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WO2008010528A1 - agent d'orientation de cristaux liquides, film orienté de cristaux liquides et élément d'affichage à cristaux liquides L'utilisant - Google Patents

agent d'orientation de cristaux liquides, film orienté de cristaux liquides et élément d'affichage à cristaux liquides L'utilisant Download PDF

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Publication number
WO2008010528A1
WO2008010528A1 PCT/JP2007/064207 JP2007064207W WO2008010528A1 WO 2008010528 A1 WO2008010528 A1 WO 2008010528A1 JP 2007064207 W JP2007064207 W JP 2007064207W WO 2008010528 A1 WO2008010528 A1 WO 2008010528A1
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WO
WIPO (PCT)
Prior art keywords
amine compound
liquid crystal
solvent
formula
mass
Prior art date
Application number
PCT/JP2007/064207
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English (en)
Japanese (ja)
Inventor
Kimiaki Tsutsui
Hirobumi Shida
Mariko Yamada
Kosuke Takazawa
Original Assignee
Nissan Chemical Industries, Ltd.
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 Nissan Chemical Industries, Ltd. filed Critical Nissan Chemical Industries, Ltd.
Priority to JP2008525889A priority Critical patent/JP5428336B2/ja
Priority to CN2007800270738A priority patent/CN101490188B/zh
Priority to KR1020097000976A priority patent/KR101426100B1/ko
Publication of WO2008010528A1 publication Critical patent/WO2008010528A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents
    • C08G73/1017—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents in the form of (mono)amine
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723—Polyimide, polyamide-imide

Definitions

  • the present invention relates to a coating liquid suitable as a liquid crystal aligning agent, and further relates to a liquid crystal alignment film and a liquid crystal display element obtained using this coating liquid.
  • a liquid crystal alignment film used in a liquid crystal display element or the like is generally made of polyimide, and is usually manufactured by applying a solution called a liquid crystal alignment agent and baking it. Yes.
  • the liquid crystal aligning agent is generally a solution containing a polyimide precursor such as polyamic acid or a solvent-soluble polyimide, but contains both a polyamic acid and a solvent-soluble polyimide (see Patent Document 1).
  • polyamic acids and those containing two or more types of imidopolymers having different imidication ratios obtained by dehydrating and ring-closing polyamic acids see Patent Document 2.
  • the liquid crystal aligning power which contains several kinds of resin components
  • the obtained liquid crystal aligning film has several required properties such as liquid crystal orientation, liquid crystal pretilt angle, and various electric characteristics of the liquid crystal cell. It is known that can be realized simultaneously.
  • Patent Document 1 Japanese Patent Laid-Open No. 8-220541
  • Patent Document 2 Japanese Patent Laid-Open No. 9-2937312
  • Patent Document 3 International Publication No. 2004Z090016 pamphlet
  • the problem to be solved by the present invention is to improve the stability during moisture absorption with respect to a coating solution containing both a polyamic acid and an imidized polymer soluble in a solvent.
  • An object of the present invention is to provide a coating liquid suitable as a liquid crystal aligning agent, to provide a high-quality liquid crystal alignment film, and to provide a high-quality liquid crystal display element.
  • the present inventors have made a specific amine compound react with a solvent-soluble polyimide, or a raw material for producing a solvent-soluble polyimide. It has been found that the use of a specific amine compound improves the hygroscopic stability of the mixed solution with the polyamic acid, and the present invention has been completed. That is, the present invention has the following features.
  • a coating solution comprising: an imidized polymer that is soluble in the obtained solvent and at least one selected amine compound strength; and (B) component: polyamic acid.
  • Amine compound (a) In the molecule, at least one primary amino group selected from formula [K1] and formula [K2] and at least an imino group selected from formula [K3] and formula [K4] One amine compound.
  • the bonding direction of —CH—NH— is opposite.
  • Amine compound (b) an amine compound having at least two primary amino groups selected from the above formulas [K1] and [K2] in the molecule.
  • the component (A) is composed of at least one of a side chain and a molecular end of a solvent-soluble polyimide obtained by the ability of a tetracarboxylic dianhydride and a diamine compound, and the amine compound (a) and The coating solution according to the above (1), which is an imidized polymer soluble in a solvent obtained by binding an amine compound (b) with at least one amine compound that also has a selected force.
  • the component (A) is at least one selected from the amine compound (a) and the amine compound (b) as a solvent-soluble polyimide obtained by combining tetracarboxylic dianhydride and diamine compound.
  • the component (A) is a solvent-soluble imido compound obtained by imidizing a polyimide precursor obtained by reacting a tetracarboxylic dianhydride with a diamine compound containing an amine compound (c).
  • the component (A) is a solvent obtained by using, as the amine compound (a), at least one amine compound selected from amine compounds represented by the following formulas (i) and (ii):
  • the coating solution according to the above (1) which is an imidized polymer soluble in water.
  • R 1 in the formula is CH CH (CH) or one CH (CH CH) —
  • X 1 represents a single bond or an aliphatic hydrocarbon having 120 carbon atoms
  • —NH 2 may be contained in the aliphatic hydrocarbon.
  • X 2 represents an organic group having 120 carbon atoms, an alkyl group having 120 carbon atoms, and a cyclic aliphatic group.
  • Organic group consisting of a group, aromatic group, heterocyclic group, carboxyl group and combinations thereof, and unsaturated bond, ether bond (one O), ketone bond (one CO), ester bond (one COO), An amino bond (one NH 3), an amine bond (one N), a silyl bond (one Si—), a siloxane bond (SiO 2), and the like may be included. Furthermore, even if the alkyl group of X 2 forms a heterocyclic structure with any of —R 1 , X 1 —, —CH 1, and NH
  • the component (A) is at least one amine compound selected from amine compounds represented by the following formulas (m) to (V) as the amine compound (b):
  • R 1 in the formula is CH —, one CH (CH 2) one, or one CH (CH 2 CH 2) —
  • X 3 represents a single bond or an organic group having 1 to 20 carbon atoms, an alkylene group having 1 to 20 carbon atoms, an aliphatic ring, an aromatic ring, a heterocyclic ring, and an organic group having a combination force thereof, and , Unsaturated bond, ether bond (one 0—), ketone bond (one CO), ester bond (COO), thioether bond (one S), silyl bond (one Si—), siloxane bond (one SiO), etc. May be included.
  • x 4 , x 5 , X 6 , X 7 and X 8 each independently represent an aliphatic hydrocarbon having 1 to 20 carbon atoms, and may be the same or different.
  • the component (A) is at least one amine compound selected from amine compounds represented by the following formulas (i), (ii), Gv) and (V) as the amine compound (c):
  • Ratio power of imidized polymer of component (A) and polyamic acid of component (B) In the total mass of component (A) and component (B), the ratio of polyamic acid of component (B) is The coating solution according to any one of (1), (2), and (4) to (7), which is 20 to 99% by mass.
  • the component (A) is composed of tetracarboxylic dianhydride and diamine compound, and the solvent-soluble polyimide obtained is 100 parts by mass with respect to the amine compound (a) and amine compound (b).
  • the coating liquid according to (3) above which is a product obtained by reacting 1 to 15 parts by mass of at least one amine compound selected from
  • the component (A) is soluble in a solvent obtained by imidizing a polyimide precursor obtained by reacting a tetracarboxylic dianhydride and a diamine containing the amine compound (c) represented above.
  • a liquid crystal aligning agent comprising the coating liquid according to any one of (1) to (10) above.
  • the coating liquid of the present invention precipitation of the resin component due to moisture absorption is suppressed, stable printability can be obtained, and it can be suitably used as a liquid crystal aligning agent.
  • the coating of the present invention Since the liquid crystal alignment film obtained using the cloth liquid has improved rubbing resistance and improved ease of stored charge release, a liquid crystal display element of higher quality than before can be obtained.
  • FIG. 1 is a graph showing a comparison of the ease of escape of accumulated charges in a liquid crystal cell using a liquid crystal aligning agent having a coating solution force of Example 4 or Comparative Example 1.
  • the solvent-soluble imidized polymer component is particularly suitable for forming a liquid crystal alignment film at a low firing temperature.
  • the polyamic acid component contributes to printability, adhesion to the substrate, reduction of charge accumulation and ease of charge removal when used as a liquid crystal alignment film.
  • the concentration of soluble polyimide and polyamic acid in the film thickness direction has a gradient, which makes it difficult to obtain with a single resin component.
  • the liquid crystal aligning agent staying on the printing press is concentrated by volatilization of the solvent and further absorbs moisture as described above.
  • the aggregation and precipitation of the fat component is thought to be one of the causes of printing defects. Therefore, the present inventors have moderately suppressed this phase separation by the action of a specific amine compound, so that the advantage of containing both the solvent-soluble polyimide and the polyamic acid is not lost. As a result, the present invention has been completed.
  • the present invention relates to a solvent obtained from tetracarboxylic dianhydride, diamine compound, and an amine compound (a) and amine compound (b) represented by the following formula:
  • a preferred embodiment of the component (A) is that the solvent-soluble polyimide obtained from tetracarboxylic dianhydride and a diamine compound includes a specific amine compound (a) and an amine compound.
  • the following amine compound (a) and amine compound (b) are added to ⁇ 1 ⁇ solvent-soluble polyimide.
  • a force that contains an imidized polymer that is soluble in a solvent which is a product obtained by reacting at least one selected amine compound, and a polyamic acid, or ⁇ 2 ⁇ tetracarboxylic acid It contains a polyimide precursor soluble in a solvent obtained by imidizing a polyimide precursor obtained by reacting an anhydride with a diamine containing the following amine compound (c), and a polyamic acid.
  • the polyamic acid is the same.
  • the amine compound (a) has one primary amino group selected from the formula [K1] and formula [K2] and an imino group selected from the formula [K3] and formula [K4] in the molecule.
  • Amine compound (b) is an amine compound having at least two primary amino groups selected from the formulas [K1] and [K2] in the molecule.
  • the amine compound (c) has at least one primary amino group having the formula [K1] and formula [K2] forces selected in the molecule and an imino group selected from the formula [K3] and formula [K4]. It is an amine compound with at least one.
  • the amine compound (c) is the same as the amine compound (a) when it has one primary amino group represented by the formula [K1] or the formula [K2]. And having at least two primary amino groups selected from the formulas [K1] and [K2] are compounds contained in the amine compound (b).
  • the amine compound (a) has the following formula —I ⁇ NH (R 1 is CH —, —CH (CH
  • amine compound having at least one imino group represented by —R 2 —NH—R 3 — (R 2 and R 3 are divalent organic groups, at least one of which is methylene).
  • the amine compound (b) is represented by the following formula: —I ⁇ —NH (R 1 is —CH—, —CH
  • the amine compound (c) has the following formula —I ⁇ —NH (R 1 is —CH—, —C
  • the coating solution of ⁇ 1 ⁇ a predetermined amount of the amine compound (a) or amine compound (b) is added to a polyimide solution, and the solution is heated at room temperature or under heating conditions. It is a solution obtained by mixing the imidyl polymer soluble in the solvent of the reaction product obtained by stirring and the polyamic acid solution in an arbitrary ratio.
  • the specific amine compound (a) and amine compound (b) used in the present invention have at least two action points. One is a site chemically bonded to the solvent-soluble polyimide, and the other is a site that forms a hydrogen bond or salt formation with the polyamic acid. This improves the compatibility between the imidopolymer and polyamic acid that are soluble in the solvent reacted with the specific amine compound, and suppresses phase separation when the coating solution is concentrated.
  • the primary amino group represented by the formula [K1] and the formula [K2] is an aliphatic amino group
  • the imide carbonyl group in the polyimide is When the imidization ratio of the polyimide is less than 100% as described later, in addition to the reaction described above, the carboxyl group or amic acid ester group of the amic acid group It binds to the carboxyester group by a reaction involving elimination of water or alcohol.
  • R 1 represents one CH CH (CH) CH (CH CH)
  • Aliphatic rings include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, and cyclododecane.
  • R 1 of this amino group is most preferably methylene because it increases the nucleophilicity of the amino group and has less steric hindrance.
  • aliphatic rings cyclopropane, cyclobutane, cyclopentane, cyclohexane and the like are preferable.
  • the imino group acts with the carboxyl group in polyamic acid, such as hydrogen bonding and salt formation.
  • amine compound (a) In the amine compound (a), it is represented by —CH—NH or NH—CH—.
  • One or more imino groups may be contained, but 1 to 4 is suitable from the viewpoint of availability and stability of the compound, and 1 to 2 is particularly preferable.
  • the imino group represented by —R 2 —NH—R 3 contained in the amine compound (a) described above has a function of forming a hydrogen bond or salt formation with the carboxyl group in the polyamic acid. . Therefore, R 2 and R 3 of this imino group need to have at least one of R 2 and R 3 methylene because it is necessary to give the nitrogen atom of the imino group a certain electron density.
  • structures of the other is not particularly limited, for example, exemplified in R 1 - CH -, - CH (CH) -, - CH (CH CH) -, aliphatic ring, or off
  • both R 2 and R 3 are styrene.
  • the amine compound (a) it is sufficient that at least one imino group represented by R 2 —NH—R 3 is present, but 1 to 4 is appropriate from the viewpoint of availability and stability of the compound. There are 1 to 2 pieces, especially.
  • the amine compound (b) has at least two primary amino groups selected from the formulas [K1] and [K2].
  • the first primary amino group reacts with the solvent-soluble polyimide
  • the migration of the amine compound is suppressed, so the remaining amino group reacts with another solvent-soluble polyimide. It becomes difficult.
  • the amino group not reacting with the solvent-soluble polyimide has the same action as the imino group contained in the amine compound (a). It becomes.
  • the amine compound (b) there are 2 or more primary amino groups as described above, but 2 to 5 from the viewpoint of availability and stability of the compound. Is suitable, and 2 to 3 is particularly preferable.
  • the amine compound (b) further has one or more imino groups selected from the formulas [K3] and [K4] because the compatibility with the polyamic acid becomes higher.
  • This imino group is preferably an imino group represented by R 2 —NH—R 3 as in the amine compound (a).
  • the definitions of R 2 and R 3 are the same as in the amine compound (a).
  • the primary amino group reacts with tetracarboxylic dianhydride, so that the amine compound (c) is taken into the polyimide.
  • One or more amino groups may be contained in the molecule, but 1 to 5 is suitable from the viewpoint of availability and stability of the compound, and 1 to 2 is particularly preferable.
  • the amine compound (c) with one amino group is located at either the side chain or the terminal of the polymer molecule, it has less steric hindrance when it forms a hydrogen bond or salt with the polyamic acid. Most preferred for reasons. If the number of amino groups is 3 or more, the resulting soluble polyimide has a three-dimensional structure. When this coating solution is used as a liquid crystal alignment film, the reason for obtaining uniform orientation of the liquid crystal is preferred to have less branching of the main chain. Therefore, two or less amino groups are preferred.
  • This amino group is an amino group represented by R 1 —NH.
  • R 1 is the same as the amine compound (a).
  • the imino group selected from the formula [K3] and the formula [K4] contained in the amine compound (c) is the above-mentioned amine compound (a) with regard to its constitution, action and preferred form. It is the same as the imino group contained in. That - R 2 - NH-R 3 in the preferred instrument R 2 be an imino group represented,
  • R 3 is the same as in the amine compound (a).
  • amine compound (a) in the present invention for example, amine compounds represented by the following formulas (i) and (ii) can be exemplified.
  • R 1 is CH—, 1 CH (CH 2) —, or 1 CH (CH 2 CH 2) —
  • X 1 represents a single bond or a divalent organic group
  • specific examples of the divalent organic group include an alkylene, an aliphatic ring, an aromatic ring, Heterocycles and organic groups that combine these, and unsaturated bonds, ether bonds (one O—), ketone bonds (one CO), ester bonds (one COO), thioether bonds (one S— ), Amino bonds (one NH), amide bonds (one CONH), silyl bonds (one Si—), siloxane bonds (SiO 2), and the like.
  • X 2 is a monovalent organic group, and specific examples thereof include an alkyl group, an alkoxy group, a cycloaliphatic group, an aromatic group, a heterocyclic group, and an organic group having a combination force thereof.
  • Unsaturated bond, ether bond (one O), ketone bond (one CO), ester bond (one COO), thioether bond (one S), amino bond (one NH), amide bond (one CON H), silyl bond (One Si—), a siloxane bond (one SiO 2), and the like may be included.
  • X 2 is - R 1 -, - X 1 -, -CH-, and - double and one selected from NH
  • examples of the aliphatic ring or cycloaliphatic group include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, cyclododecane, adamantane, decahydronaphthalene, and norobornane.
  • examples of the aromatic ring or aromatic group include ring structures such as benzene and naphthalene.
  • heterocyclic ring or heterocyclic group examples include ring structures such as pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyrazole, pyrroline, pyrrolidine, pyridine, and pyrimidine.
  • alkyl group, alkoxy group, and alkylene examples include an alkyl group having 1 to 20 carbon atoms, an alkoxy group, and alkylene.
  • X 1 and X 2 may have a substituent! /.
  • substituents include alkyl Group, alkoxy group, hydroxyl group, carboxyl group, and the like.
  • amine compound (b) in the present invention for example, amine compounds represented by the following formulas (m) to (V) can be exemplified.
  • R 1 in the formula is CH—, 1 CH (CH 2) —, or 1 CH (CH 2 CH 2) —
  • X 3 , X 4 , X 5 , X 6 , X 7 and X 8 represent a single bond or a divalent organic group, and specific examples of the divalent organic group include alkylene, an aliphatic ring, Organic groups consisting of aromatic rings, heterocycles, and combinations of these include unsaturated bonds, ether bonds (one o-), ketone bonds (one CO), ester bonds (one COO), thioethers.
  • a bond (one S—), an amino bond (NH), an amide bond (one CONH), a silyl bond (one Si—), a siloxane bond (one SiO—), and the like may be included.
  • aliphatic ring or cycloaliphatic group cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, cyclododecane, adamantane, deca And ring structures such as hydronaphthalene and norobornane.
  • aromatic ring or aromatic group include ring structures such as benzene and naphthalene.
  • heterocyclic ring or heterocyclic group examples include ring structures such as pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyrazole, pyrroline, pyrrolidine, pyridine, and pyrimidine.
  • alkylene examples include alkylene having 1 to 20 carbon atoms.
  • X 3 , X 4 , X 5 , X 6 , X 7 and X 8 may have a substituent.
  • substituents include an alkyl group, an alkoxy group, a hydroxyl group, and a carboxyl group.
  • amine compound (c) in the present invention include amine compounds represented by the following formulas (i), (ii), (iv) and (V).
  • R 1 in the formula is CH—, 1 CH (CH 2) —, or 1 CH (CH 2 CH 2) —
  • X 1 , X 4 , X 5 , X 6 , X 7 and X 8 represent a single bond or a divalent organic group, and specific examples of the divalent organic group include alkylene, an aliphatic ring, Organic groups consisting of aromatic rings, heterocycles, and combinations of these include unsaturated bonds, ether bonds (one o-), ketone bonds (one CO), ester bonds (one COO), thioethers.
  • a bond (one S—), an amino bond (NH), an amide bond (one CONH), a silyl bond (one Si—), a siloxane bond (one SiO—), and the like may be included.
  • X 2 is a monovalent organic group, and specific examples thereof include an alkyl group, an alkoxy group, a cycloaliphatic group, an aromatic group, a heterocyclic group, and an organic group having a combination force thereof. Bond, ether bond (one O), ketone bond (one CO), ester bond (one COO), thioether bond (one S), amino bond (one NH), amide bond (one CON H), silyl bond (Si) , Including siloxane bonds (SiO 2), etc.
  • examples of the aliphatic ring or cycloaliphatic group include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, cyclododecane, adamantane, decahydronaphthalene, and norobornane.
  • examples of the aromatic ring or aromatic group include ring structures such as benzene and naphthalene.
  • heterocyclic ring or heterocyclic group examples include ring structures such as pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyrazole, pyrroline, pyrrolidine, pyridine, and pyrimidine.
  • alkyl group, alkoxy group, and alkylene examples include an alkyl group having 1 to 20 carbon atoms, an alkoxy group, and alkylene.
  • X 1 , X 4 , X 5 , X 6 , X 7 and X 8 may have a substituent! /.
  • substituent include an alkyl group, an alkoxy group, a hydroxyl group, and a carboxyl group.
  • the molecular weight of the compound is preferably 1000 or less. Preferably it is 500 or less, Especially preferably, it is 300 or less.
  • amine compound (a) or the amine compound (b) include the following, but are not limited thereto. Two or more amine compounds may be used in combination.
  • Specific examples of the amine compound (c) include No. 1 to No. 50, No. 71 to No. 76, No. 93 to N ⁇ .102, and ⁇ .106 to ⁇ .108. It is not limited to these. Two or more amine compounds may be used in combination.
  • the solvent-soluble polyimide and the imidyl polymer soluble in the solvent are polymers having an imide bond in the repeating unit, and an organic solvent. It refers to what can be dissolved.
  • a solvent-soluble polyimide used in the present invention and a solvent-soluble imide include those in which a part of the imide group contained in the repeating unit is ring-opened to form an amic acid group or an amic acid ester group. Included in the category of chemical polymers. Imi contained in polymers having these imide bonds The ratio of dodo groups can be expressed as an imidization rate as shown in the following formula.
  • Imide ratio number of imide groups ⁇ (number of imide groups + number of amide acid groups + number of amide acid ester groups) These imidation rates are determined by dissolving the polyimide in d-DMSO (dimethylsulfoxide d).
  • the imidation ratio of the solvent-soluble polyimide used in the coating solution of the present invention and the imidized polymer soluble in the solvent is not particularly limited. Usually, the higher the imidization rate, the lower the solubility of the polyimide in the solvent. As a result, if the solution cannot be dissolved at the required concentration, the imidization rate may be lowered appropriately. In view of the purpose of using a polymer that has been imidized in advance, the imidization rate is preferably 10% or more. In addition, when used as a liquid crystal aligning agent, the reason for obtaining good liquid crystal alignment or good electrical properties.
  • the imidity ratio is preferably 40% or more, more preferably 60% or more. Particularly preferably, it is 80% or more.
  • the molecular weight of the solvent-soluble polyimide and the solvent-soluble imidopolymer is not particularly limited, but it is 2 in terms of weight average molecular weight from the viewpoints of handling and stability of characteristics when a film is formed. 000 to 200,000 force, more preferably 4,000 to 50,000.
  • the molecular weight is determined by GPC (gel permeation chromatography).
  • the structure of the solvent-soluble polyimide used in the coating solution of ⁇ 1 ⁇ of the present invention is not particularly limited, but can be obtained relatively easily by using tetracarboxylic dianhydride and diamine as raw materials. For this reason, a polyimide having a repeating unit represented by the following formula (I) is preferred.
  • the imidized polymer soluble in the solvent used in the coating solution of ⁇ 2 ⁇ of the present invention is a reaction between tetraforce rubonic acid dianhydride and diamine containing an amine compound (c).
  • the force obtained by imidizing the polyimide precursor obtained is obtained using diamine as a main raw material, and the polyimide having a repeating unit represented by the following formula (I) is used as a basic structure in the same manner as ⁇ 1 ⁇ . Yes.
  • the imidized polymer soluble in the solvent used in the coating solution of ⁇ 1 ⁇ of the present invention is a specific amine polymer in a part of the polyimide having a repeating unit represented by the following formula (I).
  • the polyimide has a structure bonded to the imide carbonyl group by a reaction involving ring opening of the imide group, or the polyimide has an imido ratio of less than 100%, the carboxyl group or amide acid of the amide acid group It has a structure in which the ester group is bonded to the carboxyester group.
  • the imidyl polymer soluble in the solvent used in the coating solution of ⁇ 2 ⁇ is selected from a specific amine compound (c) force on a polyimide having a repeating unit represented by the following formula (I).
  • A represents a tetravalent organic group
  • B represents a divalent organic group
  • the structure of A is not particularly limited.
  • the structure of A may be one type, or multiple types may be mixed. Specific examples of A are as follows.
  • A-6, A-16, A-18 to A-22, and A-25 are preferable because they have high solubility even with polyimide having a high imidization rate.
  • the voltage holding ratio of the liquid crystal cell is improved when it is used as a liquid crystal alignment film. Good.
  • the structure of B is not particularly limited.
  • the structure of B may be one type or a mixture of multiple types. Specific examples of B are as follows.
  • the pretilt angle of the liquid crystal can be increased when the liquid crystal alignment film is formed.
  • the polyimide having the repeating unit represented by the above formula (I) corresponds to the tetracarboxylic dianhydride having the corresponding structure of A as represented by the following formula (II) and the following formula (III) according to a conventional method. It can be obtained by reacting with a diamine having the structure of B to obtain a polyimide precursor, which is dehydrated and cyclized.
  • 15 mol% or less is preferable, more preferably 10 mol% or less, particularly preferably 5 mol% or less, and the amine compound (c) having 2 or more primary amino groups contained in the molecule is Since it plays the role of diamine of formula (III), di of formula (III) Be replaced by Min and Amini ⁇ was the total amount of (c) in this,.
  • the reaction for obtaining the polyimide precursor is usually carried out in an organic solvent at ⁇ 20 to 150 ° C., preferably 0 to 100 ° C., more preferably 10 to 80 ° C.
  • the proportion of tetracarboxylic dianhydride and diamine used is such that the acid anhydride group contained in tetracarboxylic dianhydride is 0.5 to 1 equivalent of amino group contained in diamine. It is preferable that it is -1.5 equivalent, More preferably, it is 0.8-1.2 equivalent.
  • a polyimide precursor to be generated is dissolved. That is not particularly limited.
  • a solvent that does not dissolve the polyamic acid may be used by mixing with the above solvent as long as the produced polyamic acid does not precipitate.
  • water in the organic solvent inhibits the polymerization reaction and further causes hydrolysis of the generated polyamic acid, it is preferable to use an organic solvent that has been dehydrated and dried as much as possible.
  • Common methods for dehydrating and ring-closing polyimide precursors include thermal imidization by heating the polyimide precursor solution as it is, and chemical imidization by adding a catalyst to the polyimide precursor solution, but imidization at a relatively low temperature. Chemical imidization, in which the reaction proceeds, is preferred because the molecular weight of the resulting polyimide is less likely to decrease.
  • Chemical imidization can be performed by stirring a polyimide precursor in an organic solvent in the presence of a basic catalyst and an acid anhydride.
  • the reaction temperature at this time is 20 to 250 ° C, preferably 0 to 180 ° C. Higher reaction temperature Force of S-imide is too high. If it is too high, the molecular weight of the polyimide may decrease.
  • the amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times of the amic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol of the amido acid group. Is double. If the amount of the basic catalyst or acid anhydride is small, the reaction does not proceed sufficiently.
  • the basic catalyst to be used examples 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 examples include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated.
  • the organic solvent the solvent used in the polyamic acid polymerization reaction described above can be used. The imidity ratio due to chemical imidization can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.
  • the added catalyst remains in the solution of the polyimide solution obtained in this way, it is preferable to throw this polyimide solution into a stirring poor solvent and recover the precipitate. Yes.
  • a poor solvent used for the precipitation collection recovery of a polyimide, Methanol, acetone, hexane, a butyl cellosolve, a heptane, a methyl ethyl ketone, a methyl isobutyl ketone, ethanol, toluene, benzene etc. can be illustrated.
  • the polyimide precipitated by adding it to a poor solvent can be recovered by filtration and washing, and then dried at normal temperature or under reduced pressure at room temperature or by heating.
  • reaction between the solvent-soluble polyimide and the amine compound (a) or the amine compound (b) can be performed as follows in the coating solution of ⁇ 1 ⁇ .
  • solvent-soluble polyimide is dissolved in an organic solvent to obtain a solution.
  • the polyimide may be heated. If the heating temperature is too high, the molecular weight of the polyimide may decrease, so 30-100 ° C is preferred.
  • the concentration of the polyimide solution is preferably 1 to 20% by mass, more preferably 3 to 15% by mass, because the polyimide and the amine compound can be reacted efficiently and uniformly. Preferably it is 3-10 mass%.
  • the amine compound is represented by —R 1 —NH.
  • the polyimide concentration is too high, the polyimides may form a three-dimensional structure with the amine compound and the solubility may be reduced. It is preferable to be less than mass%.
  • the solvent is not particularly limited as long as the resin is completely dissolved within the above concentration range.
  • Specific examples include N, N dimethylformamide, N, N dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolatatam, 2-pyrrolidone, N-ethylpyrrolidone, N vinylpyrrolidone, dimethyl sulfoxide, tetramethylurea.
  • Pyridine dimethylsulfone, hexamethylsulfoxide, y-butyrolatatone, 1,3 dimethylimidazolidinone. Two or more of these solvents may be used in combination.
  • Lataton solvents such as y-petit-mouthed rataton react easily with aliphatic amino groups and may consume amine compounds, N, N dimethylformamide is N-methyl 2-pyrrolidone, etc. It is preferable to use the solvent. If you want to use a rataton solvent such as y-petit-mouth rataton as the main solvent, first react the amine compound with the polyimide using a solvent other than the rataton solvent, and then put this solution into an appropriate poor solvent for recovery. Then, it may be dissolved again in the rataton solvent.
  • Examples include butanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, and benzene.
  • the polyimide precipitated by pouring into a poor solvent can be recovered by filtration, washing, and drying at normal temperature or reduced pressure at room temperature or by heating.
  • an amine compound selected from the amine compound (a) and the amine compound (b) is added to the polyimide solution, and the mixture is stirred at room temperature or under heating conditions.
  • the amount of the amine compound added is too small, the effect of the moisture absorption stability of the coating solution will not be sufficiently exerted, and if it is too large, for example, in the liquid crystal alignment film, the orientation of the liquid crystal will be reduced. 1 to 15 parts by mass is more preferable, and 2 to 5 parts by mass is particularly preferable, with respect to 100 parts by mass of the solvent-soluble polyimide, because the characteristics are deteriorated.
  • the amine compound may be added directly to the solvent-soluble polyimide solution, but it is preferable to add the aminey compound after making a solution with a concentration of 0.1 to 10% by mass with an appropriate solvent. Examples of the solvent include the solvent of the solvent-soluble polyimide described above.
  • latonic solvents such as petit latatotone may react with the aliphatic amino group and consume the aminic compound immediately. Therefore, solvents such as ⁇ , ⁇ ⁇ ⁇ ⁇ dimethylformamide ⁇ methyl-2-pyrrolidone, etc. Preferred to use.
  • the temperature during the reaction is preferably 25 to 150 ° C, more preferably 30 to 100 ° C, because the polyimide and the amine compound react efficiently and side reactions do not easily occur. It is particularly preferably 40 to 80 ° C. If the temperature is too high, the soluble polyimide may be hydrolyzed.
  • the reaction time varies depending on the reactivity between the solvent-soluble polyimide and the amine compound and the temperature at which the reaction is carried out. To give a standard example, it is 6 to 48 hours at 40 to 80 ° C.
  • the structure of the polyamic acid used in the coating solution is not particularly limited, but is represented by the following formula (IV) because it can be obtained relatively easily by using tetraforce rubonic acid dianhydride and diamine as raw materials.
  • Preferable is a polyamic acid having a repeating unit.
  • a ' represents a tetravalent organic group
  • B' represents a divalent organic group
  • the polyamic acid having a repeating unit represented by the above formula (IV) is a tetracarboxylic acid having the structure of A ′, as shown in the method for synthesizing a polyimide precursor for obtaining the solvent-soluble polyimide described above. It can be obtained by reacting a dianhydride and a diamine having the structure of B ′ in an organic solvent.
  • the molecular weight of the polyamic acid is not particularly limited, but a weight average molecular weight of 2,000 to 200,000 is more preferable and 5 is more preferable from the viewpoints of handling and stability of characteristics when a film is formed. , 00000 to 100,000.
  • the molecular weight was determined by GPC (gel permeation chromatography).
  • the structure of A ′ is not particularly limited. Further, the structure of A ′ may be one type, or may have different A ′ structures and a plurality of different types of repeating units may be mixed. As a specific example of A ′, the structure exemplified in the above A can be mentioned.
  • the structure of B ′ is not particularly limited. Further, the structure of B ′ may be one type, or may have a different B ′ structure, and a plurality of different types may be mixed as a repeating unit. If the specific example of B 'is given, the structure illustrated by said B will be mentioned.
  • the coating solution of the present invention is soluble in a solvent of a product obtained by reacting a solvent-soluble polyimide with an amine compound selected from amine compounds (a) and (b). What is necessary is just to mix the solution of an imidyl polymer (henceforth a specific product) and the solution of a polyamic acid in arbitrary ratios.
  • an imidyl polymer hereinafter referred to as a specific polyimide
  • a solution of polyamic acid may be mixed at an arbitrary ratio.
  • the reaction solution is put into an appropriate poor solvent, and after the specific product is recovered, it is dissolved in the solvent and used again. May be.
  • the poor solvent at this time include water, methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, and benzene.
  • Solvents for re-dissolution include N, N dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolatatam, 2-pyrididone, N ethylpyrrolidone, N bull pyrrolidone Dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, ⁇ -butyrolacton, 1,3 dimethylimidazolidinone, and the like. These redissolving solvents can also be used as solvents for dissolving the specific polyimide.
  • the specific product and the specific polyimide may be used in combination.
  • the ratio of the specific product, specific polyimide, and polyamic acid is arbitrary. Because a liquid crystal alignment film with good characteristics can be obtained, the polyamic mass in the mass of the specific product, the specific polyimide, and the polyamic acid is combined.
  • the acid ratio is more preferably 20 to 99% by mass, more preferably 40 to 95% by mass, and particularly preferably 60 to 90% by mass.
  • the ratio of the polyamic acid in the mass of the specific product and the soot or the specific polyimide and the polyamic acid is preferably 20 to 99% by mass, more preferably 40 to 95% by mass, and particularly preferably. Is 60-90% by mass.
  • the concentration of the solid component in the coating solution can be appropriately changed depending on the thickness of the coating film to be formed. To obtain a uniform coating film, 0.1 is required. From the viewpoint of storage stability that is preferably at least 30% by mass, it is preferably at most 30% by mass. In addition, 1 to 10% by mass is preferable because a coating film having an appropriate thickness can be obtained as a liquid crystal alignment film.
  • the solvent contained in the coating solution of the present invention may contain a solvent for improving the printability in addition to the above-described re-dissolving solvent for the specific product.
  • a solvent for improving the printability in addition to the above-described re-dissolving solvent for the specific product.
  • Specific examples thereof include ethinorecerosonolev, butinorecellosonoleb, ethinorecanorebitonore, butinorecanolebitonore, ethenorecarbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1-etoxy-2- Propanol, 1-butoxy 2-propanol, 1-phenoxy 2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene Lopyleneglycol 1 Monomethylolate 2—Acetate, Propylene glycol 1 —Monoethyl ether—2-Acetate, Dipropylene glycol, 2-
  • an amide solvent such as N, N dimethylformamide N-methyl-2pyrrolidone is contained in an amount of 50% by mass or more of the coating liquid.
  • the film thickness uniformity is improved, which is preferable.
  • the liquid crystal aligning agent of the present invention comprises the above coating solution, and an additive such as a silane coupling agent may be added to improve the adhesion of the liquid crystal aligning film to the substrate.
  • an additive such as a silane coupling agent may be added to improve the adhesion of the liquid crystal aligning film to the substrate.
  • the liquid crystal aligning agent needs to form a thin film of 300 nm or less on the substrate, when using the coating liquid as the liquid crystal aligning agent, it is filtered with a membrane filter having a pore diameter of 0.1 m to l ⁇ m. U prefer that.
  • the liquid crystal aligning agent of the present invention increases the entanglement of the polymer by appropriately suppressing the phase separation between the imidyl copolymer soluble in the solvent and the polyamic acid when formed into a coating film. In addition, it has the effect of being sharpened against the rubbing process. Furthermore, compared with the case where no amine compound is used, the electrical characteristics of the liquid crystal display element, such as the ease of draining the stored charge and the voltage holding ratio, tend to be improved.
  • the liquid crystal alignment film of the present invention is a coating film obtained by applying the liquid crystal aligning agent obtained as described above to a substrate, drying and baking, and is used for aligning liquid crystals in a predetermined direction. .
  • the substrate on which the liquid crystal aligning agent is applied 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, a polycarbonate substrate, or the like can be used. Use of a substrate on which is formed is also preferable from the viewpoint of simplifying the process.
  • the reflective liquid crystal display element can be used with an opaque object such as a silicon wafer as long as it is only on one side of the substrate. Can also use materials that reflect light, such as aluminum.
  • Examples of the method for applying the liquid crystal aligning agent include spin coating, printing, and ink jet. Industrially, transfer printing such as flexographic printing is widely used from the viewpoint of productivity.
  • the liquid crystal aligning agent of the present invention is also preferably used.
  • the drying process after applying the liquid crystal aligning agent is not necessarily required, but if the time from application to baking is constant for each substrate, or is not baked immediately after coating! It is preferable to include a drying step.
  • the drying means 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 due to transport of 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 used.
  • the substrate coated with the liquid crystal aligning agent can be baked at any temperature of 100 to 350 ° C, preferably 150 ° C to 300 ° C, more preferably 180 ° C to 250 ° C. It is. Also, it is more preferable to fire at a temperature of 10 ° C or higher than the heat treatment temperature required for the liquid crystal cell manufacturing process, such as curing the sealant.
  • the thickness of the coating film after firing is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered, so it is preferably 5 to 300 nm. , More preferably 10: LOOnm.
  • the fired coating film is treated with rubbing or irradiation with polarized ultraviolet rays.
  • the liquid crystal display element of the present invention is a liquid crystal display element obtained by obtaining a liquid crystal alignment agent-powered substrate with a liquid crystal alignment film 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 prepared, and a spacer is dispersed on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is on the inside. Then, the other substrate is bonded and sealed by injecting liquid crystal under reduced pressure, or after dropping the liquid crystal on the surface of the liquid crystal alignment film on which the spacer is dispersed, the substrate is bonded and sealed.
  • the method etc. which perform can be illustrated.
  • the thickness of the spacer at this time is preferably 1 to 30 m, more preferably 2 to 10 ⁇ m.
  • the liquid crystal display element of the present invention includes a TN liquid crystal display element, an STN liquid crystal display element, a TFT liquid crystal display element, an OCB liquid crystal display element, a horizontal electric field type liquid crystal display element, and a vertical alignment type liquid crystal display. It is suitably used for display elements of various methods using nematic liquid crystal such as elements. Further, by selecting the liquid crystal to be used, it can also be used for a ferroelectric and antiferroelectric liquid crystal display element.
  • AM2 (No.37) (Aminoethylaminomethyl) phenethyltrimethoxysilane
  • AM3 (No.32) N- (2-aminoethyl) -3-aminominotrimethoxysilane
  • AM4 (No. 47) (3-Trimethoxysilylpropyl) diethylenetriamine
  • AM5 (No.34) N- (2-aminoethyl) -3-amino
  • AM6 (No.35) N- (2-aminoethyl) -3-amino AM7: (No.95): ⁇ , ⁇ , -bis (2-aminoethinole) -1,3-propanediamin
  • the molecular weights of the solvent-soluble polyimide, the solvent-soluble imidopolymer, and the polyamic acid in the synthesis examples are as follows: Shodex's room temperature gel permeation chromatography (GPC) apparatus (GPC-101), Shodex's column ( Measurement was performed as follows using KD-803 and KD-805).
  • Standard sample for preparing calibration curve TSK standard polyethylene oxide (molecular weight: about 900,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation, and polyethylene glycol (molecular weight: about 12,000, 4,000, 1,000) manufactured by Polymer Laboratory.
  • the imido ratio of the solvent-soluble polyimide in the synthesis example and the imido polymer soluble in the solvent was measured as follows. Add 20 mg of polyimide powder to the NMR sample tube (N MR sampling tube standard ⁇ 5 manufactured by Kusano Kagakusha) and add 0.53 ml of deuterated dimethyl sulfoxide (DMSO-d, 0.05% TMS (tetramethylsilane) mixture) Hesitate and apply ultrasound It was completely dissolved. This solution was measured for proton NMR at 500 MHz with an NMR measuring instrument (JNM-ECA 500) manufactured by JEOL Datum.
  • JNM-ECA 500 JNM-ECA 500
  • the imidation rate is determined based on protons derived from structures that do not change before and after imidation as reference protons, and the peak integrated value of these protons and the proton peak integrated value derived from the NH group of amic acid that appears in the vicinity of 9.5 to 10.0 ppm. It was calculated by the following formula using and.
  • X is the proton peak integrated value derived from the NH group of the amic acid
  • y is the peak integrated value of the reference proton
  • a is one NH group proton of the amic acid in the case of polyamic acid (imido ratio is 0%). Is the number ratio of the reference proton to.
  • a polyamic acid solution was prepared by reacting 150.14 g (0.5 mol) of TDA, 48.67 g (0.45 mol) of DA1, and 18.83 g (0.05 mol) of DA2 in 1233 g of NMP at 50 ° C. for 24 hours.
  • This polyamic acid solution was diluted to 5% by mass with NMP, and 237.9 g of pyridine and 510.6 g of acetic anhydride were further added as an imido catalyst and reacted at 40 ° C. for 3 hours.
  • This solution was put into 17.4 L of methanol, and the resulting precipitate was filtered off and dried to obtain a white polyimide powder.
  • the obtained solvent-soluble polyimide had a number average molecular weight of 9,273 and a weight average molecular weight of 18,815.
  • the imidization ratio was 84%.
  • CBDA 98.05 g (0.5 mol), PMDA 95.98 g (0.44 mol) and DA3 198.27 g (1.0 mol) were reacted in a mixed solvent of NMP lll lg and GBL lll lg at room temperature for 5 hours to polyamic.
  • An acid solution was prepared. This polyamic acid had a number average molecular weight of 11,067 and a weight average molecular weight of 26,270.
  • NMP, GBL and BCS were added to 40 g of the polyamic acid solution obtained in Synthesis Example 2 to prepare a polyamic acid power of 3% by mass, NMP of 59% by mass, GBL of 20% by mass and BCS of 15% by mass.
  • a polyamic acid solution was prepared by reacting 30.03 g (0.1 mol) of TDA and 19.83 g (0.1 mol) of DA3 in 283 g of NMP at 50 ° C. for 24 hours. 50 g of this polyamic acid solution was diluted to 5% by mass with NMP, and 7.1 g of pyridine and 15.4 g of acetic anhydride were further added as an imido catalyst and reacted at 40 ° C. for 3 hours. This solution was poured into 0.6 L of methanol, and the resulting precipitate was filtered and dried to obtain a white polyimide powder.
  • the solvent-soluble polyimide obtained had a number average molecular weight of 13,651 and a weight average molecular weight of 48,092. The imidation ratio was 81%.
  • a coating solution of the present invention was obtained in the same manner as in Example 1 except that the polyimide powder obtained in Synthesis Example 3 was used.
  • a coating solution of the present invention was obtained in the same manner as in Example 1 except that the addition amount or type of the amine compound was changed as follows. When 3 parts by mass of the amine compound is added, a 3% by weight NMP solution of the amine compound is added. When 2 parts by mass is added, the same 2% by weight NMP solution is added. When 1 part by mass of the mass% NMP solution was added, the same 1 mass% NMP solution was added.
  • Example 1 except that the amine compound was not added to the solvent-soluble polyimide solution and diluted to 6% by mass with NMP, and this was mixed with the dilute solution of polyamic acid. A coating solution for comparison was obtained in the same manner as in 1.
  • Example 2 A coating solution for comparison was obtained in the same manner as in Example 1, except that 3-aminopropylmethyljetoxysilane was used as the amine compound in Example 1.
  • a coating solution for comparison was obtained in the same manner as in Example 1 except that 2- (4-aminophenol) ethylamine was used as the amine compound in Example 1.
  • a coating solution for comparison was obtained in the same manner as in Example 1 except that bis (trimethoxysilylpropyl) amine was used as the amine compound in Example 1.
  • a coating solution for comparison was obtained in the same manner as in Example 1 except that N-methylaminopropyltrimethoxysilane was used as the amine compound in Example 1.
  • Example 1 except that the dilute solution of polyamic acid to be mixed was prepared so that polyamic acid was 6% by mass, NMP was 39.5% by mass, GBL was 39.5% by mass, and BCS was 15% by mass. Similarly, the coating liquid of the present invention was obtained.
  • Example 1 the dilute solution of polyamic acid to be mixed was prepared in the same manner as in Example 1 except that the polyamic acid was adjusted to 6% by mass, NMP 20% by mass, GBL 59% by mass, and BCS 15% by mass. Similarly, the coating liquid of the present invention was obtained.
  • NMP, GBL and BCS were added to 40 g of the polyamic acid solution obtained in Synthesis Example 2 to prepare a polyamic acid strength of 3% by mass, NMP of 20% by mass, GBL of 59% by mass and BCS of 15% by mass.
  • a coating solution of the present invention was obtained in the same manner as in Example 30, except that the type of amine compound was changed as follows.
  • a coating solution of the present invention was obtained in the same manner as in Example 31 except that the type of amine compound was changed as follows.
  • a coating solution of the present invention was obtained in the same manner as in Example 32 except that the type of amine compound was changed as follows.
  • a polyamic acid solution was prepared by reacting 30.03 g (0.1 mol) of TDA, 9.46 g (0.0875 mol) of DA1, and 4.71 g (0.0125 mol) of DA2 in 251 g of NMP at 50 ° C. for 24 hours. 50 g of this polyamic acid solution was diluted to 5% by mass with NMP, and 8.1 g of pyridine and 17.3 g of acetic anhydride were further added as an imido catalyst and reacted at 40 ° C. for 3 hours. This solution was put into 0.6 L of methanol, and the resulting precipitate was separated by filtration and dried to obtain a white polyimide powder. The resulting solvent-soluble polyimide had a number average molecular weight of 9,195 and a weight average molecular weight of 19,235. The imidation ratio was 83%.
  • a polyamic acid solution was prepared by reacting 30.03 g (0.1 mol) of TDA, 9.19 g (0.085 mol) of DA1, and 5.65 g (0.015 mol) of DA2 in 254 g of NMP at 50 ° C. for 24 hours. 50 g of this polyamic acid solution was diluted to 5% by mass with NMP, and 7.9 g of pyridine and 17. lg of acetic anhydride were further added as an imido catalyst and reacted at 40 ° C. for 3 hours. This solution was put into 0.6 L of methanol, and the resulting precipitate was separated by filtration and dried to obtain a white polyimide powder. The resulting solvent-soluble polyimide had a number average molecular weight of 9,324 and a weight average molecular weight of 19,244. The imidation ratio was 83%.
  • a polyamic acid solution was prepared by reacting 30.03 g (0.1 mol) of TDA, 8.56 g (0.08 mol) of DA1, and 5.85 g (0.02 mol) of DA5 in NMP 252 g at 50 ° C for 24 hours. . 50 g of this polyamic acid solution was diluted to 5% by mass with NMP, and further 8.0 g of pyridine and 17.2 g of anhydrous acetic acid were added as an imido catalyst and reacted at 40 ° C. for 3 hours. This solution was poured into 0.6 L of methanol, and the resulting precipitate was filtered off and dried to obtain a white polyimide powder. The resulting solvent-soluble polyimide had a number average molecular weight of 9,111 and a weight average molecular weight of 18,045. Further, the imido ratio was 83%.
  • a polyamic acid solution was prepared by reacting 30.03 g (0.1 mol) of TDA, 8.65 g (0.08 mol) of DA1, and 7.61 g (0.02 mol) of DA6 in NMP 185 g at 50 ° C. for 24 hours. . 50 g of this polyamic acid solution was diluted to 5% by mass with NMP, 10.3 g of pyridine and 22. lg of acetic anhydride were further added as an imido catalyst and reacted at 35 ° C. for 3 hours. This solution was put into 0.8 L of methanol, and the resulting precipitate was separated by filtration and dried to obtain a white polyimide powder. The resulting solvent-soluble polyimide had a number average molecular weight of 6,446 and a weight average molecular weight of 13,971. The imidation ratio was 74%.
  • a polyamic acid solution was prepared by reacting 30.03 g (0.1 mol) of TDA, 9.19 g (0.085 mol) of DA1, and 5.71 g (0.015 mol) of DA6 in NMP 255 g at 50 ° C. for 24 hours. 50 g of this polyamic acid solution was diluted to 5% by mass with NMP, and 7.9 g of pyridine and 17.0 g of acetic anhydride were further added as an imido catalyst and reacted at 35 ° C. for 3 hours. This solution in 0.6 L methanol The precipitate obtained was filtered off and dried to obtain a white polyimide powder. The resulting solvent-soluble polyimide had a number average molecular weight of 7,943 and a weight average molecular weight of 14,365. The imidation ratio was 76%.
  • a polyamic acid solution was prepared by reacting 30.03 g (0.1 mol) of TDA, 9.19 g (0.085 mol) of DA1, and 6.11 g (0.015 mol) of DA7 in 257 g of NMP at 50 ° C. for 24 hours. 50 g of this polyamic acid solution was diluted to 5% by mass with NMP, and 7.9 g of pyridine and 16.9 g of acetic anhydride were further added as an imido catalyst and reacted at 40 ° C. for 3 hours. This solution was put into 0.6 L of methanol, and the resulting precipitate was separated by filtration and dried to obtain a white polyimide powder. The resulting solvent-soluble polyimide had a number average molecular weight of 5,735 and a weight average molecular weight of 12,670. The imidation ratio was 83%.
  • a polyamic acid solution was prepared by reacting 30.03 g (0.1 mol) of TDA, 9.19 g (0.085 mol) of DA1, and 5.92 g (0.015 mol) of DA8 in 256 g of NMP at 50 ° C. for 24 hours. 50 g of this polyamic acid solution was diluted to 5% by mass with NMP, and 7.9 g of pyridine and 17.0 g of acetic anhydride were added as an imido catalyst and reacted at 40 ° C. for 3 hours. This solution was put into 0.6 L of methanol, and the resulting precipitate was separated by filtration and dried to obtain a white polyimide powder. The resulting solvent-soluble polyimide had a number average molecular weight of 8,495 and a weight average molecular weight of 22,294. The imidization ratio was 84%.
  • a polyamic acid solution was prepared by reacting 30.03 g (0.1 mol) of TDA, 9.19 g (0.085 mol) of DA1, and 6.04 g (0.015 mol) of DA9 in 257 g of NMP at 50 ° C. for 24 hours. 50 g of this polyamic acid solution was diluted to 5% by mass with NMP, and 7.9 g of pyridine and 16.9 g of acetic anhydride were further added as an imido catalyst and reacted at 40 ° C. for 3 hours. This solution was put into 0.6 L of methanol, and the resulting precipitate was separated by filtration and dried to obtain a white polyimide powder. The resulting solvent-soluble polyimide had a number average molecular weight of 8,775 and a weight average molecular weight of 23,308. The imidization ratio was 84%.
  • a polyamic acid solution was prepared by reacting 30.03 g (0.1 mol) of TDA, 9.19 g (0.085 mol) of DAI, and 5.44 g (0.015 mol) of DA10 in 253 g of NMP at 50 ° C. for 24 hours. 50 g of this polyamic acid solution was diluted to 5% by mass with NMP, and 8.0 g of pyridine and 17.1 g of acetic anhydride were further added as an imido catalyst and reacted at 40 ° C. for 3 hours. This solution was put into 0.6 L of methanol, and the resulting precipitate was separated by filtration and dried to obtain a white polyimide powder. The resulting solvent-soluble polyimide had a number average molecular weight of 7,367 and a weight average molecular weight of 18,959. The imidization ratio was 84%.
  • a polyamic acid solution was prepared by reacting 30.03 g (0.1 mol) of TDA, 9.19 g (0.085 mol) of DA1, and 5.80 g (0.015 mol) of DA11 in NMP 255 g at 50 ° C. for 24 hours. 50 g of this polyamic acid solution was diluted to 5% by mass with NMP, and 7.9 g of pyridine and 17.0 g of acetic anhydride were further added as an imido catalyst and reacted at 40 ° C. for 3 hours. This solution was put into 0.6 L of methanol, and the resulting precipitate was separated by filtration and dried to obtain a white polyimide powder. The resulting solvent-soluble polyimide had a number average molecular weight of 7,203 and a weight average molecular weight of 18,298. The imidization ratio was 84%.
  • a polyamic acid solution was prepared by reacting 30.03 g (0.1 mol) of TDA, 12.26 g (0.09 mol) of DA12, and 3.77 g (0.01 mol) of DA2 in 261 g of NMP at 50 ° C. for 24 hours. 50 g of this polyamic acid solution was diluted to 5% by mass with NMP, and further 7.7 g of pyridine and 16.6 g of acetic anhydride were added as an imido catalyst and reacted at 40 ° C. for 3 hours. This solution was put into 0.6 L of methanol, and the resulting precipitate was separated by filtration and dried to obtain a white polyimide powder. The resulting solvent-soluble polyimide had a number average molecular weight of 8,634 and a weight average molecular weight of 17,655. The imidation ratio was 81%.
  • a polyamic acid solution was prepared by reacting 19.22 g (0.098 mol) of CBDA, 16.26 g (0.08 mol) of DA14, and 5.85 g (0.02 mol) of DA5 in 234 g of NMP at room temperature for 24 hours.
  • This polyamic Mick acid solution 50g diluted five mass 0/0 by NMP, pyridine 2.3 g, acetic anhydride 5.5g added as further imidization catalyst, and reacted for 3 hours at 50 ° C.
  • This solution was put into 0.6 L of methanol, and the resulting precipitate was separated by filtration and dried to obtain a white polyimide powder.
  • the resulting solvent-soluble polyimide had a number average molecular weight of 12,988 and a weight average molecular weight of 30,324.
  • the imidation ratio was 94%.
  • a polyamic acid solution was prepared by reacting 18.43 g (0.094 mol) of CBDA and 19.83 g (0.1 mol) of DA3 in a mixed solvent of 108 g of NMP and 108 g of GBL at room temperature for 5 hours.
  • This polyamic acid had a number average molecular weight of 16,951 and a weight average molecular weight of 37,292.
  • a polyamic acid solution was prepared by reacting 18.43 g (0.094 mol) of CBDA and 20.02 g (0.1 mol) of DA15 in a mixed solvent of 109 g of NMP and 109 g of GBL at room temperature for 5 hours.
  • This polyamic acid had a number average molecular weight of 15,139 and a weight average molecular weight of 31,565.
  • a polyamic acid solution was prepared by reacting 18.04 g (0.092 mol) of CBDA and 19.93 g (0.1 mol) of DA16 in a mixed solvent of NMP 171 g and GBL 17 lg at room temperature for 5 hours.
  • This polyamic acid had a number average molecular weight of 20,821 and a weight average molecular weight of 49,970.
  • 3 g of the polyimide powder obtained in Synthesis Example 4 was dissolved in 34.5 g of NMP by stirring at 50 ° C. for 20 hours.
  • 3 wt 0 / oNMP solution was added (0.09 g as Amini ⁇ product) to 3.0 g, further polyimide concentration in the solution is 6 mass triethylenetetramine (Amin compound of No.94) the NMP 9.5 g so that the 0/0 Ka ⁇ E and 20h stirred at 50 ° C.
  • the added amount of the amine compound at this time is 3 parts by mass with respect to 100 parts by mass of the polyimide.
  • NMP, GBL and BCS were added to 40 g of the polyamic acid solution obtained in Synthesis Example 2 to prepare a polyamic acid power of 3% by mass, NMP of 59% by mass, GBL of 20% by mass and BCS of 15% by mass.
  • Example NoNMPZGBLZBCS 66Zl6Zl2.
  • a coating solution of the present invention was obtained in the same manner as in Example 47 except that the polyimide powder was changed as follows.
  • NMP, GBL and BCS were added to 40 g of the polyamic acid solution obtained in Synthesis Example 19 to prepare a polyamic acid power of 3% by mass, NMP of 20% by mass, GBL of 59% by mass and BCS of 15% by mass.
  • 3 g of the polyimide powder obtained in Synthesis Example 17 was dissolved in 34.5 g of GBL by stirring at 50 ° C. for 20 hours. To this solution was added 3.0 g (0.15 g as an amine compound) of 3 mass 0 / oGBL solution of triethylenetetraamine (No. 94 amine compound), and the polyimide concentration in this solution was 6%. GBL 9.5g was added so that it might become the amount%, and it stirred at 50 degreeC for 20 hours. The amount of the amine compound added at this time is 3 parts by mass with respect to 100 parts by mass of the polyimide.
  • NMP, GBL, and BCS were added to 40 g of the polyamic acid solution obtained in Synthesis Example 20 to prepare a polyamic acid power of 3% by mass, NMP of 20% by mass, GBL of 59% by mass, and BCS of 15% by mass.
  • NMP, GBL, and BCS were added to 40 g of the polyamic acid solution obtained in Synthesis Example 19 to prepare a polyamic acid power of 3 mass%, NMP of 59 mass%, GBL of 20 mass%, and BCS of 15 mass%.
  • Example 62 NMP, GBL, and BCS were added to 40 g of the polyamic acid solution obtained in Synthesis Example 21 as a dilute solution of the polyamic acid to be mixed, and the polyamic acid strength was 3 ⁇ 4 mass%, NMP was 39.5 mass%, A coating solution of the present invention was obtained in the same manner as in Example 62 except that GBL was 39.5% by mass and BCS was 15% by mass.
  • a polyamic acid solution was prepared by reacting 9.81 g (0.05 mol) of CBDA, 9.60 g (0.044 mol) of PMDA, and 19.83 g (0.1 mol) of DA3 in 222 g of NMP at room temperature for 5 hours.
  • This polyamic acid had a number average molecular weight of 10,893 and a weight average molecular weight of 25,972.
  • NMP and BCS were added to 40 g of the polyamic acid solution obtained in Synthesis Example 22 to prepare 6 mass% polyamic acid, 79 mass% NMP, and 15 mass% BCS.
  • NMP, GBL and BCS were added to 40 g of the polyamic acid solution obtained in Synthesis Example 2 to prepare a polyamic acid strength of 3% by mass, NMP of 20% by mass, GBL of 59% by mass and BCS of 15% by mass.
  • the obtained imidized polymer soluble in the solvent had a number average molecular weight of 5,951 and a weight average molecular weight of 22,992.
  • the imidation ratio was 81%.
  • NMP, GBL and BCS were added to 40 g of the polyamic acid solution obtained in Synthesis Example 2 to prepare a polyamic acid power of 3% by mass, NMP of 59% by mass, GBL of 20% by mass and BCS of 15% by mass.
  • the coating liquids prepared in Examples 1 to 66 and Comparative Examples 1 to 5 were pressure filtered through a membrane filter having a pore size of 1 ⁇ m to obtain a liquid crystal aligning agent.
  • a liquid crystal aligning agent is spin-coated on a glass substrate with an ITO electrode, dried on a hot plate at 80 ° C for 5 minutes, and then baked in a hot air circulation oven at 230 ° C for 30 minutes.
  • An Onm coating was formed. This coating surface was rubbed with a rayon cloth with a rubbing machine having a roll diameter of 120 mm 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 .
  • the surface of the liquid crystal alignment film was observed with a real-time scanning laser microscope 1LM21D (objective lens 10 ⁇ ) manufactured by Lasertec (magnification magnification 340 ⁇ on the monitor).
  • the surface of the liquid crystal alignment film obtained using the liquid crystal aligning agent having the coating liquid force of Examples 1 to 64 and Example 66 was strong enough to show no scratches or film peeling. Although peeling of the film was not observed on the surface of the liquid crystal alignment film obtained by using the liquid crystal aligning agent comprising the coating liquids of Comparative Examples 1 to 5, many fine scratches were observed. Further, the surface of the liquid crystal alignment film obtained using the liquid crystal aligning agent having the coating liquid force of Example 65 was observed to have fine scratches although no film peeling was observed.
  • Example 65 This is because in Example 65, ⁇ -petit-mouth rataton was used as the solvent for reacting the solvent-soluble polyimide and the amine compound, so that the amine compound was consumed by reacting with ⁇ -petit-mouth rataton. It is considered that a sufficient amount of the added amount by mass did not react with the solvent-soluble polyimide.
  • liquid crystal aligning agents having the coating liquid power of Examples 30 to 32 were subjected to a printability test by the flexographic printing method as follows.
  • Printing conditions -The width of the pop was 0.2 mm.
  • the tact time was set to 30 seconds, and printing was first performed on six 100 mm ⁇ 100 mm glass substrates, followed by printing on four Cr film-formed glass substrates of the same size. Finally, the printed substrate is dried on a hot plate at 80 ° C for 5 minutes and viewed with a microscope at 50x magnification.
  • the liquid crystal aligning agent having the coating solution power of Example 30 was superior in in-plane film thickness uniformity to the other two liquid crystal aligning agents.
  • a liquid crystal aligning agent is spin-coated on a glass substrate with a ⁇ electrode, dried on a hot plate at 80 ° C for 5 minutes, and then baked in a hot air circulation oven at 230 ° C for 30 minutes.
  • An Onm coating was formed.
  • the coated surface was rubbed with a rayon cloth using a rubbing machine having a roll diameter of 120 mm 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. .
  • the temperature of the liquid crystal cell produced above is 90 using the VHR-1 voltage holding ratio measuring device manufactured by Toyo Tech-Riki. C, voltage: ⁇ 4V, pulse width: 60 ⁇ s, flame period: measured at a setting of 16.67ms, voltage holding of how much can be maintained after 16.6ms of voltage force of 4VZ60s at a temperature of 90 ° C Calculated as a rate.
  • Example 5 93% Example 3 0 943 ⁇ 4 Example 5 5 933 ⁇ 4
  • Example 1 0 943 ⁇ 4
  • Example 3 5 943 ⁇ 4
  • Example 6 0 953 ⁇ 4
  • Example 1 1 953 ⁇ 4
  • Example 3 6 943 ⁇ 4
  • Example 6 1 953 ⁇ 4
  • Example 1 2 933 ⁇ 4 Example 3 7 943 ⁇ 4 Example 6 2 943 ⁇ 4
  • Example 1 4 953 ⁇ 4
  • Example 3 9 943 ⁇ 4
  • Example 6 4 953 ⁇ 4
  • Example 1 5 943 ⁇ 4
  • Example 4 0 943 ⁇ 4
  • Example 6 5 933 ⁇ 4
  • Example 1 6 953 ⁇ 4
  • Example 4 1 943 ⁇ 4
  • Example 6 6 94X
  • Example 2 1 943 ⁇ 4 Example 4 6 943 ⁇ 4 Comparative Example 5 933 ⁇ 4
  • liquid crystal cell of the liquid crystal aligning agent liquid crystal display element of the present invention
  • liquid crystal cell of the liquid crystal aligning agent that is the coating liquid of Example 4
  • the liquid crystal cell of the liquid crystal aligning agent that is the coating liquid force of Comparative Example 1 the liquid for comparison
  • the crystal display element was compared with the ease of stored charge release as follows.
  • the coating solution of the present invention precipitation of the rosin component due to moisture absorption can be suppressed, stable printability can be obtained, and it can be suitably used as a liquid crystal aligning agent.
  • the liquid crystal alignment film of the present invention can provide a liquid crystal display element of higher quality than before, and this liquid crystal display element can be suitably used for various display devices.

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Abstract

L'invention concerne un film orienté de cristaux liquides dans lequel la déposition de composant de résine par absorption d'humidité est inhibée, et qui a une capacité d'impression stable de même que des caractéristiques comme la résistance au frottement et la facilité d'extraction de la charge stockée. Un liquide d'application, caractérisé en ce qu'il contient un composant (A) : un soluble polymère imidé dans un solvant obtenu à partir d'au moins un type de composé aminé sélectionné parmi le groupe consistant en un dianhydrure tétracarboxylique, un composé diaminé, un composé aminé (a), un composé aminé (b), et un composé aminé (c) décrits ci-dessous, et un composant (B) : acide polyamique. Composé aminé (a): composé aminé possédant dans sa molécule un groupe aminé primaire sélectionné parmi la formule [K1] et la formule [K2], et au moins un groupe iminé sélectionné parmi la formule [K3] et la formule [K4]. Dans la formule [K3] et la formule [K4], la direction d'accouplement de -CH2-NH- est opposée l'une à l'autre. Composé aminé (b) : composé aminé possédant dans sa molécule au moins deux groupes aminés primaires sélectionnés parmi la formule [K1] et la formule [K2]. Composé aminé (c): composé aminé possédant dans sa molécule au moins un groupe aminé primaire sélectionné parmi la formule [K1] et la formule [K2], et au moins un groupe iminé sélectionné parmi la formule [K3] et la formule [K4].
PCT/JP2007/064207 2006-07-18 2007-07-18 agent d'orientation de cristaux liquides, film orienté de cristaux liquides et élément d'affichage à cristaux liquides L'utilisant WO2008010528A1 (fr)

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CN2007800270738A CN101490188B (zh) 2006-07-18 2007-07-18 液晶定向剂、使用了该定向剂的液晶定向膜及液晶显示元件
KR1020097000976A KR101426100B1 (ko) 2006-07-18 2007-07-18 액정 배향제 그리고 그것을 사용한 액정 배향막 및 액정 표시 소자

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WO2011132751A1 (fr) * 2010-04-22 2011-10-27 日産化学工業株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides
JP5282573B2 (ja) * 2006-12-27 2013-09-04 日産化学工業株式会社 液晶配向剤、それを用いた液晶配向膜及び液晶表示素子
CN101747907B (zh) * 2008-12-02 2013-09-25 Jsr株式会社 液晶取向剂、液晶显示元件、聚酰胺酸及其酰亚胺化聚合物
WO2013146890A1 (fr) * 2012-03-29 2013-10-03 日産化学工業株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
KR101613751B1 (ko) 2008-09-24 2016-04-19 닛산 가가쿠 고교 가부시키 가이샤 액정 배향 처리제 및 그것을 사용한 액정 표시 소자

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TW201534594A (zh) * 2010-06-30 2015-09-16 Nissan Chemical Ind Ltd 液晶配向劑、液晶配向膜、液晶顯示元件及液晶顯示元件之製造方法，以及聚合性化合物
KR101824283B1 (ko) * 2010-07-13 2018-01-31 닛산 가가쿠 고교 가부시키 가이샤 액정 배향 처리제, 액정 배향막 및 액정 표시 소자
KR101875240B1 (ko) * 2010-08-31 2018-07-05 닛산 가가쿠 고교 가부시키 가이샤 디아민, 폴리이미드 전구체, 폴리이미드, 액정 배향제, 액정 배향막 및 액정 표시 소자
KR20200105976A (ko) * 2012-11-16 2020-09-09 닛산 가가쿠 가부시키가이샤 폴리이미드 수지필름 및 폴리이미드 수지필름으로 이루어지는 전자디바이스용 기판
KR20150118527A (ko) * 2014-04-14 2015-10-22 제이엔씨 주식회사 액정 배향제, 액정 배향막 및 액정 표시 소자
EP3242904B1 (fr) * 2015-01-05 2022-02-09 SHPP Global Technologies B.V. Polyimide réactif friable et son procédé de production
JP7494537B2 (ja) * 2019-04-26 2024-06-04 Jnc株式会社 光配向用液晶配向剤、液晶配向膜、および液晶表示素子

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CN101747907B (zh) * 2008-12-02 2013-09-25 Jsr株式会社 液晶取向剂、液晶显示元件、聚酰胺酸及其酰亚胺化聚合物
WO2011132751A1 (fr) * 2010-04-22 2011-10-27 日産化学工業株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides
JP5713009B2 (ja) * 2010-04-22 2015-05-07 日産化学工業株式会社 液晶配向処理剤、液晶配向膜及び液晶表示素子
KR101775182B1 (ko) 2010-04-22 2017-09-05 닛산 가가쿠 고교 가부시키 가이샤 액정 배향 처리제, 액정 배향막 및 액정 표시 소자
KR101775181B1 (ko) 2010-04-22 2017-09-05 닛산 가가쿠 고교 가부시키 가이샤 액정 배향 처리제, 액정 배향막 및 액정 표시 소자
WO2013146890A1 (fr) * 2012-03-29 2013-10-03 日産化学工業株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
CN104380188A (zh) * 2012-03-29 2015-02-25 日产化学工业株式会社 液晶取向剂、液晶取向膜及液晶显示元件
JPWO2013146890A1 (ja) * 2012-03-29 2015-12-14 日産化学工業株式会社 液晶配向剤、液晶配向膜及び液晶表示素子
CN104380188B (zh) * 2012-03-29 2017-05-31 日产化学工业株式会社 液晶取向剂、液晶取向膜及液晶显示元件

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CN101490188A (zh) 2009-07-22
TW200819509A (en) 2008-05-01
JPWO2008010528A1 (ja) 2009-12-17
CN101490188B (zh) 2012-07-04
JP5428336B2 (ja) 2014-02-26
KR20090031737A (ko) 2009-03-27
KR101426100B1 (ko) 2014-08-01

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