 part by weight with respect to 100 parts by weight of the resin of the polymer solution P-7. The mixture was stirred for 1 hour to obtain a liquid crystal aligning agent. Using this liquid crystal alignment material, a liquid crystal cell was prepared in the same manner as in Example 1 and pre-tilted in the same manner as in Example 1, and the same evaluation was performed using this liquid crystal alignment treatment agent. The results are shown in Table 1. VHR after UV irradiation became high by adding a specific compound.
• Example 15 20 g of polymer solution P-6 and 80 g of polymer solution P-7 were mixed and stirred at room temperature for 20 hours.
• Ciba Japan's hydroxyphenyltriazine-based UV absorber Tinuvin (R) 400 was added to 100 parts by weight of the resin of the polymer solution so that the specific compound was added in an amount of 5 parts by weight, and the mixture was stirred at room temperature for 1 hour. Stirring to obtain a liquid crystal aligning agent. Using this liquid crystal aligning agent, a liquid crystal cell was prepared in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 1. VHR after UV irradiation became high by adding a specific compound.
• Example 16 20 g of polymer solution P-6 and 80 g of polymer solution P-7 were mixed and stirred at room temperature for 20 hours.
• Ciba Japan's hydroxyphenyltriazine-based UV absorber Tinuvin (R) 479 is added to 100 parts by weight of the resin of the polymer solution so that the specific compound is added in an amount of 5 parts by weight.
• Stirring to obtain a liquid crystal aligning agent Using this liquid crystal aligning agent, a liquid crystal cell was prepared in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 1. VHR after UV irradiation became high by adding a specific compound.
• Example 1 A liquid crystal cell was produced in the same manner as in Example 1 using the polymer solution P-1 as a liquid crystal alignment treatment agent, and the same evaluation was performed. The results are shown in Table 1. The VHR after UV irradiation was low compared to the system to which the specific compound was added.
• Example 2 A benzotriazole UV absorber JF-83 manufactured by Johoku Chemical Industry Co., Ltd. was added to 100 parts by weight of the resin of the polymer solution P-1 so that the addition amount was 5 parts by weight, and the mixture was stirred at room temperature for 1 hour, An alignment treatment agent was obtained. Using this liquid crystal aligning agent, a liquid crystal cell was prepared in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 1. Both the initial VHR and the VHR after UV irradiation were low.
• Example 3 (Comparative Example 3) Using the polymer solution P-3 as a liquid crystal alignment agent, the pretilt angle, rubbing resistance, VHR, and VHR after UV irradiation were evaluated in the same manner as in Example 1. The results are shown in Table 1. The rubbing resistance was poor and VHR was lower than the specific compound of the present invention.
• the liquid crystal alignment treatment agent of the present invention has a light resistance property, a rubbing resistance property, etc., and can form a liquid crystal alignment film having an effect of not greatly increasing the amount of ions in the liquid crystal cell.
• the film is industrially useful as a TN element, an STN element, a TFT liquid crystal element, and a vertical alignment type liquid crystal display element.

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