WO2013081064A1 - Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element using same - Google Patents

Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element using same Download PDF

Info

Publication number
WO2013081064A1
WO2013081064A1 PCT/JP2012/080975 JP2012080975W WO2013081064A1 WO 2013081064 A1 WO2013081064 A1 WO 2013081064A1 JP 2012080975 W JP2012080975 W JP 2012080975W WO 2013081064 A1 WO2013081064 A1 WO 2013081064A1
Authority
WO
WIPO (PCT)
Prior art keywords
liquid crystal
aligning agent
weight
crystal aligning
crystal alignment
Prior art date
Application number
PCT/JP2012/080975
Other languages
French (fr)
Japanese (ja)
Inventor
拓郎 小田
皇晶 筒井
Original Assignee
日産化学工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日産化学工業株式会社 filed Critical 日産化学工業株式会社
Priority to JP2013547215A priority Critical patent/JP6206187B2/en
Priority to CN201280058354.0A priority patent/CN103959153B/en
Priority to KR1020147014360A priority patent/KR102044049B1/en
Publication of WO2013081064A1 publication Critical patent/WO2013081064A1/en

Links

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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Liquid Crystal (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Provided is a liquid crystal aligning agent which has good rubbing resistance and is capable of providing a liquid crystal alignment film that has high resistance to a process for aligning liquid crystals by the irradiation of ultraviolet light, said process being popular in recent processes for manufacturing a liquid crystal display element. A liquid crystal aligning agent which contains a specific compound that contains a triazine skeleton and a hydroxyl group. (In the formula [1], each of R1-R14 independently represents a hydrogen atom or a monovalent organic group, and one or more groups among the R1-R14 groups are organic groups, each of which contains an alkyl group having 4 or more carbon atoms.)

Description

液晶配向処理剤、液晶配向膜及びそれを用いた液晶表示素子Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element using the same
　本発明は、液晶配向処理剤、該液晶配向処理剤を用いて得られる液晶配向膜及びそれを用いた液晶表示素子に関するものである。 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.
　現在、液晶表示素子の液晶配向膜としては、ポリアミック酸などのポリイミド前駆体や可溶性ポリイミドの溶液を主成分とする液晶配向処理剤を塗布し、焼成した、いわゆるポリイミド系の液晶配向膜が主として用いられている。液晶配向膜は、液晶の配向状態を制御する目的で使用される。
　液晶配向膜に求められる特性として、液晶の配向を制御できること、電圧保持率（以下、ＶＨＲとも言う）が優れていること、直流電圧により蓄積した電荷の緩和が早いこと、液晶セル内のイオン量が少ないこと、などが挙げられる。
　さらに近年、液晶表示素子の大型化に伴い、長期間の使用に耐えうる液晶表示素子が求められるようになってきた。長期間使用できるためには、バックライトユニットからの光や、紫外線を含む太陽光を長期間照射しても、特性が変化しないことが求められる。そのため、バックライト光や紫外線照射によって、表示特性が大きく変化しない液晶配向膜が求められるようになってきた。 Currently, as a 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.
In recent years, with the increase in size of liquid crystal display elements, liquid crystal display elements that can withstand long-term use have been demanded. In order to be able to be used for a long period of time, it is required that the characteristics do not change even if light from the backlight unit or sunlight including ultraviolet rays is irradiated for a long period. For this reason, there has been a demand for a liquid crystal alignment film whose display characteristics do not change greatly by backlight light or ultraviolet irradiation.
　これらの特性以外にも、近年の液晶表示素子の作製プロセスでは、紫外線を照射して液晶を配向させるプロセスが取り入れられるようになってきた（例えば、非特許文献１参照）。
　また、近年の液晶表示素子の作製プロセスにおいて、液晶滴下工法（ＯＤＦ）やＰＳＡ（Ｐｏｌｉｍｅｒ　Ｓｕｓｔａｉｎｅｄ　Ａｌｉｇｎｍｅｎｔ）処理などで、紫外線を照射するプロセスが取り入れられるようになり、紫外線に対して耐性のある材料が求められるようになってきた（例えば、非特許文献２参照）。 In addition to these characteristics, 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).
In addition, in a process for manufacturing a liquid crystal display element in recent years, 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. (See, for example, Non-Patent Document 2).
　液晶表示素子の光耐性を高める取り組みとして、例えば、特許文献１及び２には、液晶配向処理剤にベンゾトリアゾール系紫外線吸収剤やベンゾフェノン系紫外線吸収剤等の添加剤を添加し、液晶の寿命を長くする試みが行われている。
　また、特許文献３には、ベンゾトリアゾール系紫外線吸収剤やベンゾフェノン系紫外線吸収剤に、さらに酸化防止剤を添加して、液晶の寿命を長くする試みが行われている。
　また、特許文献４には、ベンゾトリアゾール系紫外線吸収剤、ベンゾフェノン系紫外線吸収剤、ジアルキルジチオカルバミン酸金属塩等を液晶配向処理剤に添加することにより、得られる配向膜の紫外線による分解を防ぐことが出来ることが報告されている。
　さらに、特許文献５及び６には、ベンゾトリアゾール系化合物やヒンダードアミン化合物を液晶配向処理剤に添加して、耐光性に優れる液晶パネルを製造する方法が報告されている。
　しかし、これら添加剤は、ＵＶ（紫外線）照射することによるＶＨＲ低下の抑制効果はあるものの、液晶配向膜自体のＶＨＲが低下してしまう問題点があった。また焼成温度が高い場合、これら添加剤が昇華もしくは熱分解してしまうため、その効果が低減してしまう問題があった。
　これら問題を解決するために、トリアジン骨格を有するジアミンが提案されている（特許文献７）。 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. Further, when the firing temperature is high, these additives are sublimated or thermally decomposed, resulting in a problem that the effect is reduced.
In order to solve these problems, a diamine having a triazine skeleton has been proposed (Patent Document 7).
日本特開昭５６－１１６０１２号公報Japanese Unexamined Patent Publication No. 56-1116012 日本特開昭５７－８４４２９号公報Japanese Unexamined Patent Publication No. 57-84429 日本特開昭５７－１０８８２８号公報Japanese Unexamined Patent Publication No. 57-108828 日本特開平１０－１４８８３５号公報Japanese Unexamined Patent Publication No. 10-148835 日本特開２００３－２１５５９２号公報Japanese Unexamined Patent Publication No. 2003-215592 日本特開２００４－５３６８５号公報Japanese Unexamined Patent Publication No. 2004-53685 日本特開２０１１－１２８５９７号公報Japanese Unexamined Patent Publication No. 2011-128597
　しかし、トリアジン骨格を有するジアミンを用いてポリイミド前駆体を製造する場合、ＵＶ照射後のＶＨＲが高くなるが、トリアジン骨格を有するジアミンは酸二無水物との反応性が悪く、導入量を多くすることができない。多く導入した場合、ＶＨＲ低下は抑制されるものの、高分子量体が得られず、得られた液晶配向膜のラビング耐性が悪くなることが判明した。
　上記の状況を鑑み、本発明は、ラビング耐性が良好で、かつ光耐性の高い液晶配向膜を得ることの出来る液晶配向処理剤を提供することを目的とする。 However, when a polyimide precursor is produced using a diamine having a triazine skeleton, the VHR after UV irradiation is increased, but the diamine having a triazine skeleton is poor in reactivity with an acid dianhydride and increases the amount of introduction. I can't. When introduced in a large amount, it was found that although a decrease in VHR was suppressed, a high molecular weight body was not obtained, and the rubbing resistance of the obtained liquid crystal alignment film was deteriorated.
In view of the above situation, 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.
　本発明者は、上記の目的を達成する為に鋭意研究を行った結果、トリアジン骨格とヒドロキシル基を有する化合物（以下、特定化合物とも言う）を有する液晶配向処理剤を用いることで、上記目的を達成出来ることを見出した。
　すなわち、本発明は、以下の要旨を有するものである。
１．一般式（１）で表される化合物を含有することを特徴とする液晶配向処理剤。
Figure JPOXMLDOC01-appb-C000002
 （式中、Ｒ1～Ｒ14は、それぞれ独立して、水素原子、又は二価の有機基であり、かつＲ1～Ｒ14のうちいずれか一つ以上は、炭素数４以上のアルキル基を含む有機基である。）
２．前記式（１）で表される化合物と、ポリイミド前駆体及び該ポリイミド前駆体をイミド化したポリイミドからなる群より選ばれる少なくとも１種のポリマーとを含有する上記１に記載の液晶配向処理剤。
３．前記式（１）で表される化合物の含有量が、前記ポリイミド前駆体及び該ポリイミド前駆体をイミド化したポリイミドからなる群より選ばれる少なくとも１種のポリマーの量１００重量部に対して、０．５～１０重量部である上記１又は２に記載の液晶配向処理剤。
４．前記ポリイミド前駆体及び該ポリイミド前駆体をイミド化したポリイミドからなる群より選ばれる少なくとも１種のポリマーの重量平均分子量が、１０，０００～１５０，０００である上記１～３のいずれかに記載の液晶配向処理剤。 As a result of intensive studies to achieve the above object, the present inventor achieved the above object by using 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).
Figure JPOXMLDOC01-appb-C000002
 (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 liquid crystal aligning agent of said 1 containing the compound represented by said Formula (1), and at least 1 sort (s) of polymer chosen from the group which consists of a polyimide precursor and the polyimide which imidated this polyimide precursor.
3. 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. 3. The liquid crystal aligning agent according to 1 or 2 above, which is 5 to 10 parts by weight.
4). 4. 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.
５．液晶配向処理剤中に９２～９９重量％の有機溶媒を含有する上記１～４のいずれかに記載の液晶配向処理剤。
６．前記有機溶媒が、５～８０重量％の貧溶媒を含有する上記５に記載の液晶配向処理剤。
７．上記１～６のいずれかに記載の液晶配向処理剤から得られる液晶配向膜。
８．膜厚が、１０～２００μｍである上記７に記載の液晶配向膜。
９．上記７又は８に記載の液晶配向膜を具備する液晶表示素子。 5. 5. The 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 μm.
9. 9. A liquid crystal display device comprising the liquid crystal alignment film according to 7 or 8 above.
　本発明によれば、ラビング耐性が良好で、かつ光耐性の高い液晶配向膜を得ることの出来る液晶配向処理剤を提供することが可能となる。 According to the present invention, it is possible to provide a liquid crystal aligning agent capable of obtaining a liquid crystal alignment film having good rubbing resistance and high light resistance.
［特定化合物］
　本発明の液晶配向処理剤に含有される特定化合物は、下記式〔１〕で表される化合物である。
Figure JPOXMLDOC01-appb-C000003
 　式中、Ｒ１～Ｒ１４は、それぞれ独立して、水素原子、又は一価の有機基であり、かつＲ１～Ｒ１４のうちいずれか一つ以上が、炭素数４以上のアルキル基を含む有機基である。
　炭素数４以上のアルキル基を含むことで、特定化合物の有機溶媒への溶解性が高まる効果がある。さらに、焼成した塗膜表面に特定化合物が効果的に集まり、ＶＨＲ特性に影響を及ぼす表面近傍の樹脂成分（液晶配向膜）の劣化を、効果的に抑制できる効果もある。
　また、アルキル基を長くすることで、液晶配向膜にプレチルト発現能を付与させることも可能である。 [Specific compounds]
The specific compound contained in the liquid crystal aligning agent of this invention is a compound represented by following formula [1].
Figure JPOXMLDOC01-appb-C000003
 In the formula, 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.
　アルキル基は、フェニル基と直接結合していても良いが、－Ｏ－、－ＮＨＣＯ－、－ＣＯＯ－等の基を介して結合するのが、溶解性の観点から好ましい。
　アルキル基以外の他の置換基は特に限定されないが、特定化合物の耐熱性の観点からは、フェニル基が好ましく、有機溶媒への溶解性の観点では、－ＯＨ基、－ＮＨ２、－ＣＯＯＨ、－ＮＨＲ(Ｒは１価の有機基)等の極性基が好ましく、特定化合物の途膜表面への移行しやすさの観点からは、アルキル基が特に好ましい。
　好ましい具体的な構造例としては、２－［４，６－ビスＣ２，４－ジメチルフェニル）－１，３，５－トリアジン－２－イル］－５－（オクチルオキシ）フェノール、チバ・ジャパン社製チヌビン（R）４００、チヌビン（R）４０５（一般名：２－［４－［（２－ヒドロキシ－３－（２‘－エチル）ヘキシル）オキシ］－２－ヒドロキシフェニル］－４，６－ビス（２，４－ジメチルフェニル）－１，３，５－トリアジン）、チヌビン（R）４６０（一般名：２，４－ビス（２－ヒドロキシ－４－ブチルオキシフェニル）－６－（２，４－ビス－ブチルオキシフェニル）－１，３，５－トリアジン）、チヌビン（R）４７７、チヌビン（R）４７９（一般名：２－（２－ヒドロキシ－４－［１－オクチルオキシカルボニルエトキシ］フェニル）－４，６－ビス（４－フェニルフェニル）－１，３，５－トリアジン）、チヌビン（R）１５７７ＥＤ（一般名：２－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）－５－（ヘキシルオキシ）フェノール）などが挙げられる。このうち、有機溶媒への溶解性、表面への移行性の観点から、チヌビン（R）４００、チヌビン（R）４７９が特に好ましい。 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. From the viewpoint of solubility in an organic solvent, —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) -4 6-bis (4-phenylphenyl) -1,3,5-triazine), Tinuvin (R) 1577ED (generic name: 2- (4,6-diphenyl-1,3,5-triazin-2-yl)- 5- (hexyloxy) phenol) and the like. Of these, tinuvin (R) 400 and tinuvin (R) 479 are particularly preferred from the viewpoints of solubility in organic solvents and migration to the surface.
　トリアジン骨格を含有する特定化合物の導入量としては、特定化合物の溶媒に対する溶解性の観点から、本発明の液晶配向処理剤に含有される、ポリイミド前駆体及び該ポリイミド前駆体をイミド化したポリイミドからなる群より選ばれる少なくとも１種のポリマー（高分子化合物）の量１００重量部に対して、０．５～１０重量部が好ましく、０．５～５重量部がより好ましい。
　液晶配向処理剤への添加方法は特に限定されないが、液晶配向処理剤に、直接所定量の特定化合物を加え、攪拌溶解させるか、予め有機溶媒に０．５～１０重量％程度の特定化合物を溶解させ、液晶配向処理剤に加えてもよい。 As the amount of the specific compound containing the triazine skeleton, from the viewpoint of the solubility of the specific compound in the solvent, 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.
［ポリイミド及びポリイミド前駆体］
　本発明の液晶配向処理剤に含有されるポリイミド前駆体とは、ポリアミック酸（ポリアミド酸とも言う）及びポリアミック酸エステルを指す。
　ポリアミック酸は、ジアミン成分とテトラカルボン酸二無水物との反応によって得られる。
　ポリアミック酸エステルは、ジアミン成分とテトラカルボン酸ジエステルジクロリドを塩基存在下で反応させる、又はテトラカルボン酸ジエステルとジアミンを適当な縮合剤、塩基の存在下にて反応させることによって得られる。
　本発明のポリイミドは、このポリアミック酸を脱水閉環させる、あるいはポリアミック酸エステルを加熱閉環させることにより得られる。かかるポリアミック酸、ポリアミック酸エステル及びポリイミドのいずれも液晶配向膜を得るための重合体として有用である。 [Polyimide and polyimide precursor]
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.
　使用されるジアミン成分は、特に限定されない。その具体例を挙げると、以下の通りである。
　脂環式ジアミン類の例としては、１，４－ジアミノシクロヘキサン、１，３－ジアミノシクロヘキサン、４，４’－ジアミノジシクロヘキシルメタン、４，４’－ジアミノ－３，３’－ジメチルジシクロヘキシルアミン、イソホロンジアミン等が挙げられる。
　芳香族ジアミン類の例としては、ｏ－フェニレンジアミン、ｍ－フェニレンジアミン、ｐ－フェニレンジアミン、２，４－ジアミノトルエン、２，５－ジアミノトルエン、３，５－ジアミノトルエン、１，４－ジアミノ－２－メトキシベンゼン、２，５－ジアミノ－ｐ－キシレン、１，３－ジアミノ－４－クロロベンゼン、３，５－ジアミノ安息香酸、１，４－ジアミノ－２，５－ジクロロベンゼン、４，４’－ジアミノ－１，２－ジフェニルエタン、４，４’－ジアミノ－２，２’－ジメチルビベンジル、４，４’－ジアミノジフェニルメタン、３，３’－ジアミノジフェニルメタン、３，４’－ジアミノジフェニルメタン、４，４’－ジアミノ－３，３’―ジメチルジフェニルメタン、２，２’－ジアミノスチルベン、４，４’－ジアミノスチルベン、４，４’－ジアミノジフェニルエーテル、３，４’－ジアミノジフェニルエーテル、４，４’－ジアミノジフェニルスルフィド、４，４’－ジアミノジフェニルスルホン、３，３’－ジアミノジフェニルスルホン、４，４’－ジアミノベンゾフェノン、１，３－ビス（３－アミノフェノキシ）ベンゼン、１，３－ビス（４－アミノフェノキシ）ベンゼン、１，４－ビス（４－アミノフェノキシ）ベンゼン、３，５－ビス（４－アミノフェノキシ）安息香酸、４，４’－ビス（４－アミノフェノキシ）ビベンジル、２，２－ビス［（４－アミノフェノキシ）メチル］プロパン、２，２－ビス［４－（４－アミノフェノキシ）フェニル］ヘキサフロロプロパン、２，２－ビス［４－（４－アミノフェノキシ）フェニル］プロパン、ビス［４－（３－アミノフェノキシ）フェニル］スルホン、ビス［４－（４－アミノフェノキシ）フェニル］スルホン、１，１－ビス（４－アミノフェニル）シクロヘキサン、α、α’－ビス（４－アミノフェニル）－１，４－ジイソプロピルベンゼン、９，９－ビス（４－アミノフェニル）フルオレン、２，２－ビス（３－アミノフェニル）ヘキサフロロプロパン、２，２－ビス（４－アミノフェニル）ヘキサフロロプロパン、４，４’－ジアミノジフェニルアミン、２，４－ジアミノジフェニルアミン、１，８－ジアミノナフタレン、１，５－ジアミノナフタレン、１，５－ジアミノアントラキノン、１，３－ジアミノピレン、１，６－ジアミノピレン、１，８―ジアミノピレン、２，７－ジアミノフルオレン、１，３－ビス（４－アミノフェニル）テトラメチルジシロキサン、ベンジジン、２，２’－ジメチルベンジジン、１，２－ビス（４－アミノフェニル）エタン、１，３－ビス（４－アミノフェニル）プロパン、１，４－ビス（４－アミノフェニル）ブタン、１，５－ビス（４－アミノフェニル）ペンタン、１，６－ビス（４－アミノフェニル）ヘキサン、１，７－ビス（４－アミノフェニル）ヘプタン、１，８－ビス（４－アミノフェニル）オクタン、１，９－ビス（４－アミノフェニル）ノナン、１，１０－ビス（４－アミノフェニル）デカン、１，３－ビス（４－アミノフェノキシ）プロパン、１，４－ビス（４－アミノフェノキシ）ブタン、１，５－ビス（４－アミノフェノキシ）ペンタン、１，６－ビス（４－アミノフェノキシ）ヘキサン、１，７－ビス（４－アミノフェノキシ）ヘプタン、１，８－ビス（４－アミノフェノキシ）オクタン、１，９－ビス（４－アミノフェノキシ）ノナン、１，１０－ビス（４－アミノフェノキシ）デカン、ジ（４－アミノフェニル）プロパン－１，３－ジオエート、ジ（４－アミノフェニル）ブタン－１，４－ジオエート、ジ（４－アミノフェニル）ペンタン－１，５－ジオエート、ジ（４－アミノフェニル）ヘキサン－１，６－ジオエート、ジ（４－アミノフェニル）ヘプタン－１，７－ジオエート、ジ（４－アミノフェニル）オクタン－１，８－ジオエート、ジ（４－アミノフェニル）ノナン－１，９－ジオエート、ジ（４－アミノフェニル）デカン－１，１０－ジオエート、１，３－ビス〔４－（４－アミノフェノキシ）フェノキシ〕プロパン、１，４－ビス〔４－（４－アミノフェノキシ）フェノキシ〕ブタン、１，５－ビス〔４－（４－アミノフェノキシ）フェノキシ〕ペンタン、１，６－ビス〔４－（４－アミノフェノキシ）フェノキシ〕ヘキサン、１，７－ビス〔４－（４－アミノフェノキシ）フェノキシ〕ヘプタン、１，８－ビス〔４－（４－アミノフェノキシ）フェノキシ〕オクタン、１，９－ビス〔４－（４－アミノフェノキシ）フェノキシ〕ノナン、１，１０－ビス〔４－（４－アミノフェノキシ）フェノキシ〕デカン等が挙げられる。 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.
Examples of aromatic diamines 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′-diamino-3,3′-dimethyldiphenylmethane, 2,2′-diaminostilbene, 4,4′-diaminostilbene, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobenzophenone 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3,5-bis (4-aminophenoxy) ) Benzoic acid, 4,4′-bis (4-aminophenoxy) bibenzyl, 2,2-bis [(4-aminophenoxy) methyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] Hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, bis [4- (3-aminophenyl) Enoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, 1,1-bis (4-aminophenyl) cyclohexane, α, α′-bis (4-aminophenyl) -1,4- Diisopropylbenzene, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 ′ -Diaminodiphenylamine, 2,4-diaminodiphenylamine, 1,8-diaminonaphthalene, 1,5-diaminonaphthalene, 1,5-diaminoanthraquinone, 1,3-diaminopyrene, 1,6-diaminopyrene, 1,8- Diaminopyrene, 2,7-diaminofluorene, 1,3-bis (4-aminophenyl) tetramethyldisi Xanthone, benzidine, 2,2'-dimethylbenzidine, 1,2-bis (4-aminophenyl) ethane, 1,3-bis (4-aminophenyl) propane, 1,4-bis (4-aminophenyl) butane 1,5-bis (4-aminophenyl) pentane, 1,6-bis (4-aminophenyl) hexane, 1,7-bis (4-aminophenyl) heptane, 1,8-bis (4-aminophenyl) ) Octane, 1,9-bis (4-aminophenyl) nonane, 1,10-bis (4-aminophenyl) decane, 1,3-bis (4-aminophenoxy) propane, 1,4-bis (4- Aminophenoxy) butane, 1,5-bis (4-aminophenoxy) pentane, 1,6-bis (4-aminophenoxy) hexane, 1,7-bis (4-aminophenoxy) heptane 1,8-bis (4-aminophenoxy) octane, 1,9-bis (4-aminophenoxy) nonane, 1,10-bis (4-aminophenoxy) decane, di (4-aminophenyl) propane-1, 3-dioate, di (4-aminophenyl) butane-1,4-dioate, di (4-aminophenyl) pentane-1,5-dioate, di (4-aminophenyl) hexane-1,6-dioate, di (4-aminophenyl) heptane-1,7-dioate, di (4-aminophenyl) octane-1,8-dioate, di (4-aminophenyl) nonane-1,9-dioate, di (4-aminophenyl) ) Decane-1,10-dioate, 1,3-bis [4- (4-aminophenoxy) phenoxy] propane, 1,4-bis [4- (4-aminopheno) Phenoxy] butane, 1,5-bis [4- (4-aminophenoxy) phenoxy] pentane, 1,6-bis [4- (4-aminophenoxy) phenoxy] hexane, 1,7-bis [4- (4-aminophenoxy) phenoxy] heptane, 1,8-bis [4- (4-aminophenoxy) phenoxy] octane, 1,9-bis [4- (4-aminophenoxy) phenoxy] nonane, 1,10- And bis [4- (4-aminophenoxy) phenoxy] decane.
　芳香族－脂肪族ジアミンの例としては、３－アミノベンジルアミン、４－アミノベンジルアミン、３－アミノ－Ｎ－メチルベンジルアミン、４－アミノ－Ｎ－メチルベンジルアミン、３－アミノフェネチルアミン、４－アミノフェネチルアミン、３－アミノ－Ｎ－メチルフェネチルアミン、４－アミノ－Ｎ－メチルフェネチルアミン、３－（３－アミノプロピル）アニリン、４－（３－アミノプロピル）アニリン、３－（３－メチルアミノプロピル）アニリン、４－（３－メチルアミノプロピル）アニリン、３－（４－アミノブチル）アニリン、４－（４－アミノブチル）アニリン、３－（４－メチルアミノブチル）アニリン、４－（４－メチルアミノブチル）アニリン、３－（５－アミノペンチル）アニリン、４－（５－アミノペンチル）アニリン、３－（５－メチルアミノペンチル）アニリン、４－（５－メチルアミノペンチル）アニリン、２－（６－アミノナフチル）メチルアミン、３－（６－アミノナフチル）メチルアミン、２－（６－アミノナフチル）エチルアミン、３－（６－アミノナフチル）エチルアミン等が挙げられる。 Examples of 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-methylaminopentyl) aniline, 4- (5-methylaminopentyl) aniline, 2- (6-aminonaphthyl) methylamine, 3- (6-aminonaphthyl) methylamine, 2- (6 -Aminonaphthyl) ethylamine, 3- (6-aminonaphthyl) ethylamine and the like.
　複素環式ジアミン類の例としては、２，６－ジアミノピリジン、２，４－ジアミノピリジン、２，４－ジアミノ－１，３，５－トリアジン、２，７－ジアミノジベンゾフラン、３，６－ジアミノカルバゾール、２，４－ジアミノ－６－イソプロピル－１，３，５－トリアジン、２，５－ビス（４－アミノフェニル）－１，３，４－オキサジアゾール等が挙げられる。
　脂肪族ジアミン類の例としては、１，２－ジアミノエタン、１，３－ジアミノプロパン、１，４－ジアミノブタン、１，５－ジアミノペンタン、１，６－ジアミノヘキサン、１，７－ジアミノヘプタン、１，８－ジアミノオクタン、１，９－ジアミノノナン、１，１０－ジアミノデカン、１，３－ジアミノ－２，２－ジメチルプロパン、１，６－ジアミノ－２，５－ジメチルヘキサン、１，７－ジアミノ－２，５－ジメチルヘプタン、１，７－ジアミノ－４，４－ジメチルヘプタン、１，７－ジアミノ－３－メチルヘプタン、１，９－ジアミノ－５－メチルヘプタン、１，１２－ジアミノドデカン、１，１８－ジアミノオクタデカン、１，２－ビス（３－アミノプロポキシ）エタン等が挙げられる。 Examples of heterocyclic diamines 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.
Examples of aliphatic diamines 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-diaminooctadecane, 1,2-bis (3-aminopropoxy) ethane and the like.
　側鎖にアルキル基、フッ素含有アルキル基、芳香環、脂肪族環、複素環、並びにそれらからなる大環状置換体を有するジアミン化合物を併用してもよい。具体的には、下記の式［ＤＡ１］～式［ＤＡ２６］で示されるジアミンを例示することができる。
Figure JPOXMLDOC01-appb-C000004
 （式［ＤＡ１］～式［ＤＡ５］中、Ｒ６は、炭素数１～２２のアルキル基又はフッ素含有アルキル基である。）
Figure JPOXMLDOC01-appb-C000005
 （式［ＤＡ６］～式［ＤＡ９］中、Ｓ５は、－ＣＯＯ－、－ＯＣＯ－、－ＣＯＮＨ－、－ＮＨＣＯ－、－ＣＨ２－、－Ｏ－、－ＣＯ－、又は－ＮＨ－を示し、Ｒ６は炭素数１～２２のアルキル基又はフッ素含有アルキル基を示す。） You may use together the 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. Specifically, diamines represented by the following formulas [DA1] to [DA26] can be exemplified.
Figure JPOXMLDOC01-appb-C000004
 (In the formulas [DA1] to [DA5], R 6 represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group.)
Figure JPOXMLDOC01-appb-C000005
 (In the formulas [DA6] to [DA9], 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.)
Figure JPOXMLDOC01-appb-C000006
 （式［ＤＡ１０］及び式［ＤＡ１１］中、Ｓ６は、－Ｏ－、－ＯＣＨ２－、－ＣＨ２Ｏ－、－ＣＯＯＣＨ２－、又は－ＣＨ２ＯＣＯ－を示し、Ｒ７は炭素数１～２２のアルキル基、アルコキシ基、フッ素含有アルキル基又はフッ素含有アルコキシ基である。）
Figure JPOXMLDOC01-appb-C000007
 （式［ＤＡ１２］～式［ＤＡ１４］中、Ｓ７は、－ＣＯＯ－、－ＯＣＯ－、－ＣＯＮＨ－、－ＮＨＣＯ－、－ＣＯＯＣＨ２－、－ＣＨ２ＯＣＯ－、－ＣＨ２Ｏ－、－ＯＣＨ２－、又は－ＣＨ２－を示し、Ｒ８は炭素数１～２２のアルキル基、アルコキシ基、フッ素含有アルキル基又はフッ素含有アルコキシ基である。）
Figure JPOXMLDOC01-appb-C000006
 (In Formula [DA10] and Formula [DA11], S 6 represents —O—, —OCH 2 —, —CH 2 O—, —COOCH 2 —, or —CH 2 OCO—, and R 7 represents the number of carbon atoms. 1 to 22 alkyl groups, alkoxy groups, fluorine-containing alkyl groups or fluorine-containing alkoxy groups.)
Figure JPOXMLDOC01-appb-C000007
 (In the formulas [DA12] to [DA14], 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.
Figure JPOXMLDOC01-appb-C000008
 （式［ＤＡ１５］及び式［ＤＡ１６］中、Ｓ８は、－ＣＯＯ－、－ＯＣＯ－、－ＣＯＮＨ－、－ＮＨＣＯ－、－ＣＯＯＣＨ２－、－ＣＨ２ＯＣＯ－、－ＣＨ２Ｏ－、－ＯＣＨ２－、－ＣＨ２－、－Ｏ－、又は－ＮＨ－を示し、Ｒ９はフッ素基、シアノ基、トリフルオロメチル基、ニトロ基、アゾ基、ホルミル基、アセチル基、アセトキシ基、又は水酸基である。）
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000010
 （式［ＤＡ１７］～［ＤＡ２０］中、Ｒ１０は炭素数３～１２のアルキル基であり、１，４－シクロへキシレンのシス－トランス異性は、それぞれトランス体である。）
Figure JPOXMLDOC01-appb-C000008
 (In Formula [DA15] and Formula [DA16], 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.)
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000010
 (In the formulas [DA17] to [DA20], 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.)
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
　また、以下のジアミンを併用させても良い。
Figure JPOXMLDOC01-appb-C000014
 （式［ＤＡ３１］中、ｍは０～３の整数である。式［ＤＡ３４］中、ｎは１～５の整数である。）
　[ＤＡ－２７]や[ＤＡ－２８]は、これらを用いることにより、液晶表示素子の電圧保持率（ＶＨＲとも言う）を向上させることができ、[ＤＡ－２９]～［ＤＡ－３４］は、液晶表示素子の蓄積電荷低減に効果があり、好ましい。 Moreover, you may use the following diamine together.
Figure JPOXMLDOC01-appb-C000014
 (In the formula [DA31], m is an integer of 0 to 3. In the formula [DA34], 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.
　加えて、下記の式［ＤＡ３５］で示されるようなジアミノシロキサンなども挙げることができる。
Figure JPOXMLDOC01-appb-C000015
 （式［ＤＡ３５］中、ｍは、１から１０の整数である。）
　上記のジアミン化合物は、液晶配向膜とした際の液晶配向性、電圧保持特性、蓄積電荷などの特性に応じて、１種類又は２種類以上を混合して使用することもできる。 In addition, diaminosiloxanes represented by the following formula [DA35] can also be exemplified.
Figure JPOXMLDOC01-appb-C000015
 (In the formula [DA35], 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.
　本発明の液晶配向処理剤に含有されるポリアミド酸を得るために、ジアミン成分と反応させるテトラカルボン酸二無水物は特に限定されない。その具体例を以下に挙げる。
　脂環式構造又は脂肪族構造を有するテトラカルボン酸二無水物としては、１，２，３，４－シクロブタンテトラカルボン酸二無水物、１，２－ジメチル－１，２，３，４－シクロブタンテトラカルボン酸二無水物、１，３－ジメチル－１，２，３，４－シクロブタンテトラカルボン酸二無水物、１，２，３，４－テトラメチル－１，２，３，４－シクロブタンテトラカルボン酸二無水物、１，２，３，４－シクロペンタンテトラカルボン酸二無水物、２，３，４，５－テトラヒドロフランテトラカルボン酸二無水物、１，２，４，５－シクロヘキサンテトラカルボン酸二無水物、３，４－ジカルボキシ－１－シクロヘキシルコハク酸二無水物、３，４－ジカルボキシ－１，２，３，４－テトラヒドロ－１－ナフタレンコハク酸二無水物、１，２，３，４－ブタンテトラカルボン酸二無水物、ビシクロ［３，３，０］オクタン－２，４，６，８－テトラカルボン酸二無水物、３，３’，４，４’－ジシクロヘキシルテトラカルボン酸二無水物、２，３，５－トリカルボキシシクロペンチル酢酸二無水物、シス－３，７－ジブチルシクロオクタ－１，５－ジエン－１，２，５，６－テトラカルボン酸二無水物、トリシクロ［４．２．１．０２，５］ノナン－３，４，７，８－テトラカルボン酸－３，４：７，８－二無水物、ヘキサシクロ［６．６．０．１２，７．０３，６．１９，１４．０１０，１３］ヘキサデカン－４，５，１１，１２－テトラカルボン酸－４，５：１１，１２－二無水物、４－（２，５－ジオキソテトラヒドロフラン－３－イル）－１，２，３，４－テトラヒドロナフタレンー１，２－ジカルボン酸無水物などが挙げられる。 In order to obtain the polyamic acid contained in the liquid-crystal aligning agent of this invention, 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′-dicyclohexyltetra Carboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, cis-3,7-dibutylcycloocta-1,5-diene-1,2,5,6-tetracarboxylic dianhydride , Tricyclo [4.2.1.02,5] nonane-3,4,7,8-tetracarboxylic acid-3,4: 7,8-dianhydride, hexacyclo [6.6.0.12,7 .03, 6.19, 14.010, 13] hexadecane-4,5,11,12-tetracarboxylic acid-4,5: 11,12-dianhydride, 4- (2,5-dioxotetrahydrofuran- 3-yl) -1,2,3,4-tetrahydronaphth Examples include tarene-1,2-dicarboxylic acid anhydride.
　更には、上記脂環式構造又は脂肪族構造を有するテトラカルボン酸二無水物に加えて、芳香族テトラカルボン酸二無水物を使用すると、液晶配向性が向上し、かつ液晶セルの蓄積電荷を低減させることができるので好ましい。
　芳香族テトラカルボン酸二無水物としては、ピロメリット酸二無水物、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物、２，２’，３，３’－ビフェニルテトラカルボン酸二無水物、２，３，３’，４－ビフェニルテトラカルボン酸二無水物、３，３’，４，４’－ベンゾフェノンテトラカルボン酸二無水物、２，３，３’，４－ベンゾフェノンテトラカルボン酸二無水物、ビス（３，４－ジカルボキシフェニル）エーテル二無水物、ビス（３，４－ジカルボキシフェニル）スルホン二無水物、１，２，５，６－ナフタレンテトラカルボン酸二無水物、２，３，６，７－ナフタレンテトラカルボン酸二無水物などが挙げられる。
　テトラカルボン酸二無水物は、液晶配向膜にした際の液晶配向性、電圧保持特性、蓄積電荷などの特性に応じて、１種類又は２種類以上併用することができる。 Furthermore, when an aromatic tetracarboxylic dianhydride is used in addition to the tetracyclic dianhydride having the alicyclic structure or aliphatic structure, 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 can be used alone or in combination of two or more depending on the liquid crystal alignment properties, voltage holding characteristics, accumulated charge, and the like when the liquid crystal alignment film is formed.
　本発明のポリアミック酸エステルを得るために、ジアミン成分と反応させるテトラカルボン酸ジアルキルエステルは特に限定されない。その具体例を以下に挙げる。
　脂肪族テトラカルボン酸ジエステルの具体的な例としては、１，２，３，４－シクロブタンテトラカルボン酸ジアルキルエステル、１，２－ジメチル－１，２，３，４－シクロブタンテトラカルボン酸ジアルキルエステル、１，３－ジメチル－１，２，３，４－シクロブタンテトラカルボン酸ジアルキルエステル、１，２，３，４－テトラメチル－１，２，３，４－シクロブタンテトラカルボン酸ジアルキルエステル、１，２，３，４－シクロペンタンテトラカルボン酸ジアルキルエステル、２，３，４，５－テトラヒドロフランテトラカルボン酸ジアルキルエステル、１，２，４，５－シクロヘキサンテトラカルボン酸ジアルキルエステル、３，４－ジカルボキシ－１－シクロヘキシルコハク酸ジアルキルエステル、３，４－ジカルボキシ－１，２，３，４－テトラヒドロ－１－ナフタレンコハク酸ジアルキルエステル、１，２，３，４－ブタンテトラカルボン酸ジアルキルエステル、ビシクロ［３，３，０］オクタン－２，４，６，８－テトラカルボン酸ジアルキルエステル、３，３’，４，４’－ジシクロヘキシルテトラカルボン酸ジアルキルエステル、２，３，５－トリカルボキシシクロペンチル酢酸ジアルキルエステル、シス－３，７－ジブチルシクロオクタ－１，５－ジエン－１，２，５，６－テトラカルボン酸ジアルキルエステル、トリシクロ［４．２．１．０２，５］ノナン－３，４，７，８－テトラカルボン酸－３，４：７，８－ジアルキルエステル、ヘキサシクロ［６．６．０．１２，７．０３，６．１９，１４．０１０，１３］ヘキサデカン－４，５，１１，１２－テトラカルボン酸－４，５：１１，１２－ジアルキルエステル、４－（２，５－ジオキソテトラヒドロフラン－３－イル）－１，２，３，４－テトラヒドロナフタレンー１，２－ジカルボンジアルキルエステルなどが挙げられる。 In order to obtain the polyamic acid ester of this invention, 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 ester, 3,4-dicarboxy- 1-cyclohexyl succinic acid dialkyl ester, 3,4-dicarboxy 1,2,3,4-tetrahydro-1-naphthalene succinic acid dialkyl ester, 1,2,3,4-butanetetracarboxylic acid dialkyl ester, bicyclo [3,3,0] octane-2,4,6,8 Tetracarboxylic acid dialkyl ester, 3,3 ′, 4,4′-dicyclohexyl tetracarboxylic acid dialkyl ester, 2,3,5-tricarboxycyclopentylacetic acid dialkyl ester, cis-3,7-dibutylcycloocta-1,5 -Diene-1,2,5,6-tetracarboxylic acid dialkyl ester, tricyclo [4.2.1.02,5] nonane-3,4,7,8-tetracarboxylic acid-3, 4: 7,8 -Dialkyl ester, hexacyclo [6.6.0.12,7.03,6.19,14.010,13] hexadecane-4,5,11,1 2-tetracarboxylic acid-4,5: 11,12-dialkyl ester, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dialkyl Examples include esters.
　芳香族テトラカルボン酸ジアルキルエステルとしては、ピロメリット酸ジアルキルエステル、３，３’，４，４’－ビフェニルテトラカルボン酸ジアルキルエステル、２，２’，３，３’－ビフェニルテトラカルボン酸ジアルキルエステル、２，３，３’，４－ビフェニルテトラカルボン酸ジアルキルエステル、３，３’，４，４’－ベンゾフェノンテトラカルボン酸ジアルキルエステル、２，３，３’，４－ベンゾフェノンテトラカルボン酸ジアルキルエステル、ビス（３，４－ジカルボキシフェニル）エーテルジアルキルエステル、ビス（３，４－ジカルボキシフェニル）スルホンジアルキルエステル、１，２，５，６－ナフタレンテトラカルボン酸ジアルキルエステル、２，３，６，７－ナフタレンテトラカルボン酸ジアルキルエステルなどが挙げられる。 Examples of the aromatic tetracarboxylic acid dialkyl ester 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 es Le and the like.
［ポリアミック酸の合成］
　テトラカルボン酸二無水物とジアミン成分との反応により、本発明の液晶配向処理剤に含有されるポリアミック酸を得るにあたっては、公知の合成手法を用いることができる。一般的にはテトラカルボン酸二無水物とジアミン成分とを有機溶媒中で反応させる方法である。テトラカルボン酸二無水物とジアミンとの反応は、有機溶媒中で比較的容易に進行し、かつ副生成物が発生しない点で有利である。
　テトラカルボン酸二無水物とジアミンとの反応に用いる有機溶媒としては、生成したポリアミック酸が溶解するものであれば特に限定されない。その具体例を以下に挙げる。 [Synthesis of polyamic acid]
In obtaining the polyamic acid contained in the liquid-crystal aligning agent of this invention by reaction with tetracarboxylic dianhydride and a diamine component, a well-known synthesis method can be used. In general, tetracarboxylic dianhydride and a diamine component are reacted in an organic solvent. The reaction of tetracarboxylic dianhydride and diamine is advantageous in that it proceeds relatively easily in an organic solvent and no by-product is generated.
The organic solvent used for the reaction of tetracarboxylic dianhydride and diamine is not particularly limited as long as the produced polyamic acid is soluble. Specific examples are given below.
　Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチル－２－ピロリドン、Ｎ－エチル－２－ピロリドン、Ｎ－メチルカプロラクタム、ジメチルスルホキシド、テトラメチル尿素、ピリジン、ジメチルスルホン、ヘキサメチルスルホキシド、γ－ブチロラクトン、イソプロピルアルコール、メトキシメチルペンタノール、ジペンテン、エチルアミルケトン、メチルノニルケトン、メチルエチルケトン、メチルイソアミルケトン、メチルイソプロピルケトン、メチルセルソルブ、エチルセルソルブ、メチルセロソルブアセテート、エチルセロソルブアセテート、ブチルカルビトール、エチルカルビトール、エチレングリコール、エチレングリコールモノアセテート、エチレングリコールモノイソプロピルエーテル、エチレングリコールモノブチルエーテル、プロピレングリコール、プロピレングリコールモノアセテート、プロピレングリコールモノメチルエーテル、プロピレングリコール－ｔｅｒｔ－ブチルエーテル、ジプロピレングリコールモノメチルエーテル、ジエチレングリコール、ジエチレングリコールモノアセテート、ジエチレングリコールジメチルエーテル、ジプロピレングリコールモノアセテートモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノアセテートモノエチルエーテル、ジプロピレングリコールモノプロピルエーテル、ジプロピレングリコールモノアセテートモノプロピルエーテル、３－メチル－３－メトキシブチルアセテート、トリプロピレングリコールメチルエーテル、３－メチル－３－メトキシブタノール、ジイソプロピルエーテル、エチルイソブチルエーテル、ジイソブチレン、アミルアセテート、ブチルブチレート、ブチルエーテル、ジイソブチルケトン、メチルシクロへキセン、プロピルエーテル、ジヘキシルエーテル、ジオキサン、ｎ－へキサン、ｎ－ペンタン、ｎ－オクタン、ジエチルエーテル、シクロヘキサノン、エチレンカーボネート、プロピレンカーボネート、乳酸メチル、乳酸エチル、酢酸メチル、酢酸エチル、酢酸ｎ－ブチル、酢酸プロピレングリコールモノエチルエーテル、ピルビン酸メチル、ピルビン酸エチル、３－メトキシプロピオン酸メチル、３－エトキシプロピオン酸メチルエチル、３－メトキシプロピオン酸エチル、３－エトキシプロピオン酸、３－メトキシプロピオン酸、３－メトキシプロピオン酸プロピル、３－メトキシプロピオン酸ブチル、ジグライム、４－ヒドロキシ－４－メチル－２－ペンタノン、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド、３－エトキシ－Ｎ，Ｎ－ジメチルプロパンアミド、３－ブトキシ－Ｎ，Ｎ－ジメチルプロパンアミドなどが挙げられる。これらは単独で使用しても、混合して使用してもよい。さらに、ポリアミック酸を溶解させない溶媒であっても、生成したポリアミド酸が析出しない範囲で、上記溶媒に混合して使用してもよい。 N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide , Γ-butyrolactone, isopropyl alcohol, methoxymethylpentanol, 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, butyl Carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethyl 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, dipropylene glycol monoacetate monomethyl ether, dipropylene Glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropiate Lenglycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n- Hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, Ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropio Acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N, N-dimethylpropanamide, 3- Examples thereof include ethoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide and the like. These may be used alone or in combination. Furthermore, even if the solvent does not dissolve the polyamic acid, it may be used by mixing with the above solvent as long as the produced polyamic acid does not precipitate.
　また、有機溶媒中の水分は、重合反応を阻害し、さらには生成したポリアミド酸を加水分解させる原因となるので、有機溶媒はなるべく脱水乾燥させたものを用いることが好ましい。
　テトラカルボン酸二無水物とジアミン成分とを有機溶媒中で反応させる際には、ジアミン成分を有機溶媒に分散あるいは溶解させた溶液を攪拌させ、テトラカルボン酸二無水物をそのまま、又は有機溶媒に分散あるいは溶解させて添加する方法、逆にテトラカルボン酸二無水物を有機溶媒に分散あるいは溶解させた溶液にジアミン成分を添加する方法、テトラカルボン酸二無水物とジアミン成分とを交互に添加する方法などが挙げられる。これらのいずれの方法を用いても良い。また、テトラカルボン酸二無水物又はジアミン成分が、複数種の化合物からなる場合は、あらかじめ混合した状態で反応させても良く、個別に順次反応させても良く、さらに個別に反応させた低分子量体を混合反応させ高分子量体としても良い。 Moreover, since water in the organic solvent inhibits the polymerization reaction and further causes hydrolysis of the produced polyamic acid, it is preferable to use a dehydrated and dried organic solvent as much as possible.
When the tetracarboxylic dianhydride 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 dianhydride is used as it is or in an organic solvent. 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. In addition, when 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.
　その際の重合温度は、－２０～１５０℃の任意の温度を選択することができるが、好ましくは－５～１００℃の範囲である。
　また、反応は任意の濃度で行うことができるが、濃度が低すぎると高分子量の重合体を得ることが難しくなり、濃度が高すぎると反応液の粘性が高くなり過ぎて均一な攪拌が困難となるので、テトラカルボン酸二無水物とジアミン成分の反応溶液中での合計濃度が、好ましくは１～５０重量％、より好ましくは５～３０重量％である。反応初期は高濃度で行い、その後、有機溶媒を追加することができる。 In this case, 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.
　ポリアミド酸の重合反応においては、テトラカルボン酸二無水物の合計モル数と、ジアミン成分の合計モル数の比は０．８～１．２であることが好ましく、０．９～１．１がより好ましい。通常の重縮合反応と同様に、このモル比が１．０に近いほど、生成するポリアミド酸の分子量は大きくなる。
　本発明の液晶配向処理剤に含有されるポリイミドは、前記のポリアミド酸を脱水閉環させて得られるポリイミドであり、液晶配向膜を得るための重合体として有用である。
　本発明の液晶配向処理剤に含有されるポリイミドにおいて、アミド酸基の脱水閉環率（イミド化率）は、必ずしも１００％である必要はなく、用途や目的に応じて任意に調整することができる。 In the polyamic acid polymerization reaction, 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.
In the polyimide contained in the liquid crystal aligning agent of the present invention, 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. .
［ポリイミドの合成］
　ポリアミック酸をイミド化させる方法としては、ポリアミック酸の溶液をそのまま加熱する熱イミド化、ポリアミック酸の溶液に触媒を添加する触媒イミド化が挙げられる。
　ポリアミック酸を溶液中で熱イミド化させる場合の温度は、１００～４００℃、好ましくは１２０～２５０℃であり、イミド化反応により生成する水を系外に除きながら行う方法が好ましい。
　ポリアミック酸の触媒イミド化は、ポリアミック酸の溶液に、塩基性触媒と酸無水物とを添加し、－２０～２５０℃、好ましくは０～１８０℃で攪拌することにより行うことができる。塩基性触媒の量は、アミド酸基の０．５～３０モル倍、好ましくは２～２０モル倍であり、酸無水物の量は、アミド酸基の１～５０モル倍、好ましくは３～３０モル倍である。
　塩基性触媒としてはピリジン、トリエチルアミン、トリメチルアミン、トリブチルアミン、トリオクチルアミンなどを挙げることができ、中でもピリジンは反応を進行させるのに適度な塩基性を持つので好ましい。
　酸無水物としては、無水酢酸、無水トリメリット酸、無水ピロメリット酸などを挙げることができ、中でも無水酢酸を用いると、反応終了後の精製が容易となるので好ましい。
　触媒イミド化によるイミド化率は、触媒量と反応温度、反応時間を調節することにより制御することができる。 [Synthesis of polyimide]
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.
Examples of 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.
Examples of 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.
［ポリアミック酸エステルの合成］
　ポリアミック酸エステルを合成する方法としては、テトラカルボン酸ジエステルジクロリドとジアミンとの反応や、テトラカルボン酸ジエステルとジアミンを適当な縮合剤、塩基の存在下に反応させることによりポリイミドの前駆体の一種であるポリアミック酸エステルを得ることができる。又は、予めポリアミック酸を重合し、高分子反応を利用して、アミック酸中のカルボン酸をエステル化することでも得ることができる。
　具体的には、テトラカルボン酸ジエステルジクロリドとジアミンとを、塩基と有機溶剤の存在下で、－２０～１５０℃、好ましくは０～５０℃において、３０分～２４時間、好ましくは１～４時間反応させることによって合成することができる。
　前記塩基には、ピリジン、トリエチルアミン、４－ジメチルアミノピリジンなどが使用できるが、反応が穏和に進行するためにピリジンが好ましい。塩基の添加量は、除去が容易な量で、かつ高分子量体が得やすいという観点から、テトラカルボン酸ジエステルジクロリドに対して、２～４倍モルであることが好ましく、２～３倍モルがより好ましい。 [Synthesis of 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.
Specifically, 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.
As the 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.
　縮合剤の存在下に縮重合を行なう場合、縮合剤としては、トリフェニルホスファイト、ジシクロヘキシルカルボジイミド、１－エチル－３－（３－ジメチルアミノプロピル）カルボジイミド塩酸塩、Ｎ，Ｎ’－カルボニルジイミダゾール、ジメトキシ－１，３，５－トリアジニルメチルモルホリニウム、Ｏ－（ベンゾトリアゾール－１－イル）－Ｎ，Ｎ，Ｎ’，Ｎ’－テトラメチルウロニウム　テトラフルオロボラート、Ｏ－（ベンゾトリアゾール－１－イル）－Ｎ，Ｎ，Ｎ’，Ｎ’－テトラメチルウロニウムヘキサフルオロホスファート、（２，３－ジヒドロ－２－チオキソ－３－ベンゾオキサゾリル）ホスホン酸ジフェニル、４－（４，６－ジメトキシ－１，３，５－トリアジンー２－イル）４－メトキシモルホリウムクロリド　ｎ－水和物などが使用できる。
　また、上記縮合剤を用いる方法において、ルイス酸を添加剤として加えることで反応が効率的に進行する。ルイス酸としては、塩化リチウム、臭化リチウムなどのハロゲン化リチウムが好ましい。ルイス酸の添加量は、上記縮合剤に対して０．１～１．０倍モル量であることが好ましく、０．３～０．８倍モル量がより好ましい。
　上記の反応に用いる溶媒は、ポリアミック酸を重合する際に用いられる溶媒で行なうことができるが、モノマー及びポリマーの溶解性から、Ｎ－メチル－２－ピロリドン、γ－ブチロラクトン等が好ましく、これらは１種又は２種以上を混合して用いてもよい。
　合成時の濃度は、ポリマーの析出が起こりにくく、かつ高分子量体が得やすいという観点から、１～３０重量％が好ましく、５～２０重量％がより好ましい。また、テトラカルボン酸ジエステルジクロリドの加水分解を防ぐため、ポリアミック酸エステルの合成に用いる溶媒は、できるだけ脱水されていることが好ましく、反応は窒素雰囲気中で、外気の混入を防いで行うのが好ましい。 When polycondensation is performed in the presence of a condensing agent, examples of the condensing agent include triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N′-carbonyldiimidazole. , Dimethoxy-1,3,5-triazinylmethylmorpholinium, O- (benzotriazol-1-yl) -N, N, N ′, N′-tetramethyluronium tetrafluoroborate, O— ( Benzotriazol-1-yl) -N, N, N ′, N′-tetramethyluronium hexafluorophosphate, (2,3-dihydro-2-thioxo-3-benzoxazolyl) phosphonate diphenyl, 4 -(4,6-dimethoxy-1,3,5-triazin-2-yl) 4-methoxymorpholium chloride n-hydrate Can be used.
In the method using the condensing agent, the reaction proceeds efficiently by adding Lewis acid as an additive. As the 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, γ-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. In order to prevent hydrolysis of the tetracarboxylic acid diester dichloride, 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. .
［ポリマーの回収］
　ポリアミド酸、ポリアミック酸エステル、ポリイミドを含む反応溶液から、生成したポリアミド酸、ポリアミック酸エステル、ポリイミド等を回収する場合には、反応溶液を貧溶媒に投入して沈殿させれば良い。
　沈殿に用いる貧溶媒としてはメタノール、アセトン、ヘキサン、ブチルセルソルブ、ヘプタン、メチルエチルケトン、メチルイソブチルケトン、エタノール、トルエン、ベンゼン、水などを挙げることができる。中でも、メタノールが好ましい。
　貧溶媒に投入して沈殿させたポリマーは、濾過して回収した後、常圧あるいは減圧下で、常温あるいは加熱して乾燥することができる。また、沈殿回収した重合体を、有機溶媒に再溶解させ、再沈殿回収する操作を２～１０回繰り返すと、重合体中の不純物を少なくすることができる。この際の貧溶媒としては、例えば、アルコール類、ケトン類、炭化水素などが挙げられ、これらの内から選ばれる３種類以上の貧溶媒を用いると、より一層精製の効率が上がるので好ましい。
　本発明の液晶配向処理剤に含有されるポリアミド酸及びポリイミドの分子量は、そこから得られる塗膜の強度、塗膜形成時の作業性、及び塗膜の均一性を考慮した場合、ＧＰＣ（Ｇｅｌ　Ｐｅｒｍｅａｔｉｏｎ　Ｃｈｒｏｍａｔｏｇｒａｐｈｙ）法で測定した重量平均分子量で、５，０００～１，０００，０００とするのが好ましく、より好ましくは、１０，０００～１５０，０００である。 [Polymer recovery]
When recovering the produced polyamic acid, polyamic acid ester, polyimide, etc. from a reaction solution containing polyamic acid, polyamic acid ester, and polyimide, the reaction solution may be poured into a poor solvent and precipitated.
Examples of 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. In addition, when the polymer collected by precipitation is redissolved in an organic solvent and reprecipitation and collection is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of the poor solvent at this time include alcohols, ketones, hydrocarbons and the like, and it is preferable to use three or more kinds of poor solvents selected from these because purification efficiency is further improved.
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.
＜液晶配向処理剤＞
　本発明の液晶配向処理剤は、液晶配向膜を形成するための塗布液であり、上記したポリイミド前駆体及びポリイミドからなる群より選ばれる少なくとも１種の重合体と本発明の添加剤が、有機溶媒に溶解した溶液である。
　本発明の液晶配向処理剤中の固形分濃度は、形成する液晶配向膜の厚みの設定によって適宜変更することができるが、０．５～１０重量％とすることが好ましく、１～８重量％とすることがより好ましい。固形分濃度が０．５重量％未満では、均一で欠陥のない塗膜を形成させることが困難となり、１０重量％よりも多いと、溶液の保存安定性が悪くなる場合がある。
　ここで言う固形分とは、液晶配向処理剤から溶媒を除いた成分を言い、上記したポリイミド前駆体及びポリイミドからなる群より選ばれる少なくとも１種の重合体、本発明の添加剤、及び上記した各種の添加剤を意味する。 <Liquid crystal alignment agent>
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.
The term “solid content” as used herein 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.
　本発明の液晶配向処理剤の製造方法は特に限定されない。通常は、上記ポリイミド前駆体の溶液、ポリイミドの溶液、又はポリイミドの溶液とポリイミド前駆体の溶液とを混合することにより製造される。ポリアミック酸の場合、重縮合にて得られたポリアミック酸の反応溶液をそのまま使用してもよいし、また、一旦、ポリアミック酸を得てから、これを有機溶媒に再溶解させてポリアミック酸溶液として使用することができる。ポリアミック酸溶液は、所望の濃度まで希釈して使用してもよい。
　一方、可溶性ポリイミドの場合、イミド化して得られた可溶性ポリイミドの反応溶液をそのまま使用してもよいし、また、一旦、ポリイミド粉末を得てから、これを有機溶媒に再溶解させてポリイミド溶液として使用することができる。ポリイミド溶液は、所望の濃度まで希釈して使用してもよい。 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. In the case of polyamic acid, 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.
On the other hand, in the case of soluble polyimide, 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.
　本発明の液晶配向処理剤に用いる有機溶媒は、樹脂成分を溶解させる有機溶媒であれば特に限定されない。その具体例を以下に挙げる。
　Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチル－２－ピロリドン、Ｎ－メチルカプロラクタム、２－ピロリドン、Ｎ－エチル－２－ピロリドン、Ｎ－ビニルピロリドン、ジメチルスルホキシド、テトラメチル尿素、ピリジン、ジメチルスルホン、ヘキサメチルスルホキシド、γ－ブチロラクトン、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド、３－エトキシ－Ｎ，Ｎ－ジメチルプロパンアミド、３－ブトキシ－Ｎ，Ｎ－ジメチルプロパンアミド、１，３－ジメチル－イミダゾリジノン、エチルアミルケトン、メチルノニルケトン、メチルエチルケトン、メチルイソアミルケトン、メチルイソプロピルケトン、シクロヘキサノン、エチレンカーボネート、プロピレンカーボネート、ジグライム、４－ヒドロキシ－４－メチル－２－ペンタノンなどが挙げられる。これらは単独で使用しても、混合して使用してもよい。
　有機溶媒の液晶配向処理剤中における含有量は、８０～９９．５重量％であり、９０～９９.5重量％が好ましく、溶液の保存安定性、均一な塗膜の形成の点からは、より好ましくは９２～９９重量％である。 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, γ-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 isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diglyme, 4-hydroxy Such as 4-methyl-2-pentanone and the like. These may be used alone or in combination.
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.
　本発明の液晶配向処理剤は、上記以外の成分を含有してもよい。その例としては、液晶配向処理剤を塗布した際の膜厚均一性や表面平滑性を向上させる溶媒や化合物、液晶配向膜と基板との密着性を向上させる化合物、熱安定性を向上させる酸化防止剤、光耐性を向上させる光安定剤などである。 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.
　膜厚均一性や表面平滑性を向上させる溶媒（貧溶媒）の具体例としては、次のものが挙げられる。
　例えば、イソプロピルアルコール、メトキシメチルペンタノール、メチルセロソルブ、エチルセロソルブ、ブチルセロソルブ、メチルセロソルブアセテート、エチルセロソルブアセテート、ブチルカルビトール、エチルカルビトール、エチルカルビトールアセテート、エチレングリコール、エチレングリコールモノアセテート、エチレングリコールモノイソプロピルエーテル、エチレングリコールモノブチルエーテル、プロピレングリコール、プロピレングリコールモノアセテート、プロピレングリコールモノメチルエーテル、プロピレングリコール－ｔｅｒｔ－ブチルエーテル、ジプロピレングリコールモノメチルエーテル、ジエチレングリコール、ジエチレングリコールモノアセテート、ジエチレングリコールジメチルエーテル、ジプロピレングリコールモノアセテートモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノアセテートモノエチルエーテル、ジプロピレングリコールモノプロピルエーテル、ジプロピレングリコールモノアセテートモノプロピルエーテル、３－メチル－３－メトキシブチルアセテート、トリプロピレングリコールメチルエーテル、３－メチル－３－メトキシブタノール、ジイソプロピルエーテル、エチルイソブチルエーテル、ジイソブチレン、アミルアセテート、ブチルブチレート、ブチルエーテル、ジイソブチルケトン、メチルシクロへキセン、プロピルエーテル、ジヘキシルエーテル、１－ヘキサノール、ｎ－へキサン、ｎ－ペンタン、ｎ－オクタン、ジエチルエーテル、乳酸メチル、乳酸エチル、酢酸メチル、酢酸エチル、酢酸ｎ－ブチル、酢酸プロピレングリコールモノエチルエーテル、ピルビン酸メチル、ピルビン酸エチル、３－メトキシプロピオン酸メチル、３－エトキシプロピオン酸メチルエチル、３－メトキシプロピオン酸エチル、３－エトキシプロピオン酸、３－メトキシプロピオン酸、３－メトキシプロピオン酸プロピル、３－メトキシプロピオン酸ブチル、１－メトキシ－２－プロパノール、１－エトキシ－２－プロパノール、１－ブトキシ－２－プロパノール、１－フェノキシ－２－プロパノール、プロピレングリコールモノアセテート、プロピレングリコールジアセテート、プロピレングリコール－１－モノメチルエーテル－２－アセテート、プロピレングリコール－１－モノエチルエーテル－２－アセテート、ジプロピレングリコール、２－（２－エトキシプロポキシ）プロパノール、乳酸メチルエステル、乳酸エチルエステル、乳酸ｎ－プロピルエステル、乳酸ｎ－ブチルエステル、乳酸イソアミルエステルなどの低表面張力を有する溶媒などが挙げられる。
　これらの貧溶媒は、１種類でも複数種類を混合して用いてもよい。上記のような溶媒を用いる場合は、液晶配向処理剤に含まれる溶媒全体の５～８０重量％であることが好ましく、より好ましくは２０～６０重量％である。 Specific examples of the solvent (poor solvent) that improves the film thickness uniformity and the surface smoothness include the following.
For example, 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, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3 -Methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl Ether, 1-hexanol, n-hexane, n-pentane, n-octane Diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, Ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1 -Butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol- Low 1-monoethyl ether-2-acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, lactate methyl ester, lactate ethyl ester, lactate n-propyl ester, lactate n-butyl ester, lactate isoamyl ester Examples include solvents having surface tension.
These poor solvents may be used alone or in combination. When the above solvent is used, it is preferably 5 to 80% by weight, more preferably 20 to 60% by weight, based on the total amount of the solvent contained in the liquid crystal aligning agent.
　膜厚均一性や表面平滑性を向上させる化合物としては、フッ素系界面活性剤、シリコーン系界面活性剤、ノ二オン系界面活性剤などが挙げられる。
　より具体的には、例えば、エフトップＥＦ３０１、ＥＦ３０３、ＥＦ３５２（トーケムプロダクツ社製））、メガファックＦ１７１、Ｆ１７３、Ｒ－３０（大日本インキ社製）、フロラードＦＣ４３０、ＦＣ４３１（住友スリーエム社製）、アサヒガードＡＧ７１０、サーフロンＳ－３８２、ＳＣ１０１、ＳＣ１０２、ＳＣ１０３、ＳＣ１０４、ＳＣ１０５、ＳＣ１０６（旭硝子社製）などが挙げられる。
　これらの界面活性剤の使用割合は、液晶配向処理剤に含有される樹脂成分の１００重量部に対して、好ましくは０．０１～２重量部、より好ましくは０．０１～１重量部である。 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. .
　液晶配向膜と基板との密着性を向上させる化合物の具体例としては、次に示す官能性シラン含有化合物やエポキシ基含有化合物などが挙げられる。
　例えば、３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリエトキシシラン、２－アミノプロピルトリメトキシシラン、２－アミノプロピルトリエトキシシラン、Ｎ－（２－アミノエチル）－３－アミノプロピルトリメトキシシラン、Ｎ－（２－アミノエチル）－３－アミノプロピルメチルジメトキシシラン、３－ウレイドプロピルトリメトキシシラン、３－ウレイドプロピルトリエトキシシラン、Ｎ－エトキシカルボニル－３－アミノプロピルトリメトキシシラン、Ｎ－エトキシカルボニル－３－アミノプロピルトリエトキシシラン、Ｎ－トリエトキシシリルプロピルトリエチレントリアミン、Ｎ－トリメトキシシリルプロピルトリエチレントリアミン、１０－トリメトキシシリル－１，４，７－トリアザデカン、１０－トリエトキシシリル－１，４，７－トリアザデカン、９－トリメトキシシリル－３，６－ジアザノニルアセテート、９－トリエトキシシリル－３，６－ジアザノニルアセテート、Ｎ－ベンジル－３－アミノプロピルトリメトキシシラン、Ｎ－ベンジル－３－アミノプロピルトリエトキシシラン、Ｎ－フェニル－３－アミノプロピルトリメトキシシラン、Ｎ－フェニル－３－アミノプロピルトリエトキシシラン、Ｎ－ビス（オキシエチレン）－３－アミノプロピルトリメトキシシラン、Ｎ－ビス（オキシエチレン）－３－アミノプロピルトリエトキシシラン、エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、トリプロピレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、１，６－ヘキサンジオールジグリシジルエーテル、グリセリンジグリシジルエーテル、２，２－ジブロモネオペンチルグリコールジグリシジルエーテル、１，３，５，６－テトラグリシジル－２，４－ヘキサンジオール、Ｎ，Ｎ，Ｎ’，Ｎ’，－テトラグリシジル－ｍ－キシレンジアミン、１，３－ビス（Ｎ，Ｎ－ジグリシジルアミノメチル）シクロヘキサン、Ｎ，Ｎ，Ｎ’，Ｎ’，－テトラグリシジル－４、４’－ジアミノジフェニルメタンなどが挙げられる。
　これらの密着性を向上させる化合物の使用割合は、液晶配向処理剤に含有される樹脂成分の１００重量部に対して、好ましくは０．１～１０重量部、より好ましくは１～５重量部である。 Specific examples of 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.
For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxy Carbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-to Ethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltri Methoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-amino Propyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether , Polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetra Glycidyl-2,4-hexanediol, N, N, N ′, N ′,-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N Examples include ', N',-tetraglycidyl-4,4'-diaminodiphenylmethane.
The use ratio of the compound for improving the adhesion is preferably 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight with respect to 100 parts by weight of the resin component contained in the liquid crystal aligning agent. is there.
　熱安定性を向上させる化合物の具体例としては、以下に示すフェノール系化合物などが挙げられる。
　例えば、２，６－ジ－ｔｅｒｔ－ブチル－ｐ－クレゾール、２，６－ジ－ｔｅｒｔ－ブチル－フェノール、２，４，６－トリス（３’，５’－ジ－ｔｅｒｔ－ブチル－４’－ヒドロキシベンジル）メシチレン、ペンタエリスリトールテトラキス［３－（３’，５’－ジ－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオネート］、アセトンビス（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）メルカプトール、４，４’－メチレンビス（２，６－ジ－ｔｅｒｔ－ブチルフェノール）、３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオン酸メチル、４，４’－チオジ（２，６－ジ－ｔｅｒｔ－ブチルフェノール）、トリス（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジル）イソシアヌル酸、ビス（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジル）スルフィド等が挙げられる。
　これらの熱安定性を向上させる化合物の使用割合は、液晶配向処理剤に含有される樹脂成分の１００重量部に対して、好ましくは１～２０重量部、より好ましくは２～１０重量部である。 Specific examples of the compound that improves the thermal stability include the following phenol compounds.
For example, 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butyl-phenol, 2,4,6-tris (3 ′, 5′-di-tert-butyl-4 ′ -Hydroxybenzyl) mesitylene, pentaerythritol tetrakis [3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate], acetone bis (3,5-di-tert-butyl-4-hydroxy Phenyl) mercaptol, 4,4′-methylenebis (2,6-di-tert-butylphenol), methyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 4,4′-thiodi (2,6-di-tert-butylphenol), tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid, bis 3,5-di -tert- butyl-4-hydroxybenzyl) sulfide and the like.
The use ratio of the compound for improving the thermal stability is preferably 1 to 20 parts by weight, more preferably 2 to 10 parts by weight with respect to 100 parts by weight of the resin component contained in the liquid crystal aligning agent. .
［液晶配向膜］
　本発明の液晶配向処理剤は、好ましくは、基板に塗布する前に濾過した後、基板に塗布し、乾燥、焼成することで塗膜とすることができる。この塗膜面をラビング処理や光照射などの配向処理をすることにより、本発明の液晶配向膜として使用される。
　この際、用いる基板としては、透明性の高い基板であれば特に限定されず、ガラス基板、アクリル基板やポリカーボネート基板などのプラスチック基板などを用いることができる。また、液晶駆動のためのＩＴＯ電極などが形成された基板を用いることが、プロセスの簡素化の観点から好ましい。また、反射型の液晶表示素子では、片側の基板のみにならばシリコンウエハー等の不透明な基板でも使用でき、この場合の電極は、アルミ等の光を反射する材料も使用できる。 [Liquid crystal alignment film]
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.
In this case, 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. In addition, it is preferable to use a substrate on which an ITO electrode or the like for driving liquid crystal is formed from the viewpoint of simplifying the process. In the reflective liquid crystal display element, 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.
　液晶配向処理剤の塗布方法としては、スピンコート法、印刷法、インクジェット法などが挙げられるが、生産性の面から、工業的にはフレキソ印刷法が広く用いられており、本発明の液晶配向処理剤においても好適に用いられる。
　液晶配向処理剤を塗布した後の乾燥の工程は、必ずしも必要とされないが、塗布後から焼成までの時間が基板ごとに一定していない場合や、塗布後ただちに焼成されない場合には、乾燥工程を含めることが好ましい。
　乾燥は、基板の搬送等により塗膜形状が変形しない程度に溶媒が蒸発していればよく、乾燥手段については特に限定されない。具体例を挙げるならば、５０～１５０℃、好ましくは８０～１２０℃のホットプレート上で、０．５～３０分、好ましくは１～５分乾燥させる方法がとられる。 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. As a specific example, 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.
　液晶配向処理剤を塗布した基板の焼成は、１００～３５０℃の任意の温度で行うことができるが、好ましくは１５０～３００℃であり、さらに好ましくは１８０～２５０℃である。
　液晶配向処理剤中に含有されるポリアミック酸は、この焼成によって、ポリアミック酸からイミドへの転化率が変化するが、ポリアミック酸は、必ずしも１００％イミド化させる必要は無い。ただし、液晶セルの製造工程で必要とされる、シール剤硬化などの熱処理温度より、１０℃以上高い温度で焼成することが好ましい。
　焼成後の塗膜の厚みは、厚すぎると液晶表示素子の消費電力の面で不利となり、薄すぎると液晶表示素子の信頼性が低下する場合があるので、好ましくは１０～２００ｎｍ、より好ましくは５０～１００ｎｍである。
　上記のようにして基板上に形成された塗膜面のラビング処理は、既存のラビング装置を使用することができる。この際のラビング布の材質としては、コットン、レーヨン、ナイロンなどが挙げられる。 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. However, 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.
If 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.
　本発明の液晶表示素子は、上記した手法により本発明の液晶配向処理剤から液晶配向膜付き基板を得た後、公知の方法で液晶セルを作製し、液晶表示素子としたものである。
　液晶セル作製の一例を挙げるならば、液晶配向膜の形成された１対の基板を、好ましくは１～３０μｍ、より好ましくは２～１０μｍのスペーサーを挟んで、ラビング方向が０～２７０°の任意の角度となるように設置して、周囲をシール剤で固定し、液晶を注入して封止する方法が一般的である。液晶封入の方法については特に制限されず、作製した液晶セル内を減圧にした後液晶を注入する真空法、液晶を滴下した後封止を行う滴下法などが例示できる。
　このようにして得られた液晶表示素子は、バックライト光や紫外光照射に伴う電気特性の低下が軽減され、信頼性の高い液晶表示デバイスとすることができる。 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.
As an example of liquid crystal cell production, 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 μm, more preferably 2 to 10 μm. In general, 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.
　以下に実施例を示し、本発明をさらに詳細に説明するが、本発明はこれらに限定して解釈されるものではない。
　使用する略号の説明
＜テトラカルボン酸二無水物＞
ＣＢＤＡ：１，２，３，４－シクロブタンテトラカルボン酸二無水物
ＰＭＤＡ：ピロメリット酸二無水物
ＴＤＡ：３，４－ジカルボキシ－１，２，３，４－テトラヒドロ－1－ナフタレンコハク酸二無水物
TCA：２，３，５－トリカルボキシシクロペンチル酢酸－１，４：２，３－二無水物 The present invention will be described in more detail with reference to the following examples, but the present invention should not be construed as being limited thereto.
Explanation of abbreviations used <Tetracarboxylic dianhydride>
CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride PMDA: pyromellitic dianhydride TDA: 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid Anhydride
TCA: 2,3,5-tricarboxycyclopentylacetic acid-1,4: 2,3-dianhydride
＜ジアミン＞
ＤＤＭ：４，４’－ジアミノジフェニルメタン
２，４－ＤＡＡ：２，４－ジアミノ－Ｎ，Ｎ－ジアリルアミン
４－ABA：４－アミノベンジルアミン
Ｃ１２ＤＡＢ：４－ドデシルオキシ－１，３－ジアミノベンゼン
Ｃ１８ＤＡＢ：４－オクタデシルオキシ－１，３－ジアミノベンゼン
ＤＡＰＢＡ：３，５－ジアミノ－Ｎ－（ピリジン－３イルメチル）ベンズアミド（3AMPDA）
ＰＤＡ：ｐ－フェニレンジアミン
ＢＡＰＵ：１，３－ビス（４－アミノフェネチル）ウレア
ＤＡＢＦｒ：３，５－ジアミノベンジル－２－フロイレート
３－MAMＡ：3－（（N－メチルアミノ）メチル）アニリン（Ｍｅ-３ＡＢＡ）
ＰＣＢＡＤＡ：４－（トランス－４－ペンチルシクロヘキシル）ベンズアミド－2’,4’－フェニレンジアミン（CAB-2）
ＤＤＥ:４，４’－ジアミノジフェニルエーテル
ＤＴＴ：２，４－ジアミノ－６－フェニル－１，３，５－トリアジン <Diamine>
DDM: 4,4′-diaminodiphenylmethane 2,4-DAA: 2,4-diamino-N, N-diallylamine 4-ABA: 4-aminobenzylamine C12DAB: 4-dodecyloxy-1,3-diaminobenzene C18DAB: 4-Octadecyloxy-1,3-diaminobenzene DAPBA: 3,5-diamino-N- (pyridin-3-ylmethyl) benzamide (3AMPDA)
PDA: p-phenylenediamine BAPU: 1,3-bis (4-aminophenethyl) urea DABFr: 3,5-diaminobenzyl-2-furolate 3-MAMA: 3-((N-methylamino) methyl) aniline (Me -3ABA)
PCBADA: 4- (trans-4-pentylcyclohexyl) benzamide-2 ′, 4′-phenylenediamine (CAB-2)
DDE: 4,4′-diaminodiphenyl ether DTT: 2,4-diamino-6-phenyl-1,3,5-triazine
＜有機溶媒＞
ＮＭＰ：Ｎ－メチル－２－ピロリドン
ＧＢＬ：γ－ブチロラクトン（γ－ＢＬ）
ＢＳ：ブチルセロソルブ
＜分子量の測定＞
　ポリイミドの分子量は、該ポリイミドをＧＰＣ（常温ゲル浸透クロマトグラフィー）装置によって測定し、ポリエチレングリコール、ポリエチレンオキシド換算値として数平均分子量と重量平均分子量を算出した。
ＧＰＣ装置：（株）Ｓｈｏｄｅｘ社製　（ＧＰＣ－１０１）
カラム：Ｓｈｏｄｅｘ社製　（ＫＤ８０３、ＫＤ８０５の直列）
カラム温度：５０℃
溶離液：Ｎ，Ｎ－ジメチルホルムアミド（添加剤として、臭化リチウム－水和物（ＬｉＢｒ・Ｈ２Ｏ）が３０ｍｍｏｌ／Ｌ、リン酸・無水結晶（ｏ-リン酸）が３０ｍｍｏｌ／Ｌ、テトラヒドロフラン（ＴＨＦ）が１０ｍＬ／Ｌ）
流速：１．０ｍＬ／分
検量線作成用標準サンプル：東ソー社製　ＴＳＫ　標準ポリエチレンオキサイド（分子量　約９０００００、１５００００、１０００００、３００００）、および、ポリマーラボラトリー社製　ポリエチレングリコール（分子量　約１２０００、４０００、１０００）。 <Organic solvent>
NMP: N-methyl-2-pyrrolidone GBL: γ-butyrolactone (γ-BL)
BS: Butyl cellosolve <Measurement of molecular weight>
The molecular weight of the polyimide was measured with a GPC (normal temperature gel permeation chromatography) apparatus, and the number average molecular weight and weight average molecular weight were calculated as polyethylene glycol and polyethylene oxide equivalent values.
GPC device: manufactured by Shodex (GPC-101)
Column: manufactured by Shodex (series of KD803 and KD805)
Column temperature: 50 ° C
Eluent: N, N-dimethylformamide (as additives, lithium bromide-hydrate (LiBr · H 2 O) 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 .
＜イミド化率の測定＞
　ポリイミドのイミド化率は、該ポリイミドをｄ６－ＤＭＳＯ（ジメチルスルホキシド－ｄ６、ＴＭＳ（テトラメチルシラン）混合品）に溶解させ、４００ＭＨｚの１Ｈ　ＮＭＲ（バリアン社製）を用いて測定した。すなわち、イミド化前後で変化しない構造に由来するプロトンを基準プロトンとして決め、このプロトンのピーク積算値と、９.５～１０.０ｐｐｍ付近に現れるアミド酸のＮＨ基に由来するプロトンピーク積算値とを用い以下の式によって求めた。
　　イミド化率（％）＝（１－α・ｘ／ｙ）×１００
　上記式において、ｘはアミド酸のＮＨ基由来のプロトンピーク積算値、ｙは基準プロトンのピーク積算値、αはポリアミド酸（イミド化率が０％）の場合におけるアミド酸のＮＨ基プロトン１個に対する基準プロトンの個数割合である。 <Measurement of imidization ratio>
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−α · x / y) × 100
In the above formula, x is a proton peak integrated value derived from NH group of amic acid, y is a peak integrated value of reference proton, α 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.
[ポリマー溶液の製造（ポリアミック酸及びポリイミドの製造]
（製造例１）
　５００ｍｌ四口フラスコにＤＤＭを３９．６ｇ、ＮＭＰを２２２ｇ、γ－ＢＬを２２２ｇ加えて溶解し、ＣＢＤＡを１９．６ｇ、及びＰＭＤＡを１９．２ｇ添加した。窒素雰囲気下、室温で５時間反応させて、ポリマー溶液を調製した。このポリマーの数平均分子量は１０，９００、重量平均分子量は２７，３００であった。得られたポリマー溶液４００ｇにγ－ＢＬを４５０ｇ、ＢＳを１５０ｇ加え、室温で２時間攪拌し、ポリマー溶液Ｐ－１を得た。 [Production of polymer solution (Production of polyamic acid and polyimide)]
(Production Example 1)
In a 500 ml four-necked flask, 39.6 g of DDM, 222 g of NMP and 222 g of γ-BL were added and dissolved, and 19.6 g of CBDA and 19.2 g of PMDA were added. A polymer solution was prepared by reacting at room temperature for 5 hours under a nitrogen atmosphere. The number average molecular weight of this polymer was 10,900, and the weight average molecular weight was 27,300. To 400 g of the obtained polymer solution, 450 g of γ-BL and 150 g of BS were added and stirred at room temperature for 2 hours to obtain a polymer solution P-1.
（製造例２）
　１Ｌセパラブルフラスコに２，４－ＤＡＡを４０．６ｇ、４－ＡＢＡを１８．４ｇ、Ｃ１２ＤＡＢを４３．９ｇ、ＮＭＰを８１３ｇ加え溶解し、ＣＢＤＡを６７．７ｇ、ＰＭＤＡを３２．７ｇ添加した。窒素雰囲気下、室温で２２時間反応させてポリマー溶液を調製した。
　得られたポリマー溶液１９２ｇに、ＮＭＰを３４５ｇ加えて希釈し、無水酢酸２８．４ｇとピリジン１２．１ｇを加えて、５０℃にて３時間反応させてイミド化した。この反応溶液を室温程度まで冷却後、メタノール２０００ｍｌ中に投入し、沈殿した固形物を回収した。さらに、この固形物をメタノールで数回洗浄した後、１００℃で減圧乾燥して、ポリイミドの白色粉末を得た。このポリイミドの数平均分子量は１２，５００、重量平均分子量は３４，１００であった。またイミド化率は９０％であった。
　さらに得られたパウダー６ｇを、７４ｇのγ－ＢＬ、２０ｇのＢＳとの混合溶液に５０℃にて２４時間攪拌して溶解させ、樹脂成分が６重量％であるポリマー溶液Ｐ－２を得た。 (Production Example 2)
To a 1 L separable flask, 40.6 g of 2,4-DAA, 18.4 g of 4-ABA, 43.9 g of C12DAB and 813 g of NMP were added and dissolved, and 67.7 g of CBDA and 32.7 g of PMDA were added. A polymer solution was prepared by reacting at room temperature for 22 hours under a nitrogen atmosphere.
To 192 g of the obtained polymer solution, 345 g of NMP was added for dilution, and 28.4 g of acetic anhydride and 12.1 g of pyridine were added and reacted at 50 ° C. for 3 hours to imidize. 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%.
Further, 6 g of the obtained powder was dissolved in a mixed solution of 74 g of γ-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. .
（製造例３）
　５００ｍｌ四口フラスコにＤＤＭを３３．７ｇ、ＤＴＴを３．７ｇ、ＮＭＰを２２２ｇ、γ－ＢＬを２２２ｇ加えて溶解し、ＣＢＤＡを１９．６ｇ、ＰＭＤＡを１９．２ｇ添加した。窒素雰囲気下、室温で５時間反応させて、ポリマー溶液を調製した。このポリマーの数平均分子量は７，３００、重量平均分子量は１４，３００であった。得られたポリマー溶液４００ｇにγ－ＢＬを４５０ｇ、ＢＳを１５０ｇ加え、室温で２時間攪拌し、ポリマー溶液Ｐ－３を得た。 (Production Example 3)
In a 500 ml four-necked flask, 33.7 g of DDM, 3.7 g of DTT, 222 g of NMP and 222 g of γ-BL were added and dissolved, and 19.6 g of CBDA and 19.2 g of PMDA were added. A polymer solution was prepared by reacting at room temperature for 5 hours under a nitrogen atmosphere. The number average molecular weight of this polymer was 7,300, and the weight average molecular weight was 14,300. To 400 g of the obtained polymer solution, 450 g of γ-BL and 150 g of BS were added and stirred at room temperature for 2 hours to obtain a polymer solution P-3.
（製造例４）
　５００ｍｌ四口フラスコにＰＤＡを１３．０ｇ、ＤＡＰＢＡを１４．５ｇ、Ｃ１２ＤＡＢを５．８ｇ、ＮＭＰを４０７ｇ加えて溶解し、ＣＢＤＡを３８．４ｇ添加した。窒素雰囲気下、室温で５時間反応させて、ポリマー溶液を調製した。このポリマーの数平均分子量は９，８００、重量平均分子量は１８，１００であった。得られたポリマー溶液４００ｇにＮＭＰを４００ｇ、ＢＳを２００ｇ加え、室温で２時間攪拌し、ポリマー溶液Ｐ－４を得た。 (Production Example 4)
In a 500 ml four-necked flask, 13.0 g of PDA, 14.5 g of DAPBA, 5.8 g of C12DAB, and 407 g of NMP were added and dissolved, and 38.4 g of CBDA was added. A polymer solution was prepared by reacting at room temperature for 5 hours under a nitrogen atmosphere. The number average molecular weight of this polymer was 9,800, and the weight average molecular weight was 18,100. 400 g of the resulting polymer solution was added with 400 g of NMP and 200 g of BS, and stirred at room temperature for 2 hours to obtain a polymer solution P-4.
（製造例５）
　１ＬセパラブルフラスコにＰＤＡを２２．７ｇ、ＢＡＰＵを１７．９ｇ、Ｃ１８ＤＡＢを１１．３ｇ、ＮＭＰを８０３ｇ加え溶解し、ＴＤＡを８９．８ｇ、添加した。窒素雰囲気下、５０℃で２４時間反応させてポリマー溶液を調製した。
　得られたポリマー溶液２００ｇに、ＮＭＰを３００ｇ加えて希釈し、無水酢酸６４．７ｇとピリジン３０．１ｇを加えて、５０℃にて３時間反応させてイミド化した。この反応溶液を室温程度まで冷却後、メタノール２０００ｍｌ中に投入し、沈殿した固形物を回収した。さらに、この固形物をメタノールで数回洗浄した後、１００℃で減圧乾燥して、白色粉末を得た。このポリイミドの数平均分子量は１０，５００、重量平均分子量は２７，６００であった。またイミド化率は８３％であった。
　さらに得られたパウダー６ｇを、９４ｇのγ－ＢＬに５０℃にて２４時間攪拌して溶解させ、樹脂成分が６重量％であるポリマー溶液Ｐ－５を得た。 (Production Example 5)
In a 1 L separable flask, 22.7 g of PDA, 17.9 g of BAPU, 11.3 g of C18DAB and 803 g of NMP were added and dissolved, and 89.8 g of TDA was added. A polymer solution was prepared by reacting at 50 ° C. for 24 hours under a nitrogen atmosphere.
To 200 g of the obtained polymer solution, 300 g of NMP was added for dilution, 64.7 g of acetic anhydride and 30.1 g of pyridine were added, and the mixture was reacted at 50 ° C. for 3 hours to imidize. 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%.
Further, 6 g of the obtained powder was dissolved in 94 g of γ-BL by stirring at 50 ° C. for 24 hours to obtain a polymer solution P-5 having a resin component of 6% by weight.
（製造例６）
　５００mＬセパラブルフラスコにＤＡＢＦｒを９．３ｇ、３-ＭＡＭＡを２０．４ｇ、ＰＣＢＡＤＡを４．１ｇ、ＮＭＰを４１２ｇ加え溶解し、ＣＢＤＡを３８．８ｇ、添加した。窒素雰囲気下、室温で２４時間反応させてポリマー溶液を調製した。
　得られたポリマー溶液３００ｇに、ＮＭＰを７５ｇ加えて希釈し、無水酢酸６２．９ｇとピリジン１９．５ｇを加えて、７０℃にて３時間反応させてイミド化した。この反応溶液を室温程度まで冷却後、メタノール１６００ｍｌ中に投入し、沈殿した固形物を回収した。さらに、この固形物をメタノールで数回洗浄した後、１００℃で減圧乾燥して、白色粉末を得た。このポリイミドの数平均分子量は１１，５００、重量平均分子量は３８，１００であった。またイミド化率は５８％であった。
　さらに得られたパウダー６ｇを、９４ｇのγ－ＢＬに５０℃にて２４時間攪拌して溶解させ、樹脂成分が６重量％であるポリマー溶液Ｐ－６を得た。 (Production Example 6)
In a 500 mL separable flask, 9.3 g of DABFr, 20.4 g of 3-MAMA, 4.1 g of PCBADA and 412 g of NMP were added and dissolved, and 38.8 g of CBDA was added. A polymer solution was prepared by reacting at room temperature for 24 hours under a nitrogen atmosphere.
To 300 g of the obtained polymer solution, 75 g of NMP was added for dilution, 62.9 g of acetic anhydride and 19.5 g of pyridine were added, and the mixture was reacted at 70 ° C. for 3 hours to imidize. 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%.
Further, 6 g of the obtained powder was dissolved in 94 g of γ-BL by stirring at 50 ° C. for 24 hours to obtain a polymer solution P-6 having a resin component of 6% by weight.
（製造例７）
　５００ｍｌ四口フラスコにDDEを28．0ｇ、ＮＭＰを334ｇ加えて溶解し、TCAを30．8ｇ添加した。窒素雰囲気下、室温で20時間反応させて、ポリマー溶液を調製した。このポリマーの数平均分子量は９，２００、重量平均分子量は２０，８００であった。得られたポリマー溶液２００ｇにNMPを２００ｇ、ＢＳを１００ｇ加え、室温で２時間攪拌し、ポリマー溶液Ｐ－7を得た。 (Production Example 7)
In a 500 ml four-necked flask, 28.0 g of DDE and 334 g of NMP were added and dissolved, and 30.8 g of TCA was added. A polymer solution was prepared by reacting at room temperature for 20 hours under a nitrogen atmosphere. The number average molecular weight of this polymer was 9,200, and the weight average molecular weight was 20,800. 200 g of NMP and 100 g of BS were added to 200 g of the obtained polymer solution, and the mixture was stirred at room temperature for 2 hours to obtain a polymer solution P-7.
[液晶配向処理剤の調製と各種評価]
　実施例１～１６、及び比較例１～３には、各液晶配向処理剤の調製、該液晶配向処理剤を用いた各液晶配向膜の調製、得られた液晶配向膜のラビング耐性の評価、該液晶配向膜を有する各液晶セルの作製及び各液晶セルの評価について示した。
　実施例及び比較例で得られた各液晶セルのラビング耐性の評価、プレチルト角の測定、初期電圧保持率（ＶＨＲ）の測定評価、並びにＵＶ照射後の電圧保持率の測定評価は、以下のように行った。 [Preparation of liquid crystal alignment treatment agent and various evaluations]
In Examples 1 to 16 and Comparative Examples 1 to 3, preparation of each liquid crystal alignment treatment agent, preparation of each liquid crystal alignment film using the liquid crystal alignment treatment agent, evaluation of rubbing resistance of the obtained liquid crystal alignment film, The production of each liquid crystal cell having the liquid crystal alignment film and the evaluation of each liquid crystal cell are shown.
The evaluation of the rubbing resistance of each liquid crystal cell obtained in Examples and Comparative Examples, the measurement of the pretilt angle, the measurement evaluation of the initial voltage holding ratio (VHR), and the measurement evaluation of the voltage holding ratio after UV irradiation are as follows. Went to.
［液晶配向処理剤の評価］
＜液晶セルの作製＞
　液晶配向処理剤を透明電極付きガラス基板（ミネルヴァ電子社製、縦×横＝４０ｍｍ×３０ｍｍ、厚さ１．１ｍｍ）にスピンコートし、８０℃のホットプレート上で７０秒間乾燥させた後、２５０℃のホットプレート上で１０分間焼成を行い、膜厚１００ｎｍの塗膜を形成した。この塗膜面をロール径１２０ｍｍのラビング装置でレーヨン布を用いて、ロール回転数１０００ｒｐｍ、ロール進行速度５０ｍｍ／ｓｅｃ、押し込み量０．３ｍｍの条件でラビングし、液晶配向膜付き基板を得た。液晶配向膜付き基板を２枚用意し、その１枚の液晶配向膜面上に６μｍのスペーサー（日揮触媒化成社製、ＡＷ－ＩＩ６．０）を散布した後、その上からシール剤を印刷し、もう１枚の基板を液晶配向膜面が向き合いラビング方向が直行するようにして張り合わせた後、シール剤を硬化させて空セルを作製した。この空セルに減圧注入法によって、液晶ＭＬＣ－２００３（Ｃ０８０）（メルク社製）を注入し、注入口を封止して、ツイストネマティック液晶セルを得た。 [Evaluation of liquid crystal aligning agent]
<Production of liquid crystal cell>
The liquid crystal aligning agent was spin-coated on a glass substrate with a transparent electrode (Minelva Electronics, length × width = 40 mm × 30 mm, thickness 1.1 mm), dried on an 80 ° C. hot plate for 70 seconds, and then 250 Baking was performed for 10 minutes on a hot plate at 0 ° C. to form a coating film having a thickness of 100 nm. 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. Prepare two substrates with a liquid crystal alignment film, spray a 6μm spacer (manufactured by JGC Catalysts & Chemicals, AW-II 6.0) on the surface of one liquid crystal alignment film, and then print a sealant on it. Then, 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 this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain a twisted nematic liquid crystal cell.
＜ラビング耐性の評価＞
　下記の＜液晶セルの作製＞に記載の方法で液晶配向膜付き基板を作製する際、ラビング条件の押し込み量を０．５ｍｍに変更して行い、ラビング耐性評価用の液晶配向膜を作製し、表面を共焦点レーザー顕微鏡（レーザーテック社製、１ＬＭ２１Ｄ）にて観察し、下記の評価を行った。
　○：削れカスやラビング傷が観察されない。
　×：膜が剥離する又は目視でラビング傷が観察される。
＜プレチルト角の測定＞
　下記の＜液晶セルの作製＞に記載の方法で作製したツイストネマティック液晶セルのプレチルト角（°）は、Ａｘｏ　Ｍｅｔｒｉｘ社製の「Ａｘｏ　Ｓｃａｎ」にて、ミュラーマトリクス法を用いて測定した。 <Evaluation of rubbing resistance>
When producing a substrate with a liquid crystal alignment film by the method described in <Preparation of liquid crystal cell> below, the amount of rubbing conditions is changed to 0.5 mm, and a liquid crystal alignment film for rubbing resistance evaluation is produced. The surface was observed with a confocal laser microscope (manufactured by Lasertec, 1LM21D), and the following evaluation was performed.
○: Scraping and rubbing scratches are not observed.
X: A film | membrane peels or a rubbing damage | wound is observed visually.
<Measurement of pretilt angle>
The 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.
＜初期電圧保持率（ＶＨＲ）の測定＞
　下記方法で作製したツイストネマティック液晶セルの電圧保持率の測定は、６０℃の温度下で４Ｖの電圧を６０μｓ間印加し、１６．６７ｍｓｅｃ後の電圧を測定し、電圧がどのくらい保持できているかを電圧保持率（％）として計算した。なお、電圧保持率の測定には東陽テクニカ社製のＶＨＲ－１電圧保持率測定装置を使用した。 <Measurement of initial voltage holding ratio (VHR)>
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 μs 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照射＞
　下記の＜液晶セルの作製＞に記載の方法で作製したツイストネマティック液晶セルに、セン特殊光源社製、卓上用ＵＶ硬化装置ＨＣＴ３Ｂ２８ＨＥＸ－１を用いて、光照射を８３ｓｅｃ行った。そのとき、照度を、照度計（ＣＲＣ社製ＵＶ　Light　MEASUREMODEL　UV－M02）を用い、ＵＶ－３５のセンサーを用い測定すると、照度が６０．０ｍＷ／ｃｍ２であった。
＜ＵＶ照射後の電圧保持率（ＶＨＲ）の測定＞
　上記の＜ＵＶ照射＞の方法で処理したツイストネマティック液晶セルの電圧保持率の測定は、６０℃の温度下で４Ｖの電圧を６０μｓ間印加し、１６．６７ｍｓｅｃ後の電圧を測定し、電圧がどのくらい保持できているかを電圧保持率（％）として計算した。なお、電圧保持率の測定には東陽テクニカ社製のＶＨＲ－１電圧保持率測定装置を使用した。 <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 .
<Measurement of voltage holding ratio (VHR) 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 μs 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.
（実施例１）
　ポリマー溶液Ｐ－１の樹脂１００重量部に対して、特定化合物の添加量が２重量部になるように、チバ・ジャパン社製ヒドロキシフェニルトリアジン系紫外線吸収剤チヌビン（R）４００を加え、室温で１時間攪拌し、液晶配向処理剤を得た。この液晶配向処理剤を用いて、以下の方法でラビング耐性を評価したところ、ラビングカス、傷の付着は見られなかった。さらに以下の方法で液晶セルを作成し、プレチルト角、ＶＨＲ、ＵＶ照射後のＶＨＲを測定したところ、特定化合物を加えない液晶配向材と比較して、ＵＶ照射後のＶＨＲが高いことが判明した。結果を表１に示す。 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.
Figure JPOXMLDOC01-appb-T000016
Figure JPOXMLDOC01-appb-T000016
（実施例２）
　ポリマー溶液Ｐ－１の樹脂１００重量部に対して、特定化合物の添加量が５重量部になるように、チバ・ジャパン社製ヒドロキシフェニルトリアジン系紫外線吸収剤チヌビン（R）４００を加え、室温で１時間攪拌し、液晶配向処理剤を得た。この液晶配向処理剤を用いて、実施例１と同様の方法で液晶セルの作製し同様の評価を行った。結果を表１に示す。特定化合物を加えることでＵＶ照射後のＶＨＲが高くなり、プレチルト角も高くなった。 (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.
（実施例３）
　ポリマー溶液Ｐ－１の樹脂１００重量部に対して、特定化合物の添加量が１０重量部になるように、チバ・ジャパン社製ヒドロキシフェニルトリアジン系紫外線吸収剤チヌビン（R）４００を加え、室温で１時間攪拌し、液晶配向処理剤を得た。この液晶配向処理剤を用いて、実施例１と同様の方法で液晶セルの作製し同様の評価を行った。結果を表１に示す。特定化合物を加えることでＵＶ照射後のＶＨＲが高くなり、プレチルト角も高くなった。 (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.
（実施例４）
　ポリマー溶液Ｐ－１の樹脂１００重量部に対して、特定化合物の添加量が２重量部になるように、チバ・ジャパン社製ヒドロキシフェニルトリアジン系紫外線吸収剤チヌビ（R）４７９を加え、室温で１時間攪拌し、液晶配向処理剤を得た。この液晶配向処理剤を用いて、実施例１と同様の方法で液晶セルの作製し同様の評価を行った。結果を表１に示す。特定化合物を加えることでＵＶ照射後のＶＨＲが高くなった。 (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.
（実施例５）
　ポリマー溶液Ｐ－１の樹脂１００重量部に対して、特定化合物の添加量が５重量部になるように、チバ・ジャパン社製ヒドロキシフェニルトリアジン系紫外線吸収剤チヌビ（R）４７９を加え、室温で１時間攪拌し、液晶配向処理剤を得た。この液晶配向処理剤を用いて、実施例１と同様の方法で液晶セルの作製し同様の評価を行った。結果を表１に示す。特定化合物を加えることでＵＶ照射後のＶＨＲが高くなり、プレチルト角も高くなった。 (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.
（実施例６）
　ポリマー溶液Ｐ－１の樹脂１００重量部に対して、特定化合物の添加量が10重量部になるように、チバ・ジャパン社製ヒドロキシフェニルトリアジン系紫外線吸収剤チヌビン（R）４７９を加え、室温で１時間攪拌し、液晶配向処理剤を得た。この液晶配向処理剤を用いて、実施例１と同様の方法で液晶セルの作製し同様の評価を行った。結果を表１に示す。特定化合物を加えることでＵＶ照射後のＶＨＲが高くなり、プレチルト角も高くなった。 (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.
（実施例７）
　ポリマー溶液Ｐ－１の樹脂１００重量部に対して、特定化合物の添加量が１重量部になるように、チバ・ジャパン社製ヒドロキシフェニルトリアジン系紫外線吸収剤チヌビン（R）１５７７ＥＤを加え、室温で１時間攪拌し、液晶配向処理剤を得た。この液晶配向処理剤を用いて、実施例１と同様の方法で液晶セルの作製し同様の評価を行った。結果を表１に示す。特定化合物を加えることでＵＶ照射後のＶＨＲが高くなった。 (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.
（実施例８）
　ポリマー溶液Ｐ－２の樹脂１００重量部に対して、特定化合物の添加量が5重量部になるように、チバ・ジャパン社製ヒドロキシフェニルトリアジン系紫外線吸収剤チヌビン（R）４００を加え、室温で１時間攪拌し、液晶配向処理剤を得た。この液晶配向処理剤を用いて、実施例１と同様の方法で液晶セルの作製し同様の評価を行った。結果を表１に示す。特定化合物を加えることでＵＶ照射後のＶＨＲが高くなり、プレチルト角も高くなった。 (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.
（実施例９）
　ポリマー溶液Ｐ－２の樹脂１００重量部に対して、特定化合物の添加量が５重量部になるように、チバ・ジャパン社製ヒドロキシフェニルトリアジン系紫外線吸収剤チヌビン（R）４７９を加え、室温で１時間攪拌し、液晶配向処理剤を得た。この液晶配向処理剤を用いて、実施例１と同様の方法で液晶セルの作製し同様の評価を行った。結果を表１に示す。特定化合物を加えることでＵＶ照射後のＶＨＲも高くなるが、プレチルト角も高くなった。 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.
（実施例１０）
　ポリマー溶液Ｐ－２の樹脂１００重量部に対して、特定化合物の添加量が１重量部になるように、チバ・ジャパン社製ヒドロキシフェニルトリアジン系紫外線吸収剤チヌビン（R）１５７７ＥＤを加え、室温で１時間攪拌し、液晶配向処理剤を得た。この液晶配向処理剤を用いて、実施例１と同様の方法で液晶セルの作製し同様の評価を行った。結果を表１に示す。特定化合物を加えることでＵＶ照射後のＶＨＲが高くなった。 (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.
（実施例１１）
　ポリマー溶液Ｐ－４の樹脂１００重量部に対して、特定化合物の添加量が５重量部になるように、チバ・ジャパン社製ヒドロキシフェニルトリアジン系紫外線吸収剤チヌビン（R）４００を加え、室温で１時間攪拌し、液晶配向処理剤を得た。この液晶配向処理剤を用いて、実施例１と同様の方法で液晶セルの作製し同様の評価を行った。結果を表１に示す。特定化合物を加えることでＵＶ照射後のＶＨＲが高くなった。 (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.
（実施例１２）
　ポリマー溶液Ｐ－４の樹脂１００重量部に対して、特定化合物の添加量が５重量部になるように、チバ・ジャパン社製ヒドロキシフェニルトリアジン系紫外線吸収剤チヌビン（R）４７９を加え、室温で１時間攪拌し、液晶配向処理剤を得た。この液晶配向処理剤を用いて、実施例１と同様の方法で液晶セルの作製し同様の評価を行った。結果を表１に示す。特定化合物を加えることでＵＶ照射後のＶＨＲが高くなった。 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.
（実施例１３）
　ポリマー溶液Ｐ－１を８０ｇ、ポリマー溶液Ｐ－５を２０g混合させ、室温にて２０時間攪拌した。このポリマー溶液の樹脂１００重量部に対して、特定化合物の添加量が５重量部になるように、チバ・ジャパン社製ヒドロキシフェニルトリアジン系紫外線吸収剤チヌビン（R）４７９を加え、室温で１時間攪拌し、液晶配向処理剤を得た。この液晶配向処理剤を用いて、実施例１と同様の方法で液晶セルの作製し同様の評価を行った。結果を表１に示す。特定化合物を加えることでＵＶ照射後のＶＨＲが高くなった。 (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.
（実施例１４）
　ポリマー溶液Ｐ－７の樹脂１００重量部に対して、特定化合物の添加量が１重量部になるように、チバ・ジャパン社製ヒドロキシフェニルトリアジン系紫外線吸収剤チヌビン（R）１５７７EDを加え、室温で１時間攪拌し、液晶配向処理剤を得た。この液晶配向材を用いて、実施例１と同様の方法で、プレチルトこの液晶配向処理剤を用いて、実施例１と同様の方法で液晶セルの作製し同様の評価を行った。結果を表１に示す。特定化合物を加えることでＵＶ照射後のＶＨＲが高くなった。 (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.
（実施例１５）
　ポリマー溶液Ｐ－６を２０ｇ、ポリマー溶液Ｐ－７を８０g混合させ、室温にて２０時間攪拌した。このポリマー溶液の樹脂１００重量部に対して、特定化合物の添加量が５重量部になるように、チバ・ジャパン社製ヒドロキシフェニルトリアジン系紫外線吸収剤チヌビン（R）４００を加え、室温で１時間攪拌し、液晶配向処理剤を得た。この液晶配向処理剤を用いて、実施例１と同様の方法で液晶セルの作製し同様の評価を行った。結果を表１に示す。特定化合物を加えることでＵＶ照射後のＶＨＲが高くなった。 (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.
（実施例１６）
　ポリマー溶液Ｐ－６を２０ｇ、ポリマー溶液Ｐ－７を８０g混合させ、室温にて２０時間攪拌した。このポリマー溶液の樹脂１００重量部に対して、特定化合物の添加量が５重量部になるように、チバ・ジャパン社製ヒドロキシフェニルトリアジン系紫外線吸収剤チヌビン（R）４７９を加え、室温で１時間攪拌し、液晶配向処理剤を得た。この液晶配向処理剤を用いて、実施例１と同様の方法で液晶セルの作製し同様の評価を行った。結果を表１に示す。特定化合物を加えることでＵＶ照射後のＶＨＲが高くなった。 (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.
（比較例１）
　ポリマー溶液Ｐ－１を液晶配向処理剤として用いて、実施例１と同様の方法で液晶セルの作製し同様の評価を行った。結果を表１に示す。ＵＶ照射後のＶＨＲは、特定化合物を加えた系と比較すると低かった。 (Comparative 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.
（比較例２）
　ポリマー溶液Ｐ-１の樹脂１００重量部に対して、添加量が５重量部になるように、城北化学工業社製ベンゾトリアゾール系紫外線吸収剤ＪＦ-８３を加え、室温で１時間攪拌し、液晶配向処理剤を得た。この液晶配向処理剤を用いて、実施例１と同様の方法で液晶セルの作製し同様の評価を行った。結果を表１に示す。初期のＶＨＲ、ＵＶ照射後のＶＨＲともに低かった。 (Comparative 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.
（比較例３）
　ポリマー溶液Ｐ-３を液晶配向処理剤として用いて、実施例１と同様の方法で、プレチルト角、ラビング耐性、ＶＨＲ、ＵＶ照射後のＶＨＲを評価した。結果を表１に示す。ラビング耐性が悪く、ＶＨＲも本発明の特定化合物よりも低かった。 (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.
　本発明の液晶配向処理剤は、光耐性特性、ラビング耐性特性等を有し、さらに液晶セル内のイオン量を大きく増大しない効果を有する液晶配向膜の形成が可能であり、得られた液晶配向膜は、ＴＮ素子、ＳＴＮ素子、ＴＦＴ液晶素子、更には、垂直配向型の液晶表示素子などとして産業上、有用である。
　なお、２０１１年１１月２９日に出願された日本特許出願２０１１－２６０１７９号の明細書、特許請求の範囲、及び要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。 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.
The entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2011-260179 filed on November 29, 2011 are incorporated herein as the disclosure of the specification of the present invention. Is.

Claims (9)

  1. 　一般式（１）で表される化合物を含有することを特徴とする液晶配向処理剤。
    Figure JPOXMLDOC01-appb-C000001
     （式中、Ｒ1～Ｒ14は、それぞれ独立して、水素原子、又は二価の有機基であり、かつＲ1～Ｒ14のうちいずれか一つ以上は、炭素数４以上のアルキル基を含む有機基である。）     A liquid crystal aligning agent comprising a compound represented by the general formula (1).
    Figure JPOXMLDOC01-appb-C000001
     (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. 　前記式（１）で表される化合物と、ポリイミド前駆体及び該ポリイミド前駆体をイミド化したポリイミドからなる群より選ばれる少なくとも１種のポリマーとを含有する請求項１に記載の液晶配向処理剤。 The liquid crystal aligning agent of Claim 1 containing the compound represented by the said Formula (1), and the at least 1 sort (s) of polymer chosen from the group which consists of a polyimide precursor and the polyimide which imidated this polyimide precursor. .
  3. 　前記式（１）で表される化合物の含有量が、前記ポリイミド前駆体及び該ポリイミド前駆体をイミド化したポリイミドからなる群より選ばれる少なくとも１種のポリマーの量１００重量部に対して、０．５～１０重量部である請求項１又は請求項２に記載の液晶配向処理剤。 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 liquid crystal aligning agent according to claim 1 or 2, wherein the amount is from 5 to 10 parts by weight.
  4. 　前記ポリイミド前駆体及び該ポリイミド前駆体をイミド化したポリイミドからなる群より選ばれる少なくとも１種のポリマーの重量平均分子量が、１０，０００～１５０，０００である請求項１～３のいずれか一項に記載の液晶配向処理剤。 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 as described in.
  5. 　液晶配向処理剤中に９２～９９重量％の有機溶媒を含有する請求項１～４のいずれか一項に記載の液晶配向処理剤。 The liquid crystal aligning agent according to any one of claims 1 to 4, wherein the liquid crystal aligning agent contains 92 to 99% by weight of an organic solvent.
  6. 　前記有機溶媒が、５～８０重量％の貧溶媒を含有する請求項５に記載の液晶配向処理剤。 The liquid crystal aligning agent according to claim 5, wherein the organic solvent contains 5 to 80% by weight of a poor solvent.
  7. 　請求項１～６のいずれか一項に記載の液晶配向処理剤から得られる液晶配向膜。 A liquid crystal alignment film obtained from the liquid crystal alignment treatment agent according to any one of claims 1 to 6.
  8. 　膜厚が、１０～２００μｍである請求項７に記載の液晶配向膜。 The liquid crystal alignment film according to claim 7, wherein the film thickness is 10 to 200 μm.
  9. 　請求項７又は８に記載の液晶配向膜を具備する液晶表示素子。 A liquid crystal display device comprising the liquid crystal alignment film according to claim 7 or 8.
PCT/JP2012/080975 2011-11-29 2012-11-29 Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element using same WO2013081064A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2013547215A JP6206187B2 (en) 2011-11-29 2012-11-29 Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element using the same
CN201280058354.0A CN103959153B (en) 2011-11-29 2012-11-29 Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element using same
KR1020147014360A KR102044049B1 (en) 2011-11-29 2012-11-29 Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element using same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011260179 2011-11-29
JP2011-260179 2011-11-29

Publications (1)

Publication Number Publication Date
WO2013081064A1 true WO2013081064A1 (en) 2013-06-06

Family

ID=48535512

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/080975 WO2013081064A1 (en) 2011-11-29 2012-11-29 Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element using same

Country Status (5)

Country Link
JP (1) JP6206187B2 (en)
KR (1) KR102044049B1 (en)
CN (1) CN103959153B (en)
TW (1) TWI596157B (en)
WO (1) WO2013081064A1 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015046373A1 (en) * 2013-09-26 2015-04-02 日産化学工業株式会社 Liquid crystal aligning agent and liquid crystal display element using same
WO2015046374A1 (en) * 2013-09-26 2015-04-02 日産化学工業株式会社 Liquid crystal aligning agent and liquid crystal display element using same
WO2017115818A1 (en) * 2015-12-28 2017-07-06 宇部興産株式会社 Polyimide material, method for producing same, and polyimide precursor composition used for production of same
WO2019073970A1 (en) * 2017-10-11 2019-04-18 株式会社カネカ Polyimide resin composition, and polyimide film and production method therefor
EP3550357A4 (en) * 2016-11-29 2020-07-08 Boe Technology Group Co. Ltd. Alignment material composition and liquid crystal display panel and preparation methods therefor and display device using same

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111574467B (en) * 2020-06-12 2021-11-30 江苏三月科技股份有限公司 Polyamine-based compound and preparation method and application thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100197186A1 (en) * 2009-02-03 2010-08-05 Samsung Electronics Co., Ltd. Photoalignment material and method of manufacturing display substrate using the same

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56116012A (en) 1980-02-19 1981-09-11 Sharp Corp Liquid-crystal cell
JPS5784429A (en) 1980-11-14 1982-05-26 Casio Comput Co Ltd Liquid crystal display device
JPS57108828A (en) 1980-12-25 1982-07-07 Casio Comput Co Ltd Displaying device of guest-host type liquid crystal
JPH10148835A (en) 1996-11-19 1998-06-02 Hitachi Chem Co Ltd Liquid crystal alignment layer
KR20010024326A (en) * 1998-07-29 2001-03-26 고토 기치 Novel diamino compounds, polyamic acid, polyimide, liquid-crystal alignment film made from film of the polyimide, and liquid-crystal display element containing the alignment film
JP2003215592A (en) 2002-01-25 2003-07-30 Seiko Epson Corp Liquid crystal panel and liquid crystal display device
JP2004053685A (en) 2002-07-16 2004-02-19 Seiko Epson Corp Liquid crystal panel and liquid crystal display device
KR101450923B1 (en) * 2007-03-19 2014-10-14 제이에스알 가부시끼가이샤 Liquid crystal aligning agent and liquid crystal display
TWI490207B (en) * 2008-01-25 2015-07-01 Nissan Chemical Ind Ltd A diamine compound, a liquid crystal alignment treatment agent, and a liquid crystal display device using the same
KR101059138B1 (en) * 2008-03-21 2011-08-25 짓쏘 세끼유 가가꾸 가부시키가이샤 Photoaligning agent, a liquid crystal aligning film, the liquid crystal display element using this, and the manufacturing method of a liquid crystal aligning film
JP5609483B2 (en) 2009-11-18 2014-10-22 Jnc株式会社 Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100197186A1 (en) * 2009-02-03 2010-08-05 Samsung Electronics Co., Ltd. Photoalignment material and method of manufacturing display substrate using the same

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102250028B1 (en) 2013-09-26 2021-05-10 닛산 가가쿠 가부시키가이샤 Liquid crystal aligning agent and liquid crystal display element using same
WO2015046374A1 (en) * 2013-09-26 2015-04-02 日産化学工業株式会社 Liquid crystal aligning agent and liquid crystal display element using same
KR20160060732A (en) * 2013-09-26 2016-05-30 닛산 가가쿠 고교 가부시키 가이샤 Liquid crystal aligning agent and liquid crystal display element using same
KR20160060733A (en) * 2013-09-26 2016-05-30 닛산 가가쿠 고교 가부시키 가이샤 Liquid crystal aligning agent and liquid crystal display element using same
CN105765452A (en) * 2013-09-26 2016-07-13 日产化学工业株式会社 Liquid crystal aligning agent and liquid crystal display element using same
CN105765453A (en) * 2013-09-26 2016-07-13 日产化学工业株式会社 Liquid crystal aligning agent and liquid crystal display element using same
JPWO2015046374A1 (en) * 2013-09-26 2017-03-09 日産化学工業株式会社 Liquid crystal aligning agent and liquid crystal display device using the same
JPWO2015046373A1 (en) * 2013-09-26 2017-03-09 日産化学工業株式会社 Liquid crystal alignment treatment agent and liquid crystal display element using the same
WO2015046373A1 (en) * 2013-09-26 2015-04-02 日産化学工業株式会社 Liquid crystal aligning agent and liquid crystal display element using same
KR102255769B1 (en) 2013-09-26 2021-05-27 닛산 가가쿠 가부시키가이샤 Liquid crystal aligning agent and liquid crystal display element using same
CN105765453B (en) * 2013-09-26 2019-04-12 日产化学工业株式会社 Aligning agent for liquid crystal and the liquid crystal expression element for having used it
CN105765452B (en) * 2013-09-26 2019-04-12 日产化学工业株式会社 Aligning agent for liquid crystal and the liquid crystal expression element for having used it
WO2017115818A1 (en) * 2015-12-28 2017-07-06 宇部興産株式会社 Polyimide material, method for producing same, and polyimide precursor composition used for production of same
JPWO2017115818A1 (en) * 2015-12-28 2018-12-13 宇部興産株式会社 Polyimide material, method for producing the same, and polyimide precursor composition used for the production
JP7262924B2 (en) 2015-12-28 2023-04-24 Ｕｂｅ株式会社 Polyimide material, method for producing the same, and polyimide precursor composition used for producing the same
EP3550357A4 (en) * 2016-11-29 2020-07-08 Boe Technology Group Co. Ltd. Alignment material composition and liquid crystal display panel and preparation methods therefor and display device using same
WO2019073970A1 (en) * 2017-10-11 2019-04-18 株式会社カネカ Polyimide resin composition, and polyimide film and production method therefor

Also Published As

Publication number Publication date
TW201339245A (en) 2013-10-01
KR20140099460A (en) 2014-08-12
JPWO2013081064A1 (en) 2015-04-27
TWI596157B (en) 2017-08-21
JP6206187B2 (en) 2017-10-04
CN103959153A (en) 2014-07-30
CN103959153B (en) 2017-04-12
KR102044049B1 (en) 2019-11-12

Similar Documents

Publication Publication Date Title
JP6152914B2 (en) Novel dicarboxylic acid anhydride and process for producing the same
WO2009093709A1 (en) Liquid-crystal alignment material, liquid-crystal alignment film, and liquid-crystal display element
JP6083388B2 (en) Method for producing liquid crystal aligning agent
JP6206187B2 (en) Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element using the same
JP5900328B2 (en) Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element using the same
WO2013115228A1 (en) Novel diamine, polymer, liquid crystal alignment agent, and liquid crystal alignment film, and liquid crystal display element using same
KR20150068445A (en) Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
JP6065074B2 (en) Diamine compounds, polyimide precursors and polyimides
JP6146576B2 (en) Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element using the same
WO2018043326A1 (en) Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
WO2018043325A1 (en) Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element using same
JP6330662B2 (en) Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
WO2014092170A1 (en) Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
JP6056754B2 (en) Liquid crystal alignment treatment agent and liquid crystal display element using the same
JP6384663B2 (en) Polymer, liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12853722

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2013547215

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 20147014360

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12853722

Country of ref document: EP

Kind code of ref document: A1