WO2009093709A1 - Liquid-crystal alignment material, liquid-crystal alignment film, and liquid-crystal display element - Google Patents
Liquid-crystal alignment material, liquid-crystal alignment film, and liquid-crystal display element Download PDFInfo
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- 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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- 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
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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
- C08G73/1046—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
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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
- C08G73/1075—Partially aromatic polyimides
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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
- C08G73/1075—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
Description
更には、本発明は過酷な使用環境での長期使用に耐えうる信頼性の高い液晶表示素子を提供することにある。 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.
(1)ジアミン化合物(A)及びジアミン化合物(B)を含むジアミン成分とテトラカルボン酸二無水物とを反応させて得られる共重合体を含有する液晶配向剤。
ジアミン化合物(A):下記の式[T1]、式[T2]及び式[T3]からなる群より選ばれる少なくとも一種である、3級窒素原子を有するジアミン化合物、
ジアミン化合物(B):分子内にカルボキシル基を有するジアミン化合物。 The inventor has conducted extensive research to achieve the above object, and has found a liquid crystal aligning agent that achieves this. The present invention is based on such knowledge and has the following gist.
(1) 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.
Diamine compound (A): a diamine compound having a tertiary nitrogen atom, which is at least one selected from the group consisting of the following formula [T1], formula [T2] and formula [T3],
Diamine compound (B): a diamine compound having a carboxyl group in the molecule.
(2)ジアミン化合物(A)が下記の式[1]から式[4]で表される化合物である上記(1)に記載の液晶配向剤。 (In the formulas [T1] to [T3], W 1 is a benzene ring or a nitrogen-containing aromatic heterocyclic ring, and 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, and W 5 is having 2 to 5 carbon atoms. 5 is alkylene, 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 A di-substituted amino group substituted with a hydrogen atom or an aliphatic group having 1 to 6 carbon atoms, Z 2 is an alkyl group having 1 to 5 carbon atoms or a benzene ring, and g is an integer of 0 or 1; )
(2) The liquid crystal aligning agent as described in said (1) whose diamine compound (A) is a compound represented by following formula [1] to formula [4].
(3)ジアミン化合物(A)が、式[1]又は式[2]である上記(2)に記載の液晶配向剤。
(4)式[3]のA2が、ベンゼン環又は下記の式[3a]である上記(2)に記載の液晶配向剤。
(3) The liquid crystal aligning agent as described in said (2) whose diamine compound (A) is Formula [1] or Formula [2].
(4) [3] A 2 is, the liquid crystal alignment agent according to the above (2) is a benzene ring or the following formula [3a].
(5)ジアミン化合物(A)が、下記の式[5]から18]からなる群より選ばれる少なくとも一種のジアミン化合物である上記(1)又は上記(2)に記載の液晶配向剤。
(5) The liquid crystal aligning agent according to (1) or (2), wherein the diamine compound (A) is at least one diamine compound selected from the group consisting of the following formulas [5] to 18].
(6)ジアミン化合物(B)が、下記の式[19]で表されるジアミン化合物である上記(1)から上記(5)のいずれか一項に記載の液晶配向剤。
(6) The liquid crystal aligning agent as described in any one of said (1) to said (5) whose diamine compound (B) is a diamine compound represented by following formula [19].
(7)ジアミン化合物(B)が、下記の式[20]から式[24]より選ばれるジアミン化合物である上記(6)に記載の液晶配向剤。
(7) The liquid crystal aligning agent as described in said (6) whose diamine compound (B) is a diamine compound chosen from following formula [20] to formula [24].
(8)式[20]中、m1が1から2の整数である上記(7)に記載の液晶配向剤。
(9)式[21]中、X2が単結合、-CH2-、-C2H4-、-C(CH3)2-、-O-、-CO-、-NH-、-N(CH3)-、-CONH-、-NHCO-、-COO-、又は-OCO-であり、m2、m3は共に1の整数である上記(7)に記載の液晶配向剤。
(10)式[24]中、X4は単結合、-CH2-、-O-、-CO-、-NH-、-CONH-、-NHCO-、-CH2O-、-OCH2-、-COO-、又は-OCO-であり、m7は1から2の整数である上記(7)に記載の液晶配向剤。
(11)ジアミン成分中におけるジアミン化合物(B)の含有量が、ジアミン化合物(A)の1モルに対して、0.01から99モルである上記(1)から上記(10)のいずれか一項に記載の液晶配向剤。
(12)液晶配向剤中に含まれる溶媒中の5から80質量%が貧溶媒である上記(1)から上記(11)のいずれか一項に記載の液晶配向剤。
(13)液晶配向剤中の共重合体がポリアミド酸を脱水閉環させて得られるポリイミドである上記(1)から上記(12)のいずれか一項に記載の液晶配向剤。
(14)上記(1)から上記(13)のいずれか一項に記載の液晶配向剤を用いて得られる液晶配向膜。
(15)上記(14)に記載の液晶配向膜を有する液晶表示素子。 (In the formula [20], m1 is an integer of 1 to 4, and in the formula [21], 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, and 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 1 to 5, and in formula [24], X 4 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-, and m7 is an integer of 1 to 4.)
(8) The liquid crystal aligning agent as described in said (7) whose m1 is an integer of 1 to 2 in Formula [20].
(9) In the formula [21], 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.
(10) In the formula [24], X 4 represents a single bond, —CH 2 —, —O—, —CO—, —NH—, —CONH—, —NHCO—, —CH 2 O—, —OCH 2 —. , —COO—, or —OCO—, and m7 is an integer of 1 to 2, according to (7) above.
(11) 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.
(12) The liquid crystal aligning agent according to any one of (1) to (11) above, wherein 5 to 80% by mass in the solvent contained in the liquid crystal aligning agent is a poor solvent.
(13) The liquid crystal aligning agent according to any one of (1) to (12) above, wherein the copolymer in the liquid crystal aligning agent is a polyimide obtained by dehydrating and ring-closing polyamic acid.
(14) A liquid crystal alignment film obtained by using the liquid crystal aligning agent according to any one of (1) to (13).
(15) A liquid crystal display device having the liquid crystal alignment film according to (14).
本発明に用いるジアミン化合物(A)は、式[T1]から式[T3]で表される3級窒素原子を有するジアミン化合物である。本発明において3級窒素原子とは、窒素原子の3つの結合手が水素原子以外の原子、好ましくは炭素原子と結合した窒素原子を意味する。 <Diamine component>
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]. In the present invention, 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.
本発明に用いるジアミン化合物(A)は、下記の式[T1]、式[T2]及び式[T3]からなる群より選ばれる少なくとも一種の化合物である、3級窒素原子を有するジアミン化合物である。 [Diamine compound (A)]
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]. .
式[T1]から式[T3]で表されるジアミン化合物の中で、好ましい化合物としては、下記の式[1]から式[4]のジアミン化合物が挙げられる。 In the formulas [T1] to [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, and 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 A disubstituted amino group substituted with an atom or an aliphatic group having 1 to 6 carbon atoms, Z 2 is an alkyl group having 1 to 5 carbon atoms or a benzene ring, and g is an integer of 0 or 1.
Among the diamine compounds represented by the formulas [T1] to [T3], preferable compounds include the diamine compounds of the following formulas [1] to [4].
式[3]におけるA2は、好ましくは、ベンゼン環又は式[3a]で表される構造である。
A 2 in Formula [3] is preferably a benzene ring or a structure represented by Formula [3a].
式[3]の好ましい具体例を示すと、下記の式[15]から[17]のジアミン化合物が挙げられる。
Preferable specific examples of the formula [3] include diamine compounds of the following formulas [15] to [17].
式[4]におけるA4は式[4a]又は式[4b]で表される基であり、A5は炭素数2から5のアルキレンである。
式[4]の好ましい具体例は、下記の式[18]のジアミン化合物が挙げられる。
A 4 in Formula [4] is a group represented by Formula [4a] or Formula [4b], and 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].
本発明においては、ジアミン化合物(A)は、1種単独でも、又は複数種を組み合わせて用いることもできる。
In this invention, a diamine compound (A) can also be used individually by 1 type or in combination of multiple types.
本発明に用いるジアミン化合物(B)は、分子内にカルボキシル基を有するジアミン化合物である。好ましくは、分子内にカルボキシル基を1から4個有する化合物である。ジアミン化合物(B)の構造は特に限定されないが、好ましくは、式[19]で表されるジアミン化合物である。 [Diamine compound (B)]
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. Although the structure of a diamine compound (B) is not specifically limited, Preferably, it is a diamine compound represented by Formula [19].
式[19]の好ましい構造としては、下記の式[20]から[24]の構造が挙げられる。
Preferred structures of the formula [19] include the structures of the following formulas [20] to [24].
好ましくは、式[20]中、m1が1から2の整数である構造、式[21]中、X2が単結合、-CH2-、-C2H4-、-C(CH3)2-、-O-、-CO-、-NH-、-N(CH3)-、-CONH-、-NHCO-、-COO-、又は-OCO-であり、m2及びm3は共に1の整数である構造、式[24]中、X4は単結合、-CH2-、-O-、-CO-、-NH-、-CONH-、-NHCO-、-CH2O-、-OCH2-、-COO-、又は-OCO-であり、m7は1から2の整数である構造である。なかでも、式[20]で表される構造が特に好ましい。 In the formula [20], m1 is an integer of 1 to 4, and in the formula [21], 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, and 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 4 is a single bond, —CH 2 —, —C 2 H 4 —, —C (CH 3 ) 2 —, —CF 2 in the formula [24]. —, —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—, and m7 is an integer of 1 to 4.
Preferably, in the formula [20], m1 is an integer of 1 to 2, and in the formula [21], 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—, each of m2 and m3 is an integer of 1 Wherein 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. Especially, the structure represented by Formula [20] is especially preferable.
本発明においては、本発明の効果を損なわない限りにおいて、ジアミン化合物(A)、ジアミン化合物(B)以外のその他のジアミン化合物を、ジアミン成分として併用することができる。その具体例を以下に挙げる。 [Other diamine compounds]
In this invention, unless the effect of this invention is impaired, other diamine compounds other than a diamine compound (A) and a diamine compound (B) can be used together as a diamine component. Specific examples are given below.
本発明に用いるテトラカルボン酸二無水物は、テトラカルボン酸二無水物のうちの少なくとも一種の化合物であればよい。以下に具体例を挙げる。 <Tetracarboxylic dianhydride>
The tetracarboxylic dianhydride used in the present invention may be at least one compound of tetracarboxylic dianhydrides. Specific examples are given below.
本発明に用いる共重合体はポリアミド酸及びポリイミドである。ポリアミド酸は、ジアミン化合物(A)及びジアミン化合物(B)を含有するジアミン成分と、テトラカルボン酸二無水物との反応によって得られるポリアミド酸である。本発明のポリイミドはこのポリアミド酸を脱水閉環させて得られるポリイミドである。かかるポリアミド酸及びポリイミドのいずれも液晶配向剤を得るための共重合体として有用である。 <Copolymer>
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.
そして、ジアミン化合物(B)は前記の効果をより高める効果を奏する。ジアミン成分中におけるジアミン化合物(B)の含有量は、ジアミン化合物(A)の1モルに対して、0.01から99モルであることが好ましい。より好ましくは0.1から50モルであり、更に好ましくは0.5から20モルであり、最も好ましくは0.5から10モルである。 The higher the content of the diamine compound (A) in the diamine component, the higher the voltage holding ratio, and the less the residual charge that accumulates due to DC voltage, even after being exposed to a high temperature for a long time.
And a diamine compound (B) has an effect which raises the above-mentioned effect more. 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.
本発明に用いるポリアミド酸は、公知の重合方法を用いることによって得ることができる。一般的には、テトラカルボン酸二無水物とジアミン成分とを有機溶媒中で反応させる方法である。テトラカルボン酸二無水物とジアミン成分との反応は、有機溶媒中で比較的容易に進行し、かつ副生成物が生成しない点で有利である。
その際に用いる有機溶媒は、生成したポリアミド酸が溶解するものであれば良い。以下にその具体例を挙げる。 [Method for producing copolymer]
The polyamic acid used in the present invention can be obtained by using a known polymerization method. In general, 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 | generated polyamic acid melt | dissolves. Specific examples are given below.
本発明に用いるポリイミドにおいて、アミド酸基の脱水閉環率(イミド化率)は、必ずしも100%である必要はなく、用途や目的に応じて任意に調整して用いることができる。 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.
In the polyimide used in the present invention, 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.
ポリアミド酸を溶液中で熱イミド化させる場合の温度は、100℃から400℃、好ましくは120℃から250℃であり、イミド化反応により生成する水を系外に除きながら行う方が好ましい。
ポリアミド酸の触媒イミド化は、ポリアミド酸の溶液に、塩基性触媒と酸無水物とを添加し、-20から250℃、好ましくは0から180℃で攪拌することにより行うことができる。塩基性触媒の量はアミド酸基の0.5から30モル倍、好ましくは2から20モル倍であり、酸無水物の量はアミド酸基の1から50モル倍、好ましくは3から30モル倍である。 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.
本発明の液晶配向剤は、液晶配向膜を作製するための塗布液であり、その主成分が、樹脂被膜を形成するための樹脂成分と、この樹脂成分を溶解させる有機溶媒とからなる。本発明においては、前記の樹脂成分は、上記した本発明に用いるポリアミド酸及びポリイミドからなる群から選ばれる少なくとも一種の共重合体を含む樹脂成分である。その際、塗布液中の樹脂成分の含有量は1質量%から20質量%、好ましくは2質量%から10質量%である。 <Liquid crystal aligning agent>
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. In the present invention, 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. In that case, content of the resin component in a coating liquid is 1 mass% to 20 mass%, Preferably it is 2 mass% to 10 mass%.
かかる他の重合体は、例えば、テトラカルボン酸二無水物成分と反応させるジアミン成分として、ジアミン化合物(A)とジアミン化合物(B)以外のジアミンを使用して得られるポリアミド酸又はポリイミドなどが挙げられる。 In the present invention, 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. At that time, 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.
例えば、N,N’-ジメチルホルムアミド、N,N’-ジメチルアセトアミド、N-メチル-2-ピロリドン、N-メチルカプロラクタム、2-ピロリドン、N-エチルピロリドン、N-ビニルピロリドン、ジメチルスルホキシド、テトラメチル尿素、ピリジン、ジメチルスルホン、ヘキサメチルスルホキシド、γ-ブチロラクトン、1,3-ジメチル-イミダゾリジノン、ジペンテン、エチルアミルケトン、メチルノニルケトン、メチルエチルケトン、メチルイソアミルケトン、メチルイソプロピルケトン、シクロヘキサノン、エチレンカーボネート、プロピレンカーボネート、ジグライム、4-ヒドロキシ-4-メチル-2-ペンタノンなどが挙げられる。これらの溶媒は2種類以上を混合して用いてもよい。 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.
For example, N, N′-dimethylformamide, N, N′-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethyl sulfoxide, tetramethyl Urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, Examples include propylene carbonate, diglyme and 4-hydroxy-4-methyl-2-pentanone. Two or more kinds of these solvents may be mixed and used.
例えば、イソプロピルアルコール、メトキシメチルペンタノール、メチルセロソルブ、エチルセロソルブ、ブチルセロソルブ、メチルセロソルブアセテート、エチルセロソルブアセテート、ブチルカルビトール、エチルカルビトール、エチルカルビトールアセテート、エチレングリコール、エチレングリコールモノアセテート、エチレングリコールモノイソプロピルエーテル、エチレングリコールモノブチルエーテル、プロピレングリコール、プロピレングリコールモノアセテート、プロピレングリコールモノメチルエーテル、プロピレングリコール-tert-ブチルエーテル、ジプロピレングリコールモノメチルエーテル、ジエチレングリコール、ジエチレングリコールモノアセテート、ジエチレングリコールジメチルエーテル、ジプロピレングリコールモノアセテートモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノアセテートモノエチルエーテル、ジプロピレングリコールモノプロピルエーテル、ジプロピレングリコールモノアセテートモノプロピルエーテル、3-メチル-3-メトキシブチルアセテート、トリプロピレングリコールメチルエーテル、3-メチル-3-メトキシブタノール、ジイソプロピルエーテル、エチルイソブチルエーテル、ジイソブチレン、アミルアセテート、ブチルブチレート、ブチルエーテル、ジイソブチルケトン、メチルシクロへキセン、プロピルエーテル、ジヘキシルエーテル、n-へキサン、n-ペンタン、n-オクタン、ジエチルエーテル、乳酸メチル、乳酸エチル、酢酸メチル、酢酸エチル、酢酸n-ブチル、酢酸プロピレングリコールモノエチルエーテル、ピルビン酸メチル、ピルビン酸エチル、3-メトキシプロピオン酸メチル、3-エトキシプロピオン酸メチルエチル、3-メトキシプロピオン酸エチル、3-エトキシプロピオン酸、3-メトキシプロピオン酸、3-メトキシプロピオン酸プロピル、3-メトキシプロピオン酸ブチル、1-メトキシ-2-プロパノール、1-ヘキサノール、1-エトキシ-2-プロパノール、1-ブトキシ-2-プロパノール、1-フェノキシ-2-プロパノール、プロピレングリコールモノアセテート、プロピレングリコールジアセテート、プロピレングリコール-1-モノメチルエーテル-2-アセテート、プロピレングリコール-1-モノエチルエーテル-2-アセテート、ジプロピレングリコール、2-(2-エトキシプロポキシ)プロパノール、乳酸メチルエステル、乳酸エチルエステル、乳酸n-プロピルエステル、乳酸n-ブチルエステル、乳酸イソアミルエステルなどの低表面張力を有する溶媒などが挙げられる。
これらのうちで、ブチルセロソルブ、プロピレングリコールモノメチルエーテル、乳酸エチルがより好ましい。 Specific examples of the solvent (poor solvent) that improves the uniformity of the film thickness and the surface smoothness include the following.
For example, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoacetate Isopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipro Lenglycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3 -Methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl Ether, n-hexane, n-pentane, n-octane, diethyl ether Methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, 3-methoxy Ethyl propionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-hexanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol- Low 1-monoethyl ether-2-acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, lactate methyl ester, lactate ethyl ester, lactate n-propyl ester, lactate n-butyl ester, lactate isoamyl ester Examples include solvents having surface tension.
Of these, butyl cellosolve, propylene glycol monomethyl ether, and ethyl lactate are more preferable.
膜厚の均一性や表面平滑性を向上させる化合物としては、フッ素系界面活性剤、シリコーン系界面活性剤、ノ二オン系界面活性剤などが挙げられる。
より具体的には、例えば、エフトップEF301、EF303、EF352(トーケムプロダクツ社製))、メガファックF171、F173、R-30(大日本インキ社製)、フロラードFC430、FC431(住友スリーエム社製)、アサヒガードAG710、サーフロンS-382、SC101、SC102、SC103、SC104、SC105、SC106(旭硝子社製)などが挙げられる。これらの界面活性剤の使用割合は、液晶配向剤に含有される樹脂成分の100質量部に対して、好ましくは0.01から2質量部、より好ましくは0.01から1質量部である。 These poor solvents may be used alone or in combination. When using the above solvent, 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%.
Examples of compounds that improve film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.
More specifically, for example, F-top EF301, EF303, EF352 (manufactured by Tochem Products), MegaFuck F171, F173, R-30 (manufactured by Dainippon Ink), Florard FC430, FC431 (manufactured by Sumitomo 3M) ), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.). The use ratio of these surfactants is preferably 0.01 to 2 parts by 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.
例えば、3-アミノプロピルトリメトキシシラン、3-アミノプロピルトリエトキシシラン、2-アミノプロピルトリメトキシシラン、2-アミノプロピルトリエトキシシラン、N-(2-アミノエチル)-3-アミノプロピルトリメトキシシラン、N-(2-アミノエチル)-3-アミノプロピルメチルジメトキシシラン、3-ウレイドプロピルトリメトキシシラン、3-ウレイドプロピルトリエトキシシラン、N-エトキシカルボニル-3-アミノプロピルトリメトキシシラン、N-エトキシカルボニル-3-アミノプロピルトリエトキシシラン、N-トリエトキシシリルプロピルトリエチレントリアミン、N-トリメトキシシリルプロピルトリエチレントリアミン、10-トリメトキシシリル-1,4,7-トリアザデカン、10-トリエトキシシリル-1,4,7-トリアザデカン、9-トリメトキシシリル-3,6-ジアザノニルアセテート、9-トリエトキシシリル-3,6-ジアザノニルアセテート、N-ベンジル-3-アミノプロピルトリメトキシシラン、N-ベンジル-3-アミノプロピルトリエトキシシラン、N-フェニル-3-アミノプロピルトリメトキシシラン、N-フェニル-3-アミノプロピルトリエトキシシラン、N-ビス(オキシエチレン)-3-アミノプロピルトリメトキシシラン、N-ビス(オキシエチレン)-3-アミノプロピルトリエトキシシラン、エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、トリプロピレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、1,6-ヘキサンジオールジグリシジルエーテル、グリセリンジグリシジルエーテル、2,2-ジブロモネオペンチルグリコールジグリシジルエーテル、1,3,5,6-テトラグリシジル-2,4-ヘキサンジオール、N,N,N’,N’,-テトラグリシジル-m-キシレンジアミン、1,3-ビス(N,N-ジグリシジルアミノメチル)シクロヘキサン、N,N,N’,N’,-テトラグリシジル-4、4’-ジアミノジフェニルメタンなどが挙げられる。 Specific examples of the compound that improves the adhesion between the liquid crystal alignment film and the substrate include the following functional silane-containing compounds and epoxy group-containing compounds.
For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxy Carbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-to Ethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltri Methoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-amino Propyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether , Polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetra Glycidyl-2,4-hexanediol, N, N, N ′, N ′,-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N Examples include ', N',-tetraglycidyl-4,4'-diaminodiphenylmethane.
本発明の液晶配向剤は、基板上に塗布、焼成した後、ラビング処理や光照射などで配向処理をして、又は垂直配向用途などでは配向処理無しで液晶配向膜として用いることができる。この際、用いる基板としては透明性の高い基板であれば特に限定されず、ガラス基板、アクリル基板やポリカーボネート基板などのプラスチック基板などを用いることができる。また、液晶駆動のためのITO電極などが形成された基板を用いることがプロセスの簡素化の観点から好ましい。また、反射型の液晶表示素子では片側の基板のみにならばシリコンウエハー等の不透明な物でも使用でき、この場合の電極はアルミ等の光を反射する材料も使用できる。
液晶配向剤の塗布方法は特に限定されないが、工業的には、スクリーン印刷、オフセット印刷、フレキソ印刷、インクジェットなどで行う方法が一般的である。その他の塗布方法としては、ディップ、ロールコーター、スリットコーター、スピンナーなどがあり、目的に応じてこれらを用いてもよい。 <Liquid crystal alignment film / liquid crystal display element>
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. In this case, the substrate to be used is not particularly limited as long as it is a highly transparent substrate, and a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like can be used. In addition, it is preferable to use a substrate on which an ITO electrode or the like for driving liquid crystal is formed from the viewpoint of simplifying the process. Further, in the reflection type liquid crystal display element, 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.
液晶セル作製の一例を挙げると、液晶配向膜の形成された1対の基板を用意し、片方の基板の液晶配向膜上にスペーサーを散布し、液晶配向膜面が内側になるようにして、もう片方の基板を貼り合わせ、液晶を減圧注入して封止する方法、又は、スペーサーを散布した液晶配向膜面に液晶を滴下した後に基板を貼り合わせて封止を行う方法などが例示できる。このときのスペーサーの厚みは、好ましくは1から30μm、より好ましくは2から10μmである。
以上のようにして、本発明の液晶配向剤を用いて作製された液晶表示素子は、信頼性に優れたものとなり、大画面で高精細の液晶テレビなどに好適に利用できる。 The liquid crystal display element of the present invention is a liquid crystal display element obtained by obtaining a substrate with a liquid crystal alignment film from the liquid crystal aligning agent of the present invention by the method described above, and then preparing a liquid crystal cell by a known method.
As an example of liquid crystal cell production, 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 μm, more preferably 2 to 10 μm.
As described above, 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.
以下に、実施例で使用した化合物の略号と構造式を示す。
(テトラカルボン酸二無水物)
CBDA:1,2,3,4-シクロブタンテトラカルボン酸二無水物
BODA:ビシクロ[3,3,0]オクタン-2,4,6,8-テトラカルボン酸二無水物 EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples, but the interpretation of the present invention is not limited to these examples.
The abbreviations and structural formulas of the compounds used in the examples are shown below.
(Tetracarboxylic dianhydride)
CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride BODA: bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride
PCH7DAB:1,3-ジアミノ-4-〔4-(4-ヘプチルシクロヘキシル)フェノキシ〕ベンゼン
DBA:3,5-ジアミノ安息香酸
2,4-DAA:2,4-ジアミノ-N,N-ジアリルアニリン
Me-DADPA:N-メチル-4,4’-ジアミノジフェニルアミン
ジアミン(1):(下記式参照)
ジアミン(2):(下記式参照)
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)
Diamine (2): (see formula below)
NMP:N-メチル-2-ピロリドン
BCS:ブチルセロソルブ
NMP: N-methyl-2-pyrrolidone BCS: Butyl cellosolve
合成例におけるポリイミドの分子量は、昭和電工社製 常温ゲル浸透クロマトグラフィー(GPC)装置(GPC-101)、Shodex社製カラム(KD-803、KD-805)を用い以下のようにして測定した。
カラム温度:50℃
溶離液:N,N’-ジメチルホルムアミド(添加剤として、臭化リチウム-水和物(LiBr・H2O)が30mmol/L、リン酸・無水結晶(o-リン酸)が30mmol/L、テトラヒドロフラン(THF)が10ml/L)
流速:1.0ml/分
検量線作成用標準サンプル:東ソー社製 TSK 標準ポリエチレンオキサイド(分子量900,000、150,000、100,000、30,000)、および、ポリマーラボラトリー社製 ポリエチレングリコール(分子量約12,000、4,000、1,000)。 <Molecular weight measurement>
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.
Column temperature: 50 ° C
Eluent: N, N′-dimethylformamide (as additives, lithium bromide-hydrate (LiBr · H 2 O) is 30 mmol / L, phosphoric acid / anhydrous crystal (o-phosphoric acid) is 30 mmol / L, Tetrahydrofuran (THF) 10ml / L)
Flow rate: 1.0 ml / min Standard sample for preparing a calibration curve: TSK standard polyethylene oxide (molecular weight 900,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation and polyethylene glycol (molecular weight manufactured by Polymer Laboratory) About 12,000, 4,000, 1,000).
合成例におけるポリイミドのイミド化率は次のようにして測定した。ポリイミド粉末20mgをNMRサンプル管(草野科学社製 NMRサンプリングチューブスタンダード φ5)に入れ、重水素化ジメチルスルホキシド(DMSO-d6、0.05%TMS(テトラメチルシラン)混合品)0.53mlを添加し、超音波をかけて完全に溶解させた。この溶液を日本電子データム社製NMR測定器(JNW-ECA500)にて500MHzのプロトンNMRを測定した。イミド化率は、イミド化前後で変化しない構造に由来するプロトンを基準プロトンとして決め、このプロトンのピーク積算値と、9.5から10.0ppm付近に現れるアミド酸のNH基に由来するプロトンピーク積算値とを用い以下の式によって求めた。
イミド化率(%)=(1-α・x/y)×100
上記式において、xはアミド酸のNH基由来のプロトンピーク積算値、yは基準プロトンのピーク積算値、αはポリアミド酸(イミド化率が0%)の場合におけるアミド酸のNH基プロトン1個に対する基準プロトンの個数割合である。 <Measurement of imidization ratio>
The 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 φ5 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. 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 | required by the following formula | equation using the integrated value.
Imidization rate (%) = (1−α · x / y) × 100
In the above formula, x is a proton peak integrated value derived from NH group of amic acid, y is a peak integrated value of reference proton, α is one NH group proton of amic acid in the case of polyamic acid (imidation rate is 0%) Is the number ratio of the reference proton to.
BODA(18.8g,75mmol)、Me-DADPA(6.3g,30mmol)、DBA(6.1g,40mmol)、及びPCH7DAB(11.4g,30mmol)をNMP(114.0g)中で混合し、40℃で3時間反応させた後、CBDA(4.8g,25mmol)とNMP(76.0g)を加え、40℃で12時間反応させて樹脂含有量20質量%のポリアミド酸溶液[A]を得た。このポリアミド酸溶液の数平均分子量は28,100、重量平均分子量は72,300であった。 <Synthesis Example 1>
BODA (18.8 g, 75 mmol), Me-DADPA (6.3 g, 30 mmol), DBA (6.1 g, 40 mmol), and PCH7DAB (11.4 g, 30 mmol) were mixed in NMP (114.0 g), After reacting at 40 ° C. for 3 hours, CBDA (4.8 g, 25 mmol) and NMP (76.0 g) were added and reacted at 40 ° C. for 12 hours to obtain a polyamic acid solution [A] having a resin content of 20% by mass. Obtained. The number average molecular weight of this polyamic acid solution was 28,100, and the weight average molecular weight was 72,300.
合成例1で得られたポリアミド酸溶液[A](80.0g)にNMPを加え6質量%に希釈した後、イミド化触媒として無水酢酸(8.6g)、及びピリジン(6.7g)を加え、80℃で3時間反応させた。この反応溶液をメタノール(990ml)中に投入し、得られた沈殿物を濾別した。この沈殿物をメタノールで洗浄し、100℃で減圧乾燥しポリイミド粉末[B]を得た。このポリイミドのイミド化率は53%であり、数平均分子量は20,100、重量平均分子量は58,300であった。 <Synthesis Example 2>
After adding NMP to the polyamic acid solution [A] (80.0 g) obtained in Synthesis Example 1 and diluting to 6% by mass, acetic anhydride (8.6 g) and pyridine (6.7 g) were used as imidization catalysts. In addition, the mixture was reacted at 80 ° C. for 3 hours. This reaction solution was poured into methanol (990 ml), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder [B]. The imidation ratio of this polyimide was 53%, the number average molecular weight was 20,100, and the weight average molecular weight was 58,300.
BODA(18.8g,75mmol)、Me-DADPA(6.3g,30mmol)、DBA(6.1g,40mmol)、及びPCH7DAB(11.4g,30mmol)をNMP(114.0g)中で混合し、40℃で3時間反応させた後、CBDA(4.8g,25mmol)とNMP(76.0g)を加え、40℃で12時間反応させポリアミド酸溶液を得た。
このポリアミド酸溶液(80.0g)にNMPを加え6質量%に希釈した後、イミド化触媒として無水酢酸(17.2g)、及びピリジン(13.3g)を加え、90℃で3時間反応させた。この反応溶液をメタノール(1040ml)中に投入し、得られた沈殿物を濾別した。この沈殿物をメタノールで洗浄し、100℃で減圧乾燥しポリイミド粉末[C]を得た。このポリイミドのイミド化率は81%であり、数平均分子量は19,300、重量平均分子量は51,600であった。 <Synthesis Example 3>
BODA (18.8 g, 75 mmol), Me-DADPA (6.3 g, 30 mmol), DBA (6.1 g, 40 mmol), and PCH7DAB (11.4 g, 30 mmol) were mixed in NMP (114.0 g), After reacting at 40 ° C. for 3 hours, CBDA (4.8 g, 25 mmol) and NMP (76.0 g) were added and reacted at 40 ° C. for 12 hours to obtain a polyamic acid solution.
After adding NMP to this polyamic acid solution (80.0 g) and diluting to 6% by mass, acetic anhydride (17.2 g) and pyridine (13.3 g) were added as an imidization catalyst and reacted at 90 ° C. for 3 hours. It was. This reaction solution was put into methanol (1040 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder [C]. The imidation ratio of this polyimide was 81%, the number average molecular weight was 19,300, and the weight average molecular weight was 51,600.
BODA(9.4g,37mmol)、ジアミン(1)(5.9g,15mmol)、DBA(3.0g,20mmol)、及びPCH7DAB(5.7g,15mmol)をNMP(63.0g)中で混合し、80℃で3時間反応させた後、CBDA(2.3g,12mmol)とNMP(42.4g)を加え、40℃で12時間反応させポリアミド酸溶液を得た。
このポリアミド酸溶液(50.0g)にNMPを加え6質量%に希釈した後、イミド化触媒として無水酢酸(10.1g)、及びピリジン(3.9g)を加え、100℃で3時間反応させた。この反応溶液をメタノール(650ml)中に投入し、得られた沈殿物を濾別した。この沈殿物をメタノールで洗浄し、100℃で減圧乾燥しポリイミド粉末[D]を得た。このポリイミドのイミド化率は53%であり、数平均分子量は21,200、重量平均分子量は60,400であった。 <Synthesis Example 4>
BODA (9.4 g, 37 mmol), diamine (1) (5.9 g, 15 mmol), DBA (3.0 g, 20 mmol), and PCH7DAB (5.7 g, 15 mmol) were mixed in NMP (63.0 g). After reacting at 80 ° C. for 3 hours, CBDA (2.3 g, 12 mmol) and NMP (42.4 g) were added and reacted at 40 ° C. for 12 hours to obtain a polyamic acid solution.
After adding NMP to this polyamic acid solution (50.0 g) and diluting to 6% by mass, acetic anhydride (10.1 g) and pyridine (3.9 g) are added as an imidization catalyst and reacted at 100 ° C. for 3 hours. It was. This reaction solution was put into methanol (650 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder [D]. The imidation ratio of this polyimide was 53%, the number average molecular weight was 21,200, and the weight average molecular weight was 60,400.
CBDA(9.7g,50mmol)、2,4-DAA(2.0g,10mmol)、DBA(3.8g,25mmol)、及びPCH7DAB(5.7g,15mmol)をNMP(85.0g)中で混合し、23℃で20時間反応させポリアミド酸溶液を得た。
このポリアミド酸溶液(50.5g)にNMPを加え6質量%に希釈した後、イミド化触媒として無水酢酸(7.2g)、及びピリジン(3.2g)を加え、50℃で3時間反応させた。この反応溶液をメタノール(630ml)中に投入し、得られた沈殿物を濾別した。この沈殿物をメタノールで洗浄し、100℃で減圧乾燥しポリイミド粉末[E]を得た。このポリイミドのイミド化率は92%であり、数平均分子量は18,700、重量平均分子量は46,400であった。 <Synthesis Example 5>
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 | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder [E]. 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.
BODA(7.5g,30mmol)、DBA(3.7g,24mmol)、ジアミン(2)(2.8g,4.0mmol)、及びPCH7DAB(4.6g,12.0mmol)をNMP(49.2g)中で混合し、80℃で5時間反応させた後、CBDA(1.9g,10.0mmol)とNMP(32.6g)を加え、40℃で3時間反応させポリアミド酸溶液を得た。
このポリアミド酸溶液(50.0g)にNMPを加え6質量%に希釈した後、イミド化触媒として無水酢酸(5.0g)、及びピリジン(3.7g)を加え、80℃で2時間45分反応させた。この反応溶液をメタノール(600ml)中に投入し、得られた沈殿物を濾別した。この沈殿物をメタノールで洗浄し、100℃で減圧乾燥しポリイミド粉末[F]を得た。このポリイミドのイミド化率は50%であり、数平均分子量は20,800、重量平均分子量は60,200であった。 <Synthesis Example 6>
BODA (7.5 g, 30 mmol), DBA (3.7 g, 24 mmol), diamine (2) (2.8 g, 4.0 mmol), and PCH7DAB (4.6 g, 12.0 mmol) were added to NMP (49.2 g). After mixing at 80 ° C. for 5 hours, CBDA (1.9 g, 10.0 mmol) and NMP (32.6 g) were added and reacted at 40 ° C. for 3 hours to obtain a polyamic acid solution.
After adding NMP to this polyamic acid solution (50.0 g) and diluting to 6% by mass, acetic anhydride (5.0 g) and pyridine (3.7 g) were added as imidization catalysts, and the mixture was heated at 80 ° C. for 2 hours and 45 minutes. Reacted. This reaction solution was poured into methanol (600 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder [F]. The imidation ratio of this polyimide was 50%, the number average molecular weight was 20,800, and the weight average molecular weight was 60,200.
BODA(150.1g,600mmol)、DBA(60.9g,400mmol)、及びPCH7DAB(152.2g,400mmol)をNMP(1290g)中で混合し、80℃で5時間反応させた後、CBDA(38.8g,198mmol)とNMP(320g)を加え、40℃で3時間反応させポリアミド酸溶液を得た。
このポリアミド酸溶液(600.2g)にNMPを加え6質量%に希釈した後、イミド化触媒として無水酢酸(63.9g)、及びピリジン(49.6g)を加え、80℃で3時間反応させた。この反応溶液をメタノール(7700ml)中に投入し、得られた沈殿物を濾別した。この沈殿物をメタノールで洗浄し、100℃で減圧乾燥しポリイミド粉末[G]を得た。このポリイミドのイミド化率は57%であり、数平均分子量は23,000、重量平均分子量は80,200であった。 <Synthesis Example 7>
BODA (150.1 g, 600 mmol), DBA (60.9 g, 400 mmol), and PCH7DAB (152.2 g, 400 mmol) were mixed in NMP (1290 g), reacted at 80 ° C. for 5 hours, and then CBDA (38 .8 g, 198 mmol) and NMP (320 g) were added and reacted at 40 ° C. for 3 hours to obtain a polyamic acid solution.
After adding NMP to this polyamic acid solution (600.2 g) and diluting to 6% by mass, acetic anhydride (63.9 g) and pyridine (49.6 g) were added as an imidization catalyst and reacted at 80 ° C. for 3 hours. It was. This reaction solution was poured into methanol (7700 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder [G]. The imidation ratio of this polyimide was 57%, the number average molecular weight was 23,000, and the weight average molecular weight was 80,200.
合成例7で得られたポリアミド酸溶液(101.2g)にNMPを加え6質量%に希釈した後、イミド化触媒として無水酢酸(21.3g)、及びピリジン(16.5g)を加え、90℃で3時間反応させた。この反応溶液をメタノール(1300ml)中に投入し、得られた沈殿物を濾別した。この沈殿物をメタノールで洗浄し、100℃で減圧乾燥しポリイミド粉末[H]を得た。このポリイミドのイミド化率は81%であり、数平均分子量は20,400、重量平均分子量は63,000であった。 <Synthesis Example 8>
After adding NMP to the polyamic acid solution (101.2 g) obtained in Synthesis Example 7 and diluting to 6% by mass, acetic anhydride (21.3 g) and pyridine (16.5 g) were added as imidization catalysts, and 90% The reaction was carried out at 0 ° C. for 3 hours. This reaction solution was put into methanol (1300 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder [H]. The imidation ratio of this polyimide was 81%, the number average molecular weight was 20,400, and the weight average molecular weight was 63,000.
CBDA(7.8g,40mmol)、2,4-DAA(4.9g,24mmol)、及びPCH7DAB(6.1g,16mmol)をNMP(74.9g)中で混合し、23℃で20時間反応させポリアミド酸溶液を得た。
このポリアミド酸溶液(80.0g)にNMPを加え6質量%に希釈した後、イミド化触媒として無水酢酸(10.4g)、及びピリジン(4.6g)を加え、50℃で3時間反応させた。この反応溶液をメタノール(1000ml)中に投入し、得られた沈殿物を濾別した。この沈殿物をメタノールで洗浄し、100℃で減圧乾燥しポリイミド粉末[I]を得た。このポリイミドのイミド化率は97%であり、数平均分子量は18,300、重量平均分子量は44,200であった。 <Synthesis Example 9>
CBDA (7.8 g, 40 mmol), 2,4-DAA (4.9 g, 24 mmol), and PCH7DAB (6.1 g, 16 mmol) were mixed in NMP (74.9 g) and reacted at 23 ° C. for 20 hours. A polyamic acid solution was obtained.
After adding NMP to this polyamic acid solution (80.0 g) and diluting to 6% by mass, acetic anhydride (10.4 g) and pyridine (4.6 g) are added as an imidization catalyst and reacted at 50 ° C. for 3 hours. It was. This reaction solution was poured into methanol (1000 ml), and the resulting precipitate was filtered off. 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.
<実施例1>
合成例1で得られたポリアミド酸溶液[A](10.1g)にNMP(8.1g)、及びBCS(16.0g)を加え、25℃にて2時間攪拌することにより、液晶配向剤[1]を得た。この液晶配向剤に濁りや析出などの異常は見られず、樹脂成分は均一に溶解していることが確認された。
[液晶セルの作製]
上記で得た液晶配向剤[1]をITO電極付きガラス基板にスピンコートし、80℃のホットプレート上で5分間乾燥させた後、210℃の熱風循環式オーブンで1時間焼成を行い、膜厚100nmの液晶配向膜を作製した。この液晶配向膜付き基板を2枚用意し、その1枚の液晶配向膜面上に6μmのスペーサーを散布した後、その上からシール剤を印刷し、張り合わせた後、シール剤を硬化させて空セルを作製した。この空セルに減圧注入法によって、液晶MLC-6608(メルク・ジャパン社製)を注入し、注入口を封止して、ネマティック液晶セルを得た。
[電圧保持率の評価]
上記で作製した液晶セルに、80℃の温度下で4Vの電圧を60μs印加し、16.67ms後、及び1667ms後の電圧を測定し、電圧がどのくらい保持できているかを電圧保持率として計算した。なお、測定は、東陽テクニカ社製VHR-1電圧保持率測定装置を使用し、Voltage:±4V,Pulse Width:60μs、Flame Period:16.67ms又は1667msの設定で測定した。結果は、後述する表2に示す。
[残留電荷の評価]
電圧保持率測定後の液晶セルに、交流電圧5.8Vppと直流電圧1Vを30時間印加し、液晶セル内に発生している電圧(残留電荷)を直流電圧解除直後に測定した。結果は、後述する表3に示す。
[高温放置後の評価]
上記の測定を終了した液晶セルを、60℃に設定した恒温槽に10日間放置した後、電圧保持率及び残留電荷の測定を行った。結果は、後述する表2及び表3に示す。 [Preparation and Evaluation of Liquid Crystal Alignment Agent of the Present Invention]
<Example 1>
By adding NMP (8.1 g) and BCS (16.0 g) to the polyamic acid solution [A] (10.1 g) obtained in Synthesis Example 1, and stirring at 25 ° C. for 2 hours, a liquid crystal aligning agent [1] was obtained. 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.
[Production of liquid crystal cell]
The liquid crystal aligning agent [1] obtained above is spin-coated on a glass substrate with an ITO electrode, dried on an 80 ° C. hot plate for 5 minutes, and then baked for 1 hour in a 210 ° C. hot air circulation oven. 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 μm 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. for 60 μs, the voltage after 16.67 ms and after 1667 ms was measured, and the voltage holding ratio was calculated as the voltage holding ratio. . The measurement was performed using a VHR-1 voltage holding ratio measuring device manufactured by Toyo Technica Co., Ltd., with settings of Voltage: ± 4 V, Pulse Width: 60 μs, and Frame Period: 16.67 ms or 1667 ms. The results are shown in Table 2 described later.
[Evaluation of residual charge]
An AC voltage of 5.8 Vpp and a DC voltage of 1 V were applied to the liquid crystal cell after measuring the voltage holding ratio for 30 hours, and the voltage (residual charge) generated in the liquid crystal cell was measured immediately after the DC voltage was released. The results are shown in Table 3 described later.
[Evaluation after leaving at high temperature]
The liquid crystal cell after the above measurement was left in a thermostatic bath set at 60 ° C. for 10 days, and then the voltage holding ratio and the residual charge were measured. The results are shown in Tables 2 and 3 below.
合成例2で得られたポリイミド粉末[B](5.0g)にNMP(24.4g)を加え、70℃にて40時間攪拌して溶解させた。この溶液にNMP(12.3g)、及びBCS(41.7g)を加え、25℃にて2時間攪拌することにより、液晶配向剤[2]を得た。この液晶配向剤に濁りや析出などの異常は見られず、樹脂成分は均一に溶解していることが確認された。
得られた液晶配向剤[2]を用い、実施例1と同様に液晶セルを作製し、電圧保持率の評価、残留電荷の評価、高温放置後の評価を行った。結果は、後述する表2及び表3に示す。 <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.
合成例3で得られたポリイミド粉末[C](5.1g)にNMP(24.5g)を加え、70℃にて40時間攪拌して溶解させた。この溶液にNMP(23.9g)、及びBCS(30.0g)を加え、25℃にて2時間攪拌することにより、液晶配向剤[3]を得た。この液晶配向剤に濁りや析出などの異常は見られず、樹脂成分は均一に溶解していることが確認された。
得られた液晶配向剤[3]を用い、実施例1と同様に液晶セルを作製し、電圧保持率の評価、残留電荷の評価、高温放置後の評価を行った。結果は、後述する表2及び表3に示す。 <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.
合成例4で得られたポリイミド粉末[D](5.0g)にNMP(25.0g)を加え、70℃にて40時間攪拌して溶解させた。この溶液にNMP(20.1g)、及びBCS(33.2g)を加え、25℃にて2時間攪拌することにより、液晶配向剤[4]を得た。この液晶配向剤に濁りや析出などの異常は見られず、樹脂成分は均一に溶解していることが確認された。
得られた液晶配向剤[4]を用い、実施例1と同様に液晶セルを作製し、電圧保持率の評価、残留電荷の評価、高温放置後の評価を行った。結果は、後述する表2及び表3に示す。 <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.
合成例5で得られたポリイミド粉末[E](4.9g)にNMP(24.5g)を加え、70℃にて40時間攪拌して溶解させた。この溶液にNMP(29.0g)、及びBCS(25.3g)を加え、25℃にて2時間攪拌することにより、液晶配向剤[5]を得た。この液晶配向剤に濁りや析出などの異常は見られず、樹脂成分は均一に溶解していることが確認された。
得られた液晶配向剤[5]を用い、実施例1と同様に液晶セルを作製し、電圧保持率の評価、残留電荷の評価、高温放置後の評価を行った。結果は、後述する表2及び表3に示す。 <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.
合成例6で得られたポリイミド粉末[F](5.0g)にNMP(25.0g)を加え、70℃にて40時間攪拌して溶解させた。この溶液にNMP(11.5g)、及びBCS(42.9g)を加え、25℃にて2時間攪拌することにより、液晶配向剤[6]を得た。この液晶配向剤に濁りや析出などの異常は見られず、樹脂成分は均一に溶解していることが確認された。
得られた液晶配向剤[6]を用い、実施例1と同様に液晶セルを作製し、電圧保持率の評価、残留電荷の評価、高温放置後の評価を行った。結果は、後述する表2及び表3に示す。 <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.
合成例7で得られたポリイミド粉末[G](5.0g)にNMP(25.0g)を加え、70℃にて40時間攪拌して溶解させた。この溶液にNMP(23.1g)、及びBCS(28.5g)を加え、25℃にて2時間攪拌することにより、液晶配向剤[7]を得た。この液晶配向剤に濁りや析出などの異常は見られず、樹脂成分は均一に溶解していることが確認された。
得られた液晶配向剤[7]を用い、実施例1と同様に液晶セルを作製し、電圧保持率の評価、残留電荷の評価、高温放置後の評価を行った。結果は、後述する表2及び表3に示す。 <Comparative Example 1>
NMP (25.0 g) was added to the polyimide powder [G] (5.0 g) obtained in Synthesis Example 7 and dissolved by stirring at 70 ° C. for 40 hours. NMP (23.1g) and BCS (28.5g) were added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained liquid crystal aligning agent [7]. 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 [7], 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.
合成例8で得られたポリイミド粉末[H](5.1g)にNMP(25.0g)を加え、70℃にて40時間攪拌して溶解させた。この溶液にNMP(30.4g)、及びBCS(23.3g)を加え、25℃にて2時間攪拌することにより、液晶配向剤[8]を得た。この液晶配向剤に濁りや析出などの異常は見られず、樹脂成分は均一に溶解していることが確認された。
得られた液晶配向剤[8]を用い、実施例1と同様に液晶セルを作製し、電圧保持率の評価、残留電荷の評価、高温放置後の評価を行った。結果は、後述する表2及び表3に示す。 <Comparative example 2>
NMP (25.0 g) was added to the polyimide powder [H] (5.1 g) obtained in Synthesis Example 8, and dissolved by stirring at 70 ° C. for 40 hours. NMP (30.4g) and BCS (23.3g) were added to this solution, and the liquid crystal aligning agent [8] 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 [8], 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.
合成例9で得られたポリイミド粉末[I](5.1g)にNMP(24.8g)を加え、70℃にて40時間攪拌して溶解させた。この溶液にNMP(36.4g)、及びBCS(17.3g)を加え、25℃にて2時間攪拌することにより、液晶配向剤[9]を得た。この液晶配向剤に濁りや析出などの異常は見られず、樹脂成分は均一に溶解していることが確認された。
得られた液晶配向剤[9]を用い、実施例1と同様に液晶セルを作製し、電圧保持率の評価、残留電荷の評価、高温放置後の評価を行った。結果は、後述する表2及び表3に示す。
なお、表2及び表3中、イミド化率の「-」は、イミド化率を算出しなかったことを意味する。 <Comparative Example 3>
NMP (24.8 g) was added to the polyimide powder [I] (5.1 g) obtained in Synthesis Example 9 and dissolved by stirring at 70 ° C. for 40 hours. NMP (36.4g) and BCS (17.3g) were added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained liquid crystal aligning agent [9]. 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 [9], 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.
In Tables 2 and 3, “−” in the imidization rate means that the imidization rate was not calculated.
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. Available to: As a result, it is useful for TN elements, STN elements, TFT liquid crystal elements, and liquid crystal display elements of vertical alignment type and horizontal alignment type (IPS).
Claims (15)
- ジアミン化合物(A)及びジアミン化合物(B)を含むジアミン成分とテトラカルボン酸二無水物とを反応させて得られる共重合体を含有することを特徴とする液晶配向剤。
ジアミン化合物(A):下記の式[T1]、式[T2]及び式[T3]からなる群より選ばれる少なくとも一種である、3級窒素原子を有するジアミン化合物、
ジアミン化合物(B):分子内にカルボキシル基を有するジアミン化合物。
Diamine compound (A): a diamine compound having a tertiary nitrogen atom, which is at least one selected from the group consisting of the following formula [T1], formula [T2] and formula [T3],
Diamine compound (B): a diamine compound having a carboxyl group in the molecule.
- ジアミン化合物(A)が下記の式[1]から式[4]で表される化合物である請求項1に記載の液晶配向剤。
- ジアミン化合物(A)が、式[1]又は式[2]である請求項2に記載の液晶配向剤。 The liquid crystal aligning agent of Claim 2 whose diamine compound (A) is Formula [1] or Formula [2].
- 式[3]のA2が、ベンゼン環又は下記の式[3a]である請求項2に記載の液晶配向剤。
- ジアミン化合物(A)が、下記の式[5]から[18]からなる群より選ばれる少なくとも一種のジアミン化合物である請求項1又は請求項2に記載の液晶配向剤。
- ジアミン化合物(B)が、下記の式[19]で表されるジアミン化合物である請求項1から請求項5のいずれか一項に記載の液晶配向剤。
- ジアミン化合物(B)が、下記の式[20]から式[24]より選ばれるジアミン化合物である請求項6に記載の液晶配向剤。
- 式[20]中、m1が1から2の整数である請求項7に記載の液晶配向剤。 The liquid crystal aligning agent according to claim 7, wherein m1 is an integer of 1 to 2 in the formula [20].
- 式[21]中、X2が単結合、-CH2-、-C2H4-、-C(CH3)2-、-O-、-CO-、-NH-、-N(CH3)-、-CONH-、-NHCO-、-COO-、又は-OCO-であり、m2、m3は共に1の整数である請求項7に記載の液晶配向剤。 In the formula [21], X 2 is a single bond, —CH 2 —, —C 2 H 4 —, —C (CH 3 ) 2 —, —O—, —CO—, —NH—, —N (CH 3 The liquid crystal aligning agent according to claim 7, wherein m is an integer of 1, and m is an integer of 1)-, -CONH-, -NHCO-, -COO-, or -OCO-.
- 式[24]中、X4は単結合、-CH2-、-O-、-CO-、-NH-、-CONH-、-NHCO-、-CH2O-、-OCH2-、-COO-、又は-OCO-であり、m7は1から2の整数である請求項7に記載の液晶配向剤。 In the formula [24], X 4 represents a single bond, —CH 2 —, —O—, —CO—, —NH—, —CONH—, —NHCO—, —CH 2 O—, —OCH 2 —, —COO. The liquid crystal aligning agent according to claim 7, which is-or -OCO-, and m7 is an integer of 1 to 2.
- ジアミン成分中におけるジアミン化合物(B)の含有量が、ジアミン化合物(A)の1モルに対して、0.01から99モルである請求項1から請求項10のいずれか一項に記載の液晶配向剤。 The liquid crystal according to any one of claims 1 to 10, wherein the content of the diamine compound (B) in the diamine component is 0.01 to 99 mol with respect to 1 mol of the diamine compound (A). Alignment agent.
- 液晶配向剤中に含まれる溶媒中の5から80質量%が貧溶媒である請求項1から請求項11のいずれか一項に記載の液晶配向剤。 The liquid crystal aligning agent according to any one of claims 1 to 11, wherein 5 to 80% by mass of the solvent contained in the liquid crystal aligning agent is a poor solvent.
- 液晶配向剤中の共重合体がポリアミド酸を脱水閉環させて得られるポリイミドである請求項1から請求項12のいずれか一項に記載の液晶配向剤。 The liquid crystal aligning agent according to any one of claims 1 to 12, wherein the copolymer in the liquid crystal aligning agent is a polyimide obtained by dehydrating and ring-closing polyamic acid.
- 請求項1から請求項13のいずれか一項に記載の液晶配向剤を用いて得られることを特徴とする液晶配向膜。 A liquid crystal alignment film obtained by using the liquid crystal aligning agent according to any one of claims 1 to 13.
- 請求項14に記載の液晶配向膜を有することを特徴とする液晶表示素子。 A liquid crystal display element comprising the liquid crystal alignment film according to claim 14.
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JP2011154100A (en) * | 2010-01-26 | 2011-08-11 | Jnc Corp | Liquid crystal aligning agent, liquid crystal alignment layer, and liquid crystal display element |
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JP2012053394A (en) * | 2010-09-03 | 2012-03-15 | Hitachi Displays Ltd | Liquid crystal display device |
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Also Published As
Publication number | Publication date |
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TWI438226B (en) | 2014-05-21 |
KR101589322B1 (en) | 2016-01-27 |
JP5177150B2 (en) | 2013-04-03 |
CN101925850A (en) | 2010-12-22 |
KR20100103583A (en) | 2010-09-27 |
CN101925850B (en) | 2012-06-06 |
JPWO2009093709A1 (en) | 2011-05-26 |
TW200948860A (en) | 2009-12-01 |
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