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WO2009093709A1 - Matériau d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides - Google Patents

Matériau d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides Download PDF

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Publication number
WO2009093709A1
WO2009093709A1 PCT/JP2009/051116 JP2009051116W WO2009093709A1 WO 2009093709 A1 WO2009093709 A1 WO 2009093709A1 JP 2009051116 W JP2009051116 W JP 2009051116W WO 2009093709 A1 WO2009093709 A1 WO 2009093709A1
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Prior art keywords
liquid crystal
formula
integer
aligning agent
diamine compound
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PCT/JP2009/051116
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English (en)
Japanese (ja)
Inventor
Kohei Goto
Noritoshi Miki
Kenzo Yada
Masaaki Katayama
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Nissan Chemical Corp
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Nissan Chemical Corp
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Priority to JP2009550583A priority Critical patent/JP5177150B2/ja
Priority to CN2009801032007A priority patent/CN101925850B/zh
Publication of WO2009093709A1 publication Critical patent/WO2009093709A1/fr
Anticipated expiration legal-status Critical
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    • 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
    • C08G73/02—Polyamines
    • C08G73/0273—Polyamines containing heterocyclic moieties in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
    • 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
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety

Definitions

  • the present invention relates to a liquid crystal aligning agent used for producing a liquid crystal alignment film and a liquid crystal display element using the same.
  • a polyimide liquid crystal alignment film obtained by applying a liquid crystal alignment agent mainly composed of a polyimide precursor such as polyamic acid or a solution of soluble polyimide to a glass substrate or the like and baking it is mainly used. It is used.
  • the liquid crystal alignment film is used for the purpose of controlling the alignment state of the liquid crystal.
  • the liquid crystal alignment film used in the liquid crystal alignment film has a high voltage holding ratio and a direct current voltage due to demands such as a reduction in contrast of the liquid crystal display elements and a reduction in the afterimage phenomenon.
  • the characteristics that the residual charge when applied is small and / or the residual charge accumulated by the DC voltage is quickly relaxed have become increasingly important.
  • a liquid crystal aligning agent containing a tertiary amine having a specific structure in addition to polyamic acid or an imide group-containing polyamic acid was used as a short time until the afterimage generated by direct current voltage disappears.
  • a liquid crystal aligning agent containing a soluble polyimide using a specific diamine having a pyridine skeleton as a raw material for example, see Patent Document 1.
  • a compound containing one carboxylic acid group in the molecule In addition to polyamic acid and its imidized polymer, a compound containing one carboxylic acid group in the molecule, assuming that the voltage holding ratio is high and the time until the afterimage generated by direct current voltage disappears is short , Using a liquid crystal aligning agent containing a very small amount of a compound selected from a compound containing one carboxylic anhydride group in the molecule and a compound containing one tertiary amine group in the molecule (for example, a patent Document 3) is known.
  • liquid crystal display elements in such applications are more effective against afterimages than conventional displays that mainly display characters and still images.
  • the requirements are becoming stricter, and characteristics that can withstand long-term use in harsh usage environments are required. Therefore, the liquid crystal alignment film used there is required to have a higher reliability than before, and the electrical characteristics of the liquid crystal alignment film not only have good initial characteristics, but also, for example, at high temperatures. There is a need to maintain good properties even after prolonged exposure.
  • the present invention has been made in view of the above circumstances. That is, the problem to be solved by the present invention is a liquid crystal capable of obtaining a liquid crystal alignment film having a high voltage holding ratio and a small residual charge accumulated by a DC voltage even after being exposed to a high temperature for a long time. It is to provide an alignment agent. Furthermore, it is an object of the present invention to provide a highly reliable liquid crystal display element that can withstand long-term use in harsh usage environments.
  • W 1 is a benzene ring or a nitrogen-containing aromatic heterocyclic ring
  • W 2 is an aromatic having 6 to 15 carbon atoms and 1 to 2 benzene rings
  • W 3 is alkylene having 2 to 5 carbon atoms or biphenylene
  • W 4 is cycloalkylene having 4 to 6 carbon atoms substituted with a tertiary nitrogen atom
  • W 5 is having 2 to 5 carbon atoms.
  • Z 1 is a disubstituted amino group substituted with an aliphatic group having 1 to 6 carbon atoms when W 1 is a benzene ring, and when W 1 is a nitrogen-containing aromatic heterocyclic ring
  • Z 2 is an alkyl group having 1 to 5 carbon atoms or a benzene ring
  • g is an integer of 0 or 1;
  • a 1 is a nitrogen-containing aromatic heterocyclic ring
  • a 2 is an aromatic group having 6 to 15 carbon atoms and 1 to 2 benzene rings.
  • a 3 is alkylene having 2 to 5 carbons or biphenylene
  • a 4 is a group represented by the formula [4a] or [4b]
  • a 5 is alkylene having 2 to 5 carbons
  • Y 1 is a disubstituted amino group substituted with an aliphatic group having 1 to 6 carbon atoms
  • Y 2 is an alkyl group having 1 to 5 carbon atoms or a benzene ring
  • k is an integer of 0 or 1.
  • P is a bonding group selected from a single bond, —O—, —NH—, methylene, and an amide group.
  • m1 is an integer of 1 to 4
  • X 2 is a single bond, —CH 2 —, —C 2 H 4 —, —C (CH 3 ) 2 —, —CF 2 —, —C (CF 3 ) 2 —, —O—, —CO—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —CH 2 O—, —OCH 2- , -COO-, -OCO-, -CON (CH 3 )-, or -N (CH 3 ) CO-
  • m2 and m3 each represent an integer of 0 to 4
  • m2 + m3 is 1 to 4 indicates the integer, wherein [22], m4, m5 is an integer from respectively 1 5, wherein [23], X 3 is a straight-chain or branched alkyl group having 1 to 5 carbon atoms, m6 1 is an integer of
  • X 2 is a single bond, —CH 2 —, —C 2 H 4 —, —C (CH 3 ) 2 —, —O—, —CO—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —COO—, or —OCO—, wherein m2 and m3 are both integers of 1, the liquid crystal aligning agent according to (7) above.
  • X 4 represents a single bond, —CH 2 —, —O—, —CO—, —NH—, —CONH—, —NHCO—, —CH 2 O—, —OCH 2 —.
  • the content of the diamine compound (B) in the diamine component is 0.01 to 99 mol per mol of the diamine compound (A), and any one of (1) to (10) above A liquid crystal aligning agent according to item.
  • a liquid crystal display device having the liquid crystal alignment film according to (14).
  • the liquid crystal aligning agent of the present invention can be obtained by a relatively simple method. Moreover, the liquid crystal aligning agent of this invention can obtain the liquid crystal aligning film with little residual charge accumulate
  • the present invention uses a liquid crystal aligning agent containing a copolymer obtained by reacting a diamine component (A) and a diamine component containing the diamine compound (B) with tetracarboxylic dianhydride, and the liquid crystal aligning agent.
  • the obtained liquid crystal alignment film is a liquid crystal display device having the liquid crystal alignment film.
  • the diamine compound (A) used in the present invention is a diamine compound having a tertiary nitrogen atom represented by the formula [T1] to the formula [T3].
  • the tertiary nitrogen atom means a nitrogen atom in which three bonds of the nitrogen atom are bonded to an atom other than a hydrogen atom, preferably a carbon atom.
  • the tertiary nitrogen atom of the diamine compound (A) used in the present invention functions as an electron hopping site due to its conjugated structure, the movement of charges in the liquid crystal alignment film can be promoted. Further, the tertiary nitrogen atom and the carboxyl group of the diamine compound (B) in the molecule thereof are bonded by an electrostatic interaction such as salt formation or hydrogen bond, so that the tertiary nitrogen atom Charge transfer occurs between the carboxyl group and the carboxyl group. Along with this, the accumulated charge can efficiently move within and between the molecules of the copolymer.
  • the liquid crystal aligning film when used as a liquid crystal aligning film, the liquid crystal aligning film has a high voltage holding ratio and a small residual charge accumulated by a DC voltage even after being exposed to a high temperature for a long time. Can be obtained.
  • the diamine compound (A) used in the present invention is a diamine compound having a tertiary nitrogen atom, which is at least one compound selected from the group consisting of the following formula [T1], formula [T2] and formula [T3]. .
  • W 1 is a benzene ring or a nitrogen-containing aromatic heterocycle
  • W 2 is an aromatic having 6 to 15 carbon atoms and 1 to 2 benzene rings
  • W 3 is alkylene having 2 to 5 carbon atoms or biphenylene
  • W 4 is cycloalkylene having 4 to 6 carbon atoms substituted with a tertiary nitrogen atom
  • W 5 is having 2 to 5 carbon atoms.
  • Z 1 is a disubstituted amino group substituted with an aliphatic group having 1 to 6 carbon atoms when W 1 is a benzene ring, and hydrogen when W 1 is a nitrogen-containing aromatic heterocyclic ring
  • Z 2 is an alkyl group having 1 to 5 carbon atoms or a benzene ring
  • g is an integer of 0 or 1.
  • preferable compounds include the diamine compounds of the following formulas [1] to [4].
  • a 1 is a nitrogen-containing aromatic heterocyclic ring
  • a 2 is an aromatic group having 6 to 15 carbon atoms and 1 to 2 benzene rings.
  • a 3 is alkylene having 2 to 5 carbon atoms or biphenylene
  • a 4 is a group represented by the formula [4a] or [4b]
  • a 5 is alkylene having 2 to 5 carbon atoms
  • Y 1 is an aliphatic group having 2 to 12 carbon atoms containing a tertiary nitrogen atom
  • Y 2 is an alkyl group having 1 to 5 carbon atoms or a benzene ring
  • k is an integer of 0 or 1.
  • a 1 in the formula [1] is a nitrogen-containing aromatic heterocyclic ring, specifically, a pyrrole ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a pyrazoline ring, Carbazole ring, purine ring, thiadiazole ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, thionoline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring Phenothiazine ring, oxadiazole ring, and acridine ring.
  • a pyrrole ring an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring and a pyrazoline ring. More preferred are a pyrrole ring, an imidazole ring, an oxazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, and a quinoline ring. Specific examples include diamine compounds of the following formulas [5] to [12].
  • Y 1 in the formula [2] is an aliphatic group having 2 to 12 carbon atoms containing a tertiary nitrogen atom.
  • a diamine compound of the following formula [13] or formula [14] Can be mentioned.
  • a 2 in the formula [3] is an aromatic group having 6 to 15 carbon atoms and 1 to 2 benzene rings
  • a 3 is alkylene or biphenylene having 2 to 5 carbon atoms
  • Y 2 Is an alkyl group having 1 to 5 carbon atoms or a benzene ring
  • k is an integer of 0 or 1.
  • a 2 in Formula [3] is preferably a benzene ring or a structure represented by Formula [3a].
  • P represents a bonding group selected from a single bond, —O—, —NH—, methylene, and an amide group.
  • Preferable specific examples of the formula [3] include diamine compounds of the following formulas [15] to [17].
  • m and n are each an integer from 1 to 11
  • m + n is an integer from 2 to 12
  • j is an integer from 0 to 3.
  • a 4 in Formula [4] is a group represented by Formula [4a] or Formula [4b]
  • a 5 is alkylene having 2 to 5 carbon atoms.
  • Preferable specific examples of the formula [4] include diamine compounds of the following formula [18].
  • h is an integer of 1 to 5.
  • a diamine compound (A) can also be used individually by 1 type or in combination of multiple types.
  • the diamine compound (B) used in the present invention is a diamine compound having a carboxyl group in the molecule.
  • a compound having 1 to 4 carboxyl groups in the molecule is preferable.
  • the structure of a diamine compound (B) is not specifically limited, Preferably, it is a diamine compound represented by Formula [19].
  • X 1 is an organic group having an aromatic ring having 6 to 30 carbon atoms, and n is an integer of 1 to 4.
  • Preferred structures of the formula [19] include the structures of the following formulas [20] to [24].
  • m1 is an integer of 1 to 4
  • X 2 is a single bond, —CH 2 —, —C 2 H 4 —, —C (CH 3 ) 2 —, — CF 2 —, —C (CF 3 ) 2 —, —O—, —CO—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —CH 2 O—, —OCH 2 -, -COO-, -OCO-, -CON (CH 3 )-, or -N (CH 3 ) CO-
  • m2 and m3 each represent an integer from 0 to 4
  • m2 + m3 is from 1 to 4 an integer, wherein [22], m4, m5 is an integer from respectively 1 5, wherein [23], X 3 is a straight-chain or branched alkyl group having 1 to 5 carbon atoms, m6 1 And X
  • m1 is an integer of 1 to 2
  • X 2 is a single bond, —CH 2 —, —C 2 H 4 —, —C (CH 3 ).
  • X 4 is a single bond, —CH 2 —, —O—, —CO—, —NH—, —CONH—, —NHCO—, —CH 2 O—, —OCH 2 -, -COO-, or -OCO-, and m7 is a structure having an integer of 1 to 2.
  • the structure represented by Formula [20] is especially preferable.
  • diamine compound (B) examples include diamine compounds of the following formulas [25] to [35].
  • X 5 represents a single bond, —CH 2 —, —O—, —CO—, —NH—, —CONH—, —NHCO—, —CH 2 O—, —OCH 2 —, —COO. — Or —OCO—, and in formula [35], X 6 is a single bond, —CH 2 —, —O—, —CO—, —NH—, —CONH—, —NHCO—, —CH 2 O —, —OCH 2 —, —COO—, or —OCO—.
  • p-phenylenediamine 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol 4,6-diaminoresorcinol, 4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 3,3 ′ -Dihydroxy-4,4'-diaminobiphenyl, 3,3'-difluoro-4,
  • diamine examples include a diamine having an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, and a macrocyclic substituent composed of these in the side chain of the diamine.
  • diamine compound of the formula [DA26] examples include DA1].
  • R 1 is an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group.
  • R 2 represents —COO—, —OCO—, —CONH—, —NHCO—, —CH 2 —, —O—, —CO—, or —NH—.
  • R 3 represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group.
  • R 4 represents —O—, —OCH 2 —, —CH 2 O—, —COOCH 2 —, or —CH 2 OCO—
  • R 5 represents 1 carbon atom.
  • R 6 represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, —OCH. 2 — or —CH 2 —, wherein R 7 is an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group, or a fluorine-containing alkoxy group.
  • R 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 trifluoromethane group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group, or a hydroxyl group. is there.
  • examples of other diamine compounds include diaminosiloxanes represented by the following formula [DA27].
  • m is an integer of 1 to 10.
  • the above-mentioned other diamine compounds may 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.
  • the tetracarboxylic dianhydride used in the present invention may be at least one compound of tetracarboxylic dianhydrides. Specific examples are given below.
  • pyromellitic dianhydride 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalene Tetracarboxylic dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, 1,2,5,6-anthracene tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl Tetracarboxylic dianhydride, 2,3,3 ′, 4-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid Dianhydrides, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) methane, 2,2-bis (3,
  • 1,2,3,4-cyclobutanetetracarboxylic dianhydride 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride
  • Anhydride 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cycloheptanetetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran Tetracarboxylic dianhydride, 3,4-dicarboxy-1-cyclohexylsuccinic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3,4-dicarboxy-1, , 3,4-dica
  • tetracarboxylic dianhydrides can be used singly or in combination of two or more depending on the properties such as liquid crystal alignment properties, voltage holding properties, accumulated charges, etc. when the liquid crystal alignment film is formed.
  • the copolymers used in the present invention are polyamic acid and polyimide.
  • the polyamic acid is a polyamic acid obtained by reacting a diamine component containing the diamine compound (A) and the diamine compound (B) with tetracarboxylic dianhydride.
  • the polyimide of the present invention is a polyimide obtained by dehydrating and ring-closing this polyamic acid. Both the polyamic acid and the polyimide are useful as a copolymer for obtaining a liquid crystal aligning agent.
  • the content of the diamine compound (B) in the diamine component is preferably 0.01 to 99 mol with respect to 1 mol of the diamine compound (A). More preferably, it is 0.1-50 mol, More preferably, it is 0.5-20 mol, Most preferably, it is 0.5-10 mol.
  • diamine compounds other than the diamine compound (A) and the diamine compound (B) can be used in combination with the diamine component.
  • the amount of the other diamine compound used in that case is preferably 0.01 to 10 mol, more preferably 0.1 to 5 mol, relative to 1 mol of the diamine compound (A).
  • the polyamic acid used in the present invention can be obtained by using a known polymerization method.
  • tetracarboxylic dianhydride and a diamine component are reacted in an organic solvent.
  • the reaction between the tetracarboxylic dianhydride and the diamine component is advantageous in that it proceeds relatively easily in an organic solvent and no by-product is produced.
  • the organic solvent used in that case should just be a thing in which the produced
  • 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 produced polyamic acid, it is preferable to use a dehydrated and dried organic solvent.
  • a method of reacting a tetracarboxylic dianhydride and a diamine component in an organic solvent a solution in which the diamine component is dispersed or dissolved in an 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. And any of these methods may be used.
  • tetracarboxylic dianhydride or diamine component consists of multiple types of compounds
  • the multiple types of compounds may be mixed in advance and then reacted with the other component, or individually and sequentially. Furthermore, it is possible to obtain a high molecular weight body by mixing and reacting individually reacted low molecular weight bodies.
  • the temperature can be selected from -20 ° C. to 150 ° C., but is preferably in the range of ⁇ 5 ° C. to 100 ° C.
  • the reaction can be carried out at any concentration, but if the concentration is too low, it will be difficult to obtain a high molecular weight copolymer, and if the concentration is too high, the viscosity of the reaction solution will become too high and uniform stirring will occur. Since it becomes difficult, the total concentration of the tetracarboxylic dianhydride and the diamine component in the reaction solution is preferably 1 to 50% by mass, more preferably 5 to 30% by mass.
  • the initial reaction may be performed at a high concentration, and then an organic solvent may be added.
  • the number of moles of the diamine component relative to 1 mole of tetracarboxylic dianhydride is preferably 0.8 to 1.2. The closer the molar ratio is to 1.0, the larger the molecular weight of the polyamic acid produced.
  • the polyimide used in the present invention is a polyimide obtained by dehydrating and ring-closing the polyamic acid obtained by the above method, and is useful as a copolymer for obtaining a liquid crystal alignment film.
  • the dehydration cyclization rate (imidization rate) of the amic acid group is not necessarily 100%, and can be arbitrarily adjusted according to the use 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 ° C. to 400 ° C., preferably 120 ° C. to 250 ° C., and it is preferable to carry out while removing water generated by the imidation 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 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.
  • Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, etc. 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 facilitated.
  • the imidization rate by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.
  • 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. Particularly preferably, it is 50% or more.
  • the reaction solution When the produced copolymer is recovered from the reaction solution of polyamic acid or polyimide, 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.
  • the polymer precipitated in a poor solvent and collected by filtration can be dried by normal temperature or reduced pressure at room temperature or by heating.
  • the molecular weights of the polyamic acid and the polyimide used in the liquid crystal aligning agent of the present invention are GPC (Gel Permeation Chromatography) in consideration of the strength of the coating film obtained therefrom, workability when forming the coating film, and uniformity of the coating film.
  • the weight average molecular weight measured by the method is preferably 5,000 to 1,000,000, and more preferably 10,000 to 150,000.
  • the liquid crystal aligning agent of this invention is a coating liquid for producing a liquid crystal aligning film
  • the main component consists of the resin component for forming a resin film, and the organic solvent which dissolves this resin component.
  • the resin component is a resin component containing at least one copolymer selected from the group consisting of the polyamic acid and polyimide used in the present invention.
  • content of the resin component in a coating liquid is 1 mass% to 20 mass%, Preferably it is 2 mass% to 10 mass%.
  • all of the above resin components may be copolymers used in the present invention, and other polymers may be mixed with the copolymer of the present invention.
  • the content of the other polymer in the resin component is 0.5% by mass to 15% by mass, preferably 1% by mass to 10% by mass.
  • examples of such other polymers include polyamic acid or polyimide obtained by using a diamine other than the diamine compound (A) and the diamine compound (B) as the diamine component to be reacted with the tetracarboxylic dianhydride component. It is done.
  • 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 the resin component mentioned above is dissolved. Specific examples are given below.
  • Examples include
  • heating may be performed for the purpose of promoting dissolution of the polyimide. Since the molecular weight of a polyimide may fall when the temperature to heat is too high, the temperature of 30-100 degreeC is preferable.
  • the liquid crystal aligning agent of the present invention may contain components other than those described above. Examples thereof include solvents and compounds that improve the film thickness uniformity and surface smoothness when a liquid crystal aligning agent is applied, and compounds that improve the adhesion between the liquid crystal aligning film and the substrate.
  • These poor solvents may be used alone or in combination.
  • it is preferable that it is 5 to 80 mass% of the whole solvent contained in a liquid crystal aligning agent, More preferably, it is 20 to 60 mass%.
  • compounds that improve film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.
  • 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 mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the resin component contained in the liquid crystal aligning agent.
  • the compound that improves the adhesion between the liquid crystal alignment film and the substrate include the following functional silane-containing compounds and epoxy group-containing compounds.
  • the amount used is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the resin component contained in the liquid crystal aligning agent.
  • the amount is preferably 1 to 20 parts by mass. If the amount is less than 0.1 part by mass, the effect of improving the adhesion cannot be expected, and if it exceeds 30 parts by mass, the orientation of the liquid crystal may deteriorate.
  • liquid crystal aligning agent of the present invention in addition to the above, as long as the effects of the present invention are not impaired, a dielectric or conductive material for the purpose of changing electrical characteristics such as dielectric constant or conductivity of the liquid crystal aligning film, Furthermore, a crosslinkable compound for the purpose of increasing the hardness and density of the film when the liquid crystal alignment film is formed may be added.
  • the liquid crystal aligning agent of the present invention can be used as a liquid crystal alignment film after being applied and baked on a substrate and then subjected to alignment treatment by rubbing treatment, light irradiation or the like, or without alignment treatment in vertical alignment applications.
  • 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 material such as a silicon wafer can be used as long as the substrate is only on one side, and in this case, a material that reflects light such as aluminum can be used.
  • the application method of the liquid crystal aligning agent is not particularly limited, but industrially, a method of screen printing, offset printing, flexographic printing, ink jet, or the like is common. Other coating methods include dip, roll coater, slit coater, spinner and the like, and these may be used depending on the purpose.
  • Calcination after applying the liquid crystal aligning agent on the substrate can form a coating film by evaporating the solvent at 50 to 300 ° C., preferably 80 to 250 ° C., by a heating means such as a hot plate. 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. Therefore, it is preferably 5 to 300 nm, more preferably 10 to 100 nm. When the liquid crystal is horizontally or tilted, the fired coating film is treated by 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 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 liquid crystal cell production prepare a pair of substrates on which a liquid crystal alignment film is formed, spread a spacer on the liquid crystal alignment film of one substrate, and make the liquid crystal alignment film surface inside, Examples include a method in which the other substrate is attached and liquid crystal is injected under reduced pressure, or a method in which the substrate is attached to the surface after the liquid crystal is dropped on the liquid crystal alignment film surface on which spacers are dispersed, and the like is sealed.
  • 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 manufactured using the liquid crystal aligning agent of the present invention has excellent reliability and can be suitably used for a large-screen high-definition liquid crystal television.
  • PCH7DAB 1,3-diamino-4- [4- (4-heptylcyclohexyl) phenoxy] benzene
  • DBA 3,5-diaminobenzoic acid
  • 2,4-DAA 2,4-diamino-N, N-diallylaniline
  • Me —DADPA N-methyl-4,4′-diaminodiphenylamine diamine (1): (see formula below)
  • the molecular weight of the polyimide in the synthesis example was measured as follows using a normal temperature gel permeation chromatography (GPC) apparatus (GPC-101) manufactured by Showa Denko KK and a column (KD-803, KD-805) manufactured by Shodex.
  • GPC normal temperature gel permeation chromatography
  • the imidation ratio of polyimide in the synthesis example was measured as follows. Add 20 mg of polyimide powder to an NMR sample tube (NMR sampling tube standard ⁇ 5 manufactured by Kusano Kagaku Co., Ltd.) and add 0.53 ml of deuterated dimethyl sulfoxide (DMSO-d6, 0.05% TMS (tetramethylsilane) mixture). The solution was completely dissolved by applying ultrasonic waves. This solution was measured for proton NMR at 500 MHz with an NMR measuring instrument (JNW-ECA500) manufactured by JEOL Datum.
  • JNW-ECA500 JNW-ECA500
  • 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 proton peaks derived from NH groups of amic acid appearing near 9.5 to 10.0 ppm. It calculated
  • 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.
  • CBDA (9.7 g, 50 mmol), 2,4-DAA (2.0 g, 10 mmol), DBA (3.8 g, 25 mmol), and PCH7DAB (5.7 g, 15 mmol) were mixed in NMP (85.0 g). And reacted at 23 ° C. for 20 hours to obtain a polyamic acid solution. After adding NMP to this polyamic acid solution (50.5 g) and diluting to 6% by mass, acetic anhydride (7.2 g) and pyridine (3.2 g) were added as an imidization catalyst and reacted at 50 ° C. for 3 hours. It was.
  • This reaction solution was put into methanol (630 ml), and the resulting precipitate was separated by filtration. This deposit was wash
  • the imidation ratio of this polyimide was 92%, the number average molecular weight was 18,700, and the weight average molecular weight was 46,400.
  • polyimide powder [I] This precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder [I].
  • the imidation ratio of this polyimide was 97%, the number average molecular weight was 18,300, and the weight average molecular weight was 44,200.
  • a liquid crystal alignment film having a thickness of 100 nm was prepared. After preparing two substrates with the liquid crystal alignment film and spraying a spacer of 6 ⁇ m on the surface of the liquid crystal alignment film, the sealant is printed and bonded together, and then the sealant is cured to be emptied. A cell was produced. A liquid crystal MLC-6608 (manufactured by Merck Japan Co., Ltd.) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain a nematic liquid crystal cell. [Evaluation of voltage holding ratio] A voltage of 4 V was applied to the liquid crystal cell produced above at a temperature of 80 ° C.
  • Example 2 NMP (24.4 g) was added to the polyimide powder [B] (5.0 g) obtained in Synthesis Example 2, and dissolved by stirring at 70 ° C. for 40 hours. NMP (12.3g) and BCS (41.7g) were added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained liquid crystal aligning agent [2]. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal aligning agent [2], a liquid crystal cell was produced in the same manner as in Example 1, and evaluation of voltage holding ratio, evaluation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Tables 2 and 3 below.
  • Example 3 NMP (24.5 g) was added to the polyimide powder [C] (5.1 g) obtained in Synthesis Example 3, and dissolved by stirring at 70 ° C. for 40 hours. NMP (23.9g) and BCS (30.0g) were added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained liquid crystal aligning agent [3]. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal aligning agent [3], a liquid crystal cell was produced in the same manner as in Example 1, and evaluation of voltage holding ratio, evaluation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Tables 2 and 3 below.
  • Example 4 NMP (25.0 g) was added to the polyimide powder [D] (5.0 g) obtained in Synthesis Example 4, and dissolved by stirring at 70 ° C. for 40 hours. NMP (20.1g) and BCS (33.2g) were added to this solution, and the liquid crystal aligning agent [4] was obtained by stirring at 25 degreeC for 2 hours. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal aligning agent [4], a liquid crystal cell was produced in the same manner as in Example 1, and evaluation of voltage holding ratio, evaluation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Tables 2 and 3 below.
  • Example 5 NMP (24.5 g) was added to the polyimide powder [E] (4.9 g) obtained in Synthesis Example 5 and dissolved by stirring at 70 ° C. for 40 hours. NMP (29.0g) and BCS (25.3g) were added to this solution, and the liquid crystal aligning agent [5] was obtained by stirring at 25 degreeC for 2 hours. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal aligning agent [5], a liquid crystal cell was produced in the same manner as in Example 1, and evaluation of voltage holding ratio, evaluation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Tables 2 and 3 below.
  • Example 6 NMP (25.0 g) was added to the polyimide powder [F] (5.0 g) obtained in Synthesis Example 6, and dissolved by stirring at 70 ° C. for 40 hours. NMP (11.5g) and BCS (42.9g) were added to this solution, and the liquid crystal aligning agent [6] was obtained by stirring at 25 degreeC for 2 hours. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal aligning agent [6], a liquid crystal cell was prepared in the same manner as in Example 1, and evaluation of voltage holding ratio, evaluation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Tables 2 and 3 below.
  • the liquid crystal aligning agent of the present invention can provide a liquid crystal alignment film having a high voltage holding ratio and a small residual charge accumulated by a DC voltage even after being exposed to a high temperature for a long time.
  • the liquid crystal display element thus obtained can suppress display defects such as screen burn-in and display unevenness even when used for a long time, has excellent reliability, and is suitable for large-screen, high-definition liquid crystal televisions, etc.

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Abstract

L'invention porte sur un matériau d'alignement de cristaux liquides susceptible de fournir un film d'alignement de cristaux liquides ayant une retenue de tension élevée et qui, même après avoir été exposé à une atmosphère de température élevée pendant une longue période de temps, est réduite en termes de charge résiduelle accumulée par tension continue. L'invention porte également sur un élément d'affichage à cristaux liquides utilisant le film d'alignement de cristaux liquides. Le matériau d'alignement de cristaux liquides comporte un copolymère obtenu en faisant réagir un ingrédient d'hydrazine comprenant au moins un composé d'hydrazine (A) et un composé de diazane (B) avec un dianhydride tétracarboxylique. Le composé d'hydrazine (A) est au moins un composé sélectionné dans le groupe constitué par des composés représentés par les formules [T1], [T2], et [T3], lesquels sont des composés d'hydrazine disposant d'un atome d'azote tertiaire. Le composé de diazane (B) est un composé d'hydrazine doté d'un groupe carboxylique dans la molécule. (Formule chimique 1) [T1] [T2] [T3] (Dans les formules [T1] à [T3], W1 est un cycle benzénique ou un hétérocycle aromatique azoté ; W2 est un groupe aromatique possédant 6 à 15 atomes de carbone et ayant un ou deux cycles benzéniques ; W3 est un alkylène en C2-5 ou un biphénylène; W4 est un cycloalkylène présentant 4 à 6 atomes de carbone et étant substitué par un atome d'azote tertiaire ; W5 est un alkylène en C2-5 ; Z1 est un amino substitué par deux groupes aliphatiques en C1-6 lorsque W1 est un cycle benzénique, ou Z1 est un hydrogène ou un amino substitué par deux groupes aliphatiques en C1-6 lorsque W1 est un hétérocycle aromatique azoté; Z2 est un alkyle en C1-5 ou un cycle benzénique; et g est un nombre entier égal à 0 ou 1.)
PCT/JP2009/051116 2008-01-25 2009-01-23 Matériau d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides Ceased WO2009093709A1 (fr)

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