[go: up one dir, main page]

WO2010035719A1 - Agent d'alignement de cristaux liquides et élément d'affichage à cristaux liquides l'utilisant - Google Patents

Agent d'alignement de cristaux liquides et élément d'affichage à cristaux liquides l'utilisant Download PDF

Info

Publication number
WO2010035719A1
WO2010035719A1 PCT/JP2009/066422 JP2009066422W WO2010035719A1 WO 2010035719 A1 WO2010035719 A1 WO 2010035719A1 JP 2009066422 W JP2009066422 W JP 2009066422W WO 2010035719 A1 WO2010035719 A1 WO 2010035719A1
Authority
WO
WIPO (PCT)
Prior art keywords
liquid crystal
formula
carbon atoms
ring
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2009/066422
Other languages
English (en)
Japanese (ja)
Inventor
耕平 後藤
徳俊 三木
和義 保坂
幸司 園山
雅章 片山
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nissan Chemical Corp
Original Assignee
Nissan Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nissan Chemical Corp filed Critical Nissan Chemical Corp
Priority to JP2010530837A priority Critical patent/JP5382372B2/ja
Priority to CN2009801383003A priority patent/CN102165365B/zh
Publication of WO2010035719A1 publication Critical patent/WO2010035719A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • the present invention relates to a liquid crystal alignment treatment agent used for producing a liquid crystal alignment film and a liquid crystal display element using the same.
  • a so-called polyimide liquid crystal alignment film obtained by applying and baking a liquid crystal alignment treatment agent mainly composed of a polyimide precursor such as polyamic acid or a soluble polyimide solution is mainly used. ing.
  • pretilt angle control of the liquid crystal in which the alignment tilt angle of the liquid crystal molecules with respect to the substrate surface is maintained at an arbitrary value. It is known that the magnitude of the pretilt angle can be changed by selecting the structure of the polyimide constituting the liquid crystal alignment film.
  • the method using a diamine having a side chain as a part of the polyimide raw material increases the pretilt angle depending on the proportion of the diamine used, so the target pretilt angle is controlled. This is relatively easy and is useful as a means for increasing the pretilt angle.
  • a side chain structure of the diamine that increases the pretilt angle of the liquid crystal a structure containing a steroid skeleton (see, for example, Patent Document 1) and a ring structure (see, for example, Patent Document 2) such as a phenyl group or a cyclohexyl group has been proposed.
  • a diamine having 3 to 4 such ring structures in the side chain has also been proposed (see, for example, Patent Document 3).
  • the polyimide obtained by using the diamine having a side chain as described above tends to reduce the coating uniformity of the solution, it is necessary to increase the mixing amount of the coating property improving solvent such as butyl cellosolve. Also, the mixing tolerance of such a solvent is an important characteristic of polyimide.
  • liquid crystal alignment films used in the liquid crystal alignment films used in the liquid crystal display elements have a high voltage holding ratio and a direct current voltage from the viewpoint of suppressing contrast reduction and afterimage phenomenon.
  • the characteristics that the accumulated charge when applied is small and the residual charge accumulated by the DC voltage is quickly relaxed are becoming increasingly important.
  • a liquid crystal alignment treatment agent containing a tertiary amine with a specific structure in addition to polyamic acid or imide group-containing polyamic acid is 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 see, for example, Patent Document 6
  • one carboxylic acid group is contained 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.
  • Liquid crystal aligning agent containing a very small amount of a compound selected from a compound, a compound containing one carboxylic anhydride group in the molecule, and a compound containing one tertiary amino group in the molecule (for example, Patent Document 7) See).
  • liquid crystal alignment film to be used has to be more reliable than conventional liquid crystal alignment films.
  • the electrical characteristics of the liquid crystal alignment film are not only good in initial characteristics but also, for example, at a high temperature for a long time. There is a need to maintain good properties even after exposure.
  • the object of the present invention is to prevent precipitation even when a poor solvent is mixed with a liquid crystal alignment treatment coating solution, and to increase the pretilt angle of the liquid crystal.
  • Liquid crystal alignment treatment agent that can be aligned vertically, has a high voltage holding ratio, and provides a liquid crystal alignment film that can quickly relieve residual charges accumulated by DC voltage even after being exposed to a high temperature for a long time. Is to provide.
  • an object of the present invention is to provide a highly reliable liquid crystal display element that can withstand long-term use in a severe use environment by using this liquid crystal alignment treatment agent.
  • a diamine compound (A) represented by the following formula [1] a diamine compound (B) represented by the following formula [2], and a diamine compound having a carboxyl group in the molecule
  • a liquid crystal aligning agent comprising a copolymer obtained by reacting a diamine component containing (C) with tetracarboxylic dianhydride.
  • p is an integer of 0 or 1
  • X 1 is phenylene
  • X 2 is phenylene or cyclohexylene
  • X 3 is cyclohexylene
  • X 4 has 3 to 3 carbon atoms.
  • X ′′ 1 is 1,4-phenylene or 1,4-cyclohexylene
  • X ′′ 2 is an alkyl group having 3 to 12 carbon atoms, and 3 to 12 carbon atoms.
  • X 5 is an alkyl group having 3 to 12 carbon atoms, a fluoroalkyl group having 3 to 12 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, or a fluoroalkoxy group having 3 to 12 carbon atoms.
  • cis-trans isomerism of 1,4-cyclohexylene is the trans isomer.
  • X 6 represents an alkyl group having 3 to 12 carbon atoms, a fluoroalkyl group having 3 to 12 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, or a fluoroalkoxy group having 3 to 12 carbon atoms.
  • cis-trans isomerism of 1,4-cyclohexylene is the trans isomer.
  • X ′′ 3 is an alkyl group having 3 to 12 carbon atoms, a fluoroalkyl group having 3 to 12 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, or an alkyl group having 3 to 12 carbon atoms. It is a fluoroalkoxy group, and the cis-trans isomerism of 1,4-cyclohexylene is the trans isomer).
  • the liquid-crystal aligning agent as described in said (3) whose diamine compound (A '') is a diamine compound represented by following formula [1''b].
  • X ′′ 4 represents an alkyl group having 3 to 12 carbon atoms, a fluoroalkyl group having 3 to 12 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, or an alkyl group having 3 to 12 carbon atoms. It is a fluoroalkoxy group, and the cis-trans isomerism of 1,4-cyclohexylene is the trans isomer).
  • Y 1 in the formula [2] is —O—, —NH—, —CONH—, —NHCO—, —CON (CH 3 ) —, or —CH 2 O—.
  • the liquid crystal aligning agent as described in any one of 7).
  • a linear or branched alkyl group of 1 to 5 Y 3 is a single bond
  • Y 4 is a pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, or pyrimidine ring
  • n is an integer of 1 to 3
  • Y 1 in formula [2] is —O—, —NH—, —CONH—, —NHCO—, —CON (CH 3 ) —, or —CH 2 O—, and Y 2 is a benzene ring Y 3 is —O—, —CONH—, —NHCO—, —COO—, —OCO—, or —O (CH 2 ) m — (m is an integer of 1 to 5), and Y
  • the diamine compound of the formula [3] is at least one diamine compound selected from the group consisting of the following formula [3a], formula [3b], formula [3c], formula [3d] and formula [3e]
  • m 1 is an integer of 1 to 4.
  • Z 2 is a single bond, —CH 2 —, —C 2 H 4 —, —C (CH 3 ) 2 —. , —CF 2 —, —C (CF 3 ) —, —O—, —CO—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —CH 2 O—, —OCH 2- , -COO-, -OCO-, -CON (CH 3 )-, or -N (CH 3 ) CO-, m 2 and m 3 each represent an integer of 0 to 4, and m 2 + m 3 represents an integer of 1 to 4.
  • n 4 and m 5 are each an integer of 1 to 5.
  • Z 3 is a linear or branched group having 1 to 5 carbon atoms.
  • M 6 is an alkyl group and m 6 is an integer of 1 to 5.
  • Z 4 is a single bond, —CH 2 —, —C 2 H 4 —, —C (CH 3 ) 2 —, — CF 2 - -C (CF 3) -, - O -, - CO -, - NH -, - N (CH 3) -, - CONH -, - NHCO -, - CH 2 O -, - OCH 2 -, - COO- , -OCO-, -CON (CH 3 )-, or -N (CH 3 ) CO-, and m 7 is an integer of 1 to 4.
  • Z 4 represents a single bond, —CH 2 —, —O—, —CO—, —NH—, —CONH—, —NHCO—, —CH 2 O—, —OCH 2 —. , —COO—, or —OCO—, and m 7 is an integer of 1 to 2, the liquid crystal aligning agent according to the above (16).
  • the diamine compound (A) is 0.5 to 50 mol relative to 1 mol of the diamine compound (C)
  • the diamine compound (B) is 1 mol of the diamine compound (C).
  • the liquid crystal aligning agent according to any one of (2) to (19), wherein the amount is 0.5 to 10 moles.
  • a liquid crystal display device comprising the liquid crystal alignment film according to (23).
  • the liquid crystal alignment treatment agent of the present invention can be obtained by a relatively simple method, and has a characteristic of increasing the pretilt angle of the liquid crystal when formed into a liquid crystal alignment film. Can be made. In addition, even when a poor solvent is mixed with the liquid crystal aligning agent coating solution, precipitation is unlikely to occur, and therefore a uniform liquid crystal alignment film can be formed even when coating on a large substrate. Furthermore, it is possible to obtain a liquid crystal alignment film that has a high voltage holding ratio and can quickly relieve residual charges accumulated by a DC voltage even after being exposed to a high temperature for a long time. Therefore, a liquid crystal display element having a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention is excellent in reliability and can be suitably used for a large-screen, high-definition liquid crystal television.
  • the present invention relates to a liquid crystal aligning agent comprising a copolymer obtained by reacting a diamine component (A), a diamine compound (B) and a diamine component containing a diamine compound (C) with tetracarboxylic dianhydride, A liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent, and further a liquid crystal display element having the liquid crystal alignment film.
  • the diamine compound (A) is a diamine compound represented by the formula [1]
  • the diamine compound (B) is a diamine compound represented by the formula [2]
  • the diamine compound (C) is: It is a diamine compound having a carboxyl group in the molecule.
  • the diamine compound (A) used in the present invention is a specific diamine having a substituent having a characteristic of increasing the pretilt angle in the side chain (hereinafter, also referred to as a specific diamine (A)). Therefore, the liquid crystal aligning agent obtained using this specific diamine (A) can align a liquid crystal perpendicularly even if the specific diamine (A) is used in a small proportion. Further, by reducing the proportion of the polymer used, the solubility of the polymer in the organic solvent increases, and precipitation hardly occurs even when a poor solvent is mixed in the coating liquid for the liquid crystal alignment treatment agent.
  • the diamine compound (B) used in the present invention (hereinafter sometimes referred to as a specific diamine (B)) has a nitrogen-containing aromatic heterocycle in the side chain.
  • This nitrogen-containing aromatic heterocycle functions as an electron hopping site due to its conjugated structure, so that it is possible to promote charge transfer in the liquid crystal alignment film.
  • this nitrogen-containing aromatic heterocyclic ring is bonded to the carboxyl group of the diamine compound (C) (hereinafter sometimes referred to as a specific diamine (C)) by electrostatic interaction such as salt formation or hydrogen bonding.
  • charge transfer occurs between the carboxyl group and the nitrogen-containing aromatic heterocycle. Therefore, the charge transferred to the nitrogen-containing aromatic heterocyclic moiety can efficiently move within and between the molecules of the copolymer.
  • the liquid crystal aligning agent of the present invention has the property of increasing the pretilt angle of the liquid crystal when formed into a liquid crystal alignment film, and can align the liquid crystal vertically even with a small use ratio.
  • precipitation is unlikely to occur when a poor solvent is mixed in the liquid crystal aligning agent coating solution.
  • the diamine compound (A) used in the present invention is a diamine compound represented by the following formula [1].
  • p is an integer of 0 or 1
  • X 1 is phenylene, preferably 1,4-phenylene
  • X 2 is phenylene, preferably 1,4-phenylene.
  • X 3 is cyclohexylenephenylene, preferably 1,4-cyclohexylene. Phenylene and cyclohexylene may have a substituent, if necessary.
  • X 4 is an alkyl group having 3 to 12 carbon atoms, a fluoroalkyl group having 3 to 12 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, or a fluoroalkoxy group having 3 to 12 carbon atoms.
  • the alkyl group, fluoroalkyl group, alkoxy group, and fluoroalkoxy group may be linear or branched, but are preferably linear and may have a substituent.
  • the diamine compound (A) is preferably a diamine compound (A ′) represented by the following formula [1 ′] or a diamine compound (A ′′) represented by the following formula [1 ′′].
  • the diamine compound (A ′) used in the present invention is a diamine compound represented by the following formula [1 ′].
  • the bonding position of the amino group in the benzene ring to which the amino group in the formula [1 ′] is bonded is not limited.
  • the side chain linking group —CH 2 O—
  • positions 2, 4 and 2, 5, and 3, 5 are preferable.
  • the positions 2, 4 or 2, 5 are preferred.
  • the diamine compounds represented by the following formulas [1′a] and [1′b] have the effect of increasing the pretilt angle of the liquid crystal with a small use ratio. It is preferable because it is large. In particular, the diamine represented by the formula [1′a] is more preferable because of its excellent effect.
  • X 5 in the formula [1′a] is an alkyl group having 3 to 12 carbon atoms, a fluoroalkyl group having 3 to 12 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, or a fluoroalkoxy group having 3 to 12 carbon atoms. .
  • X 5 is preferably an alkyl group having 3 to 12 carbon atoms or a fluoroalkyl group having 3 to 12 carbon atoms, more preferably an alkyl group having 3 to 12 carbon atoms, and particularly an alkyl group having 3 to 7 carbon atoms. It is a group.
  • the cis-trans isomerism of 1,4-cyclohexylene in the formula [1′a] is preferably a trans isomer.
  • X 6 in the formula [1′b] is an alkyl group having 3 to 12 carbon atoms, a fluoroalkyl group having 3 to 12 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, or a fluoroalkoxy group having 3 to 12 carbon atoms.
  • X 4 is preferably an alkyl group having 3 to 12 carbon atoms or a fluoroalkyl group having 3 to 12 carbon atoms, more preferably an alkyl group having 3 to 12 carbon atoms, and particularly an alkyl group having 3 to 7 carbon atoms. It is a group.
  • the cis-trans isomerism of 1,4-cyclohexylene in the formula [1′b] is preferably a trans isomer.
  • diamine compound represented by the formula [1 ′] of the present invention are diamine compounds represented by the following formulas [1′c] to [1′f].
  • X 5 to X 8 in the following formulas are each independently an alkyl group having 3 to 12 carbon atoms, a fluoroalkyl group having 3 to 12 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, or 3 to 12 fluoroalkoxy groups.
  • X 5 to X 8 are each independently preferably an alkyl group having 3 to 12 carbon atoms or a fluoroalkyl group having 3 to 12 carbon atoms, more preferably an alkyl group having 3 to 12 carbon atoms, And an alkyl group having 3 to 7 carbon atoms.
  • the cis-trans isomerisms of 1,4-cyclohexylene in the following formulas are all trans isomers.
  • the method for producing the diamine compound represented by the formula [1 ′] is not particularly limited, but preferred methods include the following methods.
  • the method for reducing the dinitro compound is not particularly limited. Usually, palladium-carbon, platinum oxide, Raney nickel, platinum black, rhodium-alumina, platinum sulfide carbon, etc. are used as a catalyst, ethyl acetate, toluene, tetrahydrofuran, dioxane, There is a method of performing reduction with hydrogen gas, hydrazine, hydrogen chloride or the like in an alcohol-based solvent.
  • X 1 , X 2 , X 3 and X 4 in the formula [1′g] are the same as defined in the formula [1].
  • the dinitro compound of the formula [1′g] can be obtained by reacting a hydroxyl group-containing compound represented by the following formula [1′h] with dinitrochlorobenzene or the like.
  • X 1 , X 2 , X 3 , and X 4 in the formula [1′h] are the same as defined in the formula [1].
  • the method for producing the hydroxyl group-containing compound represented by the formula [1′h] can be produced by the method represented by the following reaction formula (1) to reaction formula (2), but the present invention is limited to this. It is not a thing.
  • X 2 is 1,4-cyclohexylene
  • X 1 , X 3 and X 4 in the reaction formula (1) are the same as defined in the formula [1]
  • R 1 represents a protecting group such as a methyl group or a benzyl group
  • R 2 represents MgBr. , MgCl or Li.
  • the reagent used in the dehydration reaction include inorganic acids such as hydrochloric acid or sulfuric acid, organic acids such as p-toluenesulfonic acid, and acid anhydrides such as acetic anhydride or trifluoroacetic anhydride.
  • Examples of the reduction reaction include a hydrogenation reaction using palladium (Pd) or platinum (Pt) as a catalyst, or a catalytic reduction reaction using a metal such as iron, tin, or zinc.
  • Examples of the reaction of the deprotecting group include a methyl group elimination reaction using boron tribromide (BBr 3 ), a debenzylation reaction by hydrogenation using a Pd catalyst, and the like.
  • X 2 is 1,4-phenylene
  • a synthesis route of the reaction formula (2) can be mentioned.
  • X 1 , X 3 and X 4 in the reaction formula (2) are the same as defined in the formula [1]
  • T 1 represents a protecting group such as a methyl group or a benzyl group
  • T 2 represents a halogen atom.
  • T 3 represents a halogen atom, a methanesulfonyloxy group, a benzenesulfonyloxy group, a trifluoro It represents a lomethanesulfonyloxy group, B (OH) 2 , MgBr, MgCl or Li.
  • Examples of the reaction of the deprotecting group include a methyl group elimination reaction using BBr 3 or a debenzylation reaction by hydrogenation using a Pd catalyst or the like.
  • the diamine compound (A ′′) used in the present invention is a diamine compound represented by the following formula [1 ′′].
  • X ′′ 1 is 1,4-phenylene or 1,4-cyclohexylene. 1,4-phenylene and 1,4-cyclohexylene may have a substituent, if necessary.
  • X ′′ 2 is an alkyl group having 3 to 12 carbon atoms, a fluoroalkyl group having 3 to 12 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, or a fluoroalkoxy group having 3 to 12 carbon atoms.
  • the alkyl group, fluoroalkyl group, alkoxy group and fluoroalkoxy group may be linear or branched, but are preferably linear and may have a substituent.
  • the bonding position of the amino group in the benzene ring to which the amino group in Formula [1 ′′] is bonded is not limited. Specific examples include the 2,3 position, 2,4 position, 2,5 position, 2,6 position, 3,4 on the benzene ring with respect to the side chain linking group (—O—). And positions 3, 5 and the like. Among these, from the viewpoint of reactivity when synthesizing the polyamic acid, positions 2, 4 and 2, 5, and 3, 5 are preferable. Considering the ease of synthesis of the diamine compound, the positions 2, 4 or 2, 5 are preferred.
  • the diamine compounds of the formula [1 ′′] the diamines represented by the following formula [1 ′′ a] and the formula [1 ′′ b] in which X ′′ 1 is 1,4-trans-cyclohexylene A compound is preferable because it has a large effect of increasing the pretilt angle of the liquid crystal with a small use ratio.
  • the diamine compound represented by the formula [1 ′′ a] is more preferable because of its excellent effect.
  • X ′′ 3 in the formula [1 ′′ a] represents an alkyl group having 3 to 12 carbon atoms, a fluoroalkyl group having 3 to 12 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, or a fluoroalkoxy group having 3 to 12 carbon atoms. It is a group.
  • X ′′ 3 is preferably an alkyl group having 3 to 12 carbon atoms or a fluoroalkyl group having 3 to 12 carbon atoms, more preferably an alkyl group having 3 to 12 carbon atoms, particularly 3 to 7 carbon atoms. It is an alkyl group.
  • the cis-trans isomerism of 1,4-cyclohexylene in the formula [1 ′′ a] is preferably a trans isomer.
  • X ′′ 4 in the formula [1 ′′ b] represents an alkyl group having 3 to 12 carbon atoms, a fluoroalkyl group having 3 to 12 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, or a fluoroalkoxy group having 3 to 12 carbon atoms. It is a group.
  • X ′′ 4 is preferably an alkyl group having 3 to 12 carbon atoms or a fluoroalkyl group having 3 to 12 carbon atoms, more preferably an alkyl group having 3 to 12 carbon atoms, particularly 3 to 7 carbon atoms. It is an alkyl group.
  • the cis-trans isomerism of 1,4-cyclohexylene in the formula [1 ′′ b] is preferably a trans isomer.
  • diamine compound represented by the formula [1 ′′] of the present invention are diamine compounds represented by the following formula [1 ′′ c] to formula [1 ′′ f].
  • X ′′ 5 to X ′′ 8 in the following formulas are each independently an alkyl group having 3 to 12 carbon atoms, a fluoroalkyl group having 3 to 12 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, Or a fluoroalkoxy group having 3 to 12 carbon atoms.
  • X ′′ 5 to X ′′ 8 are each independently preferably an alkyl group having 3 to 12 carbon atoms or a fluoroalkyl group having 3 to 12 carbon atoms, more preferably an alkyl group having 3 to 12 carbon atoms. In particular, an alkyl group having 3 to 7 carbon atoms.
  • the cis-trans isomerisms of 1,4-cyclohexylene in the following formulas are all trans isomers.
  • the method for reducing the dinitro compound is not particularly limited. Usually, palladium-carbon, platinum oxide, Raney nickel, platinum black, rhodium-alumina, platinum sulfide carbon, etc. are used as a catalyst, ethyl acetate, toluene, tetrahydrofuran, dioxane, There is a method of performing reduction with hydrogen gas, hydrazine, hydrogen chloride or the like in an alcohol-based solvent.
  • X ′′ 1 and X ′′ 2 in the formula [1 ′′ g] are the same as defined in the formula [1 ′′].
  • the dinitro compound of the formula [1 ′′ g] can be obtained by reacting a hydroxyl group-containing compound represented by the following formula [1 ′′ h] with dinitrochlorobenzene or the like.
  • X ′′ 1 and X ′′ 2 in the formula [1 ′′ h] are the same as defined in the formula [1 ′′].
  • the method for producing the hydroxyl group-containing compound represented by the formula [1 ′′ h] can be produced by the method represented by the following reaction formula (1) or reaction formula (2), but the present invention is limited to this. It is not something.
  • X ′′ 1 is 1,4-cyclohexylene
  • the synthesis route of the reaction formula (1) can be mentioned.
  • X ′′ 2 in the reaction formula (1) is the same as defined in the formula [1 ′′]
  • R 1 represents a protecting group such as a methyl group or a benzyl group
  • R 2 represents MgBr, MgCl or Li etc.
  • Examples of the reagent used in the dehydration reaction include inorganic acids such as hydrochloric acid or sulfuric acid, organic acids such as p-toluenesulfonic acid, and acid anhydrides such as acetic anhydride or trifluoroacetic anhydride.
  • Examples of the reduction reaction include a hydrogenation reaction using palladium (Pd) or platinum (Pt) as a catalyst, or a catalytic reduction reaction using a metal such as iron, tin, or zinc.
  • Examples of the reaction of the deprotecting group include a methyl group elimination reaction using boron tribromide (BBr 3 ), a debenzylation reaction by hydrogenation using a Pd catalyst, and the like.
  • X ′′ 1 is 1,4-phenylene
  • X 'in the reaction formula (2)' 2 has the formula [1 'is the same as defined']
  • T 1 represents a protecting group such as a methyl group or a benzyl group
  • T 2 represents a halogen atom
  • T 3 represents a halogen atom, a methanesulfonyloxy group, a benzenesulfonyloxy group, a trifluoromethanesulfonyloxy Represents a group, B (OH) 2 , MgBr, MgCl, Li or the like.
  • Examples of the reaction of the deprotecting group include a
  • the diamine compound (B) used in the present invention is a diamine compound represented by the following formula [2].
  • Y 1 represents —O—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —CH 2 O—, —OCO—, —CON (CH 3 ) —.
  • Y 2 is a single bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group, or an aromatic hydrocarbon group; 3 represents a single bond, —O—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —COO—, —OCO—, —CON (CH 3 ) —, —N (CH 3 ) CO—, or —O (CH 2 ) m — (wherein m is an integer of 1 to 5), Y 4 is a nitrogen-containing aromatic heterocyclic ring, and n is an integer of 1 to 4.
  • the bonding position of the two amino groups (—NH 2 ) in the formula [2] is not limited. Specifically, with respect to the linking group (Y 1 ) of the side chain, 2, 3 position, 2, 4 position, 2, 5 position, 2, 6 position, 3, 4 position on the benzene ring Position, 3, 5 positions. Among these, from the viewpoint of reactivity when synthesizing a polyamic acid, the positions 2, 4 and 2, 5, and 3, 5 are preferable. Considering the ease in synthesizing the diamine compound, the positions 2, 4 or 2, 5 are more preferable.
  • Y 1 represents —O—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —CH 2 O—, —OCO—, —CON (CH 3 ) —. Or —N (CH 3 ) CO—.
  • —O—, —NH—, —CONH—, —NHCO—, —CON (CH 3 ) —, —CH 2 O—, or —OCO— is preferable because a diamine compound can be easily synthesized.
  • Particularly preferred is —O—, —NH—, —CONH—, —NHCO—, —CON (CH 3 ) —, or —CH 2 O—.
  • Y 2 represents a single bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group, or an aromatic hydrocarbon group.
  • the aliphatic hydrocarbon group having 1 to 20 carbon atoms may be linear, branched or may have an unsaturated bond.
  • An aliphatic hydrocarbon group having 1 to 10 carbon atoms is preferred.
  • non-aromatic hydrocarbon group examples include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring.
  • Decane ring cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, cycloicosane ring, tricycloeicosan ring, tricyclodecosan ring, bicycloheptane ring, decahydronaphthalene ring , Norbornene ring, adamantane ring and the like.
  • aromatic hydrocarbon group examples include a benzene ring, naphthalene ring, tetrahydronaphthalene ring, azulene ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring, and phenalene ring.
  • Preferred Y 2 in the formula [2] is a single bond, a linear or branched alkylene group having 1 to 10 carbon atoms, an unsaturated alkylene group having 1 to 10 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, A cyclohexane ring, a cycloheptane ring, a norbornene ring, an adamantane ring, a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, a fluorene ring, and an anthracene ring are preferable, and a single bond, a linear or branched alkyl having 1 to 10 carbon atoms is more preferable.
  • an unsaturated alkyl group having 1 to 10 carbon atoms an unsaturated alkyl group having 1 to 10 carbon atoms, a cyclohexane ring, a norbornene ring, an adamantane ring, a benzene ring, a naphthalene ring, a fluorene ring, and an anthracene ring, and more preferably a single bond and a carbon number of 1 to 10
  • Examples include linear or branched alkyl groups, cyclohexane rings, benzene rings, and naphthalene rings. Particularly preferred are a single bond, a linear or branched alkyl group having 1 to 5 carbon atoms, and a benzene ring.
  • Y 3 represents a single bond, —O—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —COO—, —OCO—, —CON (CH 3 ).
  • Y 4 is a nitrogen-containing aromatic heterocyclic ring, and nitrogen containing at least one structure selected from the group consisting of the following formula [2a], formula [2b], and formula [2c] Containing aromatic heterocycle.
  • a 1 is a linear or branched alkyl group having 1 to 5 carbon atoms).
  • nitrogen-containing aromatic heterocycle examples include 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, an isoquinoline ring, a carbazole ring, and a purine ring.
  • Preferred Y 4 in the formula [2] is a pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring , Pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, tinoline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring
  • Y 3 is formula contained in Y 4 [2a], wherein [2b], and is preferably bonded with a substituent nonadjacent the formula [2c].
  • n is an integer of 1 to 4, preferably 1 to 3 from the viewpoint of reactivity with tetracarboxylic dianhydride.
  • a preferred combination of Y 1 , Y 2 , Y 3 , Y 4 , and n in the formula [2] is such that Y 1 is —O—, —NH—, —CONH—, —NHCO—, —CON (CH 3 ) — , —CH 2 O—, or —OCO—, wherein Y 2 is a linear or branched alkyl group having 1 to 10 carbon atoms, an unsaturated alkyl group having 1 to 10 carbon atoms, a cyclopropane ring, a cyclobutane ring, or cyclopentane Ring, cyclohexane ring, cycloheptane ring, norbornene ring, adamantane ring, benzene ring, naphthalene ring,
  • Y 1 is —O—, —NH—, —CONH—, —NHCO—, —CH 2 O—, Or —OCO—, wherein Y 2 is a linear or branched alkyl group having 1 to 10 carbon atoms, an unsaturated alkyl group having 1 to 10 carbon atoms, a cyclohexane ring, a norbornene ring, an adamantane ring, a benzene ring, a naphthalene ring, or fluorene A ring or an anthracene ring, and Y 3 is a single bond, —O—, —NH—, —CONH—, —NHCO—, —COO—, —OCO—, or —O (CH 2 ) m — (m is 1 to an integer of 5),
  • Y 1 , Y 2 , Y 3 , Y 4 , and n in the formula [2] are such that Y 1 is —O—, —NH—, —CONH—, —NHCO—, —CON (CH 3 ).
  • Y 2 is a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclohexane ring, a benzene ring, or a naphthalene ring
  • Y 3 is a single bond , —O—, —CONH—, —NHCO—, —COO—, —OCO—, or —O (CH 2 ) m — (m is an integer of 1 to 5)
  • Y 4 is a pyrrole ring, An imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, or a benzimidazole ring, and n is 1 or 2.
  • a particularly preferred combination of Y 1 , Y 2 , Y 3 , Y 4 , and n in formula [2] is that Y 1 is —O—, —NH—, —CONH—, —NHCO—, —CON (CH 3 ).
  • Y 2 is a single bond, a linear or branched alkyl group having 1 to 5 carbon atoms, or a benzene ring
  • Y 3 is a single bond, —O—, —CONH—, — NHCO—, —COO—, —OCO—, or —O (CH 2 ) m — (m is an integer of 1 to 5)
  • Y 4 represents a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, or A pyrimidine ring
  • n is 1 to 3.
  • Tables 1 to 8 The most preferred combinations of Y 1 , Y 2 , Y 3 , Y 4 , and n in the formula [2] are as shown in Tables 1 to 8 below.
  • the method for reducing the dinitro compound is not particularly limited. Usually, palladium-carbon, platinum oxide, Raney nickel, platinum black, rhodium-alumina, platinum sulfide carbon, etc. are used as a catalyst, ethyl acetate, toluene, tetrahydrofuran, dioxane, There is a method of performing reduction with hydrogen gas, hydrazine, hydrogen chloride or the like in an alcohol-based solvent.
  • Y 1 , Y 2 , Y 3 , Y 4 , and n in the formula [2d] are as defined in the formula [2].
  • Dinitro compound of formula [2d], via a Y 3 is bound to Y 2 and Y 4, then, a method of attaching dinitro section through the Y 1, the Y 2 via a connecting portion Y 1 dinitro portion It can be obtained by, for example, a method of bonding to Y 4 via Y 3 .
  • Y 1 is —O— (ether bond), —NH— (amino bond), —N (CH 3 ) — (methylated amino bond), —CONH— (amide bond), —NHCO— (reverse amide bond), —CH 2 O— (methylene ether bond), —OCO— (reverse ester bond), —CON (CH 3 ) — (N-methylated amide bond), or —N (CH 3 ) CO— (N-methylated)
  • a linking group such as a reverse amide bond), and these linking groups can be formed by ordinary organic synthetic techniques.
  • Y 1 is an ether or methylene ether bond
  • a corresponding dinitro group-containing halogen derivative is reacted with a hydroxyl group derivative containing Y 2 , Y 3 and Y 4 in the presence of an alkali, or a dinitro group-containing hydroxyl group derivative And a halogen-substituted derivative containing Y 2 , Y 3 and Y 4 in the presence of an alkali.
  • an amino bond a method of reacting a corresponding dinitro group-containing halogen derivative with an amino group-substituted derivative containing Y 2 , Y 3 and Y 4 in the presence of an alkali can be mentioned.
  • an ester bond a method of reacting a corresponding dinitro group-containing acid chloride and a hydroxyl group-substituted derivative containing Y 2 , Y 3 and Y 4 in the presence of an alkali can be mentioned.
  • a reverse ester bond a method of reacting a corresponding dinitro group-containing hydroxyl group derivative with an acid chloride containing Y 2 , Y 3 and Y 4 in the presence of an alkali can be mentioned.
  • dinitro group-containing halogen derivatives and dinitro group-containing derivatives include 3,5-dinitrochlorobenzene, 2,4-dinitrochlorobenzene, 2,4-dinitrofluorobenzene, 3,5-dinitrobenzoic acid chloride, 3,5 -Dinitrobenzoic acid, 2,4-dinitrobenzoic acid chloride, 2,4-dinitrobenzoic acid, 3,5-dinitrobenzyl chloride, 2,4-dinitrobenzyl chloride, 3,5-dinitrobenzyl alcohol, 2,4- Dinitrobenzyl alcohol, 2,4-dinitroaniline, 3,5-dinitroaniline, 2,6-dinitroaniline, 2,4-dinitrophenol, 2,5-dinitrophenol, 2,6-dinitrophenol, 2,4- And dinitrophenylacetic acid.
  • the dinitro group-containing halogen derivative and the dinitro group-containing derivative can be used by selecting one or more kinds in consideration of the availability of raw materials and the point of reaction.
  • the diamine compound (C) used in the present invention is a diamine compound having a carboxyl group in the molecule.
  • the specific structure is not particularly limited, the compound represented by the formula [3] is preferable.
  • Z 1 is an organic group having an aromatic ring having 6 to 30 carbon atoms
  • k is an integer of 1 to 4.
  • Specific examples of the compound represented by the formula [3] include diamine compounds represented by the following formula [3a], formula [3b], formula [3c], formula [3d] and formula [3e].
  • m 1 is an integer of 1 to 4.
  • Z 2 represents a single bond, —CH 2 —, —C 2 H 4 —, —C (CH 3 ) 2 —, —CF 2 —, —C (CF 3 ) —, —O—, —CO—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —CH 2 O—, —OCH 2 —, —COO—, —OCO—, —CON (CH 3 ) —, Or —N (CH 3 ) CO—, m 2 and m 3 each represent an integer of 0 to 4, and m 2 + m 3 represents an integer of 1 to 4.
  • m 4 and m 5 are each an integer of 1 to 5.
  • Z 3 is a linear or branched alkyl group having 1 to 5 carbon atoms
  • m 6 is an integer of 1 to 5.
  • Z 4 represents a single bond, —CH 2 —, —C 2 H 4 —, —C (CH 3 ) 2 —, —CF 2 —, —C (CF 3 ) —, —O—, —CO—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —CH 2 O—, —OCH 2 —, —COO—, —OCO—, —CON (CH 3 ) —, Or —N (CH 3 ) CO—, and m 7 represents an integer of 1 to 4.
  • m 1 is an integer of 1 to 2
  • Z 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 m 2 and m 3 are both integers of 1, and in formula [3e], Z 4 is A single bond, —CH 2 —, —O—, —CO—, —NH—, —CONH—, —NHCO—, —CH 2 O—, —OCH 2 —, —COO—, or —OCO—, m 7 is a structure which is an integer of 1 to 2.
  • diamine compound (C) examples include compounds of the following formula [3f] to formula [3n] and formula [3p].
  • B 1 is a single bond, —CH 2 —, —O—, —CO—, —NH—, —CONH—, —NHCO—, —CH 2 O—, —OCH 2 —, —COO. -Or -OCO-.
  • B 2 is a single bond, —CH 2 —, —O—, —CO—, —NH—, —CONH—, —NHCO—, —CH 2 O—, —OCH 2 —, —COO. -Or -OCO-.
  • the side chain includes an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, and a macrocyclic substitution composed thereof.
  • a diamine compound having a body can be used. Specifically, diamines represented by the following formulas [DA1] to [DA26] can be exemplified.
  • R 1 is an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group having 1 to 22 carbon atoms.
  • 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 having 1 to 22 carbon atoms.
  • R 4 represents —O—, —OCH 2 —, —CH 2 O—, —COOCH 2 —, or —CH 2 OCO—
  • R 5 represents 1 carbon atom.
  • alkyl group having 22 or less an alkoxy group having 1 to 22 carbon atoms, a fluorine-containing alkyl group having 1 to 22 carbon atoms, or a fluorine-containing alkoxy group having 1 to 22 carbon atoms.
  • 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 having 1 to 22 carbon atoms, a fluorine-containing alkyl group having 1 to 22 carbon atoms, or 1 or more carbon atoms. 22 or less 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 trifluorometal group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group, or a hydroxyl group It is.
  • m is an integer of 1 to 10.
  • 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 is not particularly limited. Specific examples of carboxylic acid for obtaining tetracarboxylic dianhydride are given below. Pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7 -Anthracene tetracarboxylic acid, 1,2,5,6-anthracene tetracarboxylic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 2,3,3', 4-biphenyltetracarboxylic acid, bis ( 3,4-dicarboxyphenyl) ether, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, bis (3,4-dicarboxy
  • the tetracarboxylic dianhydride can be used singly or in combination of two or more according to properties such as liquid crystal alignment properties, voltage holding properties, and accumulated charges when formed into a liquid crystal alignment film.
  • the copolymer of the present invention is a polyamic acid obtained by reacting a diamine compound (A), a diamine compound (B), a diamine component containing the diamine compound (C), and a tetracarboxylic dianhydride, And 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 alignment film.
  • the pretilt angle of the liquid crystal increases as the content ratio of the diamine compound (A) in the diamine component increases. Therefore, the content of the diamine compound (A) in the diamine component is preferably 0.01 to 99 mol with respect to 1 mol of the diamine compound (C). More preferably, it is 0.1 to 75 mol, and still more preferably 0.5 to 50 mol.
  • the liquid crystal alignment film obtained by using the copolymer of the present invention has a higher voltage holding ratio and is exposed to a high temperature for a long time as the content ratio of the diamine compound (B) in the diamine component increases. Even so, the residual charge accumulated by the DC voltage is alleviated faster.
  • the content of the diamine compound (B) is preferably 0.01 to 99 mol with respect to 1 mol of the diamine compound (C).
  • the amount is more preferably 0.1 to 50 mol, still more preferably 0.5 to 20 mol, and most preferably 0.5 to 10 mol.
  • a known synthesis method can be used.
  • tetracarboxylic dianhydride and diamine are reacted in an organic solvent.
  • the reaction of tetracarboxylic dianhydride and diamine is advantageous in that it proceeds relatively easily in an organic solvent and no by-product is generated.
  • the organic solvent used for the reaction between diamine and tetracarboxylic dianhydride is not particularly limited as long as the produced polyamic acid can be dissolved. Specific examples are given below.
  • 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.
  • the solution in which the diamine component is dispersed or dissolved in the organic solvent is stirred, and the tetracarboxylic dianhydride is used as it is or in an organic solvent.
  • a method of adding by dispersing or dissolving a method of adding a diamine component to a solution in which tetracarboxylic dianhydride is dispersed or dissolved in an organic solvent, and alternately adding a tetracarboxylic dianhydride and a diamine component. Any of these methods may be used.
  • tetracarboxylic dianhydride or diamine component when they are composed of a plurality of types of compounds, they may be reacted in a premixed state, may be individually reacted sequentially, or may be further reacted individually. May be mixed and reacted to form a high molecular weight product.
  • the polymerization temperature at that time can be selected from -20 to 150 ° C., but is preferably in the range of ⁇ 5 to 100 ° C.
  • the reaction can be carried out at any concentration, but if the concentration is too low, it is difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring is difficult. Therefore, the total of the diamine component and the tetracarboxylic dianhydride is preferably 1 to 50% by mass, more preferably 5 to 30% by mass with respect to the total reaction solution (100% by mass).
  • the initial stage of the reaction is carried out at a high concentration, and then an organic solvent can be added.
  • the ratio of the total number of moles of tetracarboxylic dianhydride to the total number of moles of the diamine component is preferably 0.8 to 1.2. Similar to the normal polycondensation reaction, the closer the molar ratio is to 1.0, the higher the molecular weight of the polyamic acid produced.
  • the polyimide of the present invention is a polyimide obtained by dehydrating and ring-closing the above polyamic acid, 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 application and purpose.
  • the method for imidizing the polyamic acid include thermal imidization in which the polyamic acid solution is heated as it is, catalytic imidization in which a catalyst is added to the polyamic acid solution, and the like.
  • the temperature at which the polyamic acid is thermally imidized in the solution is 100 to 400 ° C., preferably 120 to 250 ° C., and the method is preferably performed while removing water generated by the imidization reaction from the system.
  • Catalytic imidation of polyamic acid can be carried out by adding a basic catalyst and an acid anhydride to a polyamic acid solution and stirring at -20 to 250 ° C, preferably 0 to 180 ° C.
  • the amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times 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.
  • the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Among them, pyridine is preferable because it has an appropriate basicity for proceeding with the reaction.
  • Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated.
  • the imidization rate by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.
  • 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 copolymer recovered by precipitation is redissolved in an organic solvent and reprecipitated and recovered, the impurities in the copolymer can be reduced.
  • the poor solvent at this time include alcohols, ketones, hydrocarbons and the like, and it is preferable to use three or more kinds of poor solvents selected from these because purification efficiency is further improved.
  • the molecular weights of the polyamic acid and the polyimide contained in the liquid crystal alignment treatment agent of the present invention are GPC (Gel Permeation Chromatography) in consideration of the strength of the obtained coating film, workability during coating film formation, and uniformity of the coating film.
  • the weight average molecular weight measured by the above 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 forming a liquid crystal aligning film, and is a solution in which the resin component for forming a resin film melt
  • the resin component is a resin component containing at least one copolymer selected from the copolymers of the present invention described above.
  • the content of the resin component is preferably 1 to 20% by mass, more preferably 3 to 15% by mass, and particularly preferably 3 to 10% by mass with respect to the entire liquid crystal alignment treatment agent (100% by mass). is there.
  • all of the above resin components may be the copolymer of the present invention, and other copolymers may be mixed with the copolymer of the present invention.
  • the content of the other copolymer in the resin component is 0.5 to 15% by mass, preferably 1 to 10% by mass.
  • Such other copolymer is, for example, a polyamide obtained by using a diamine other than the diamine compound (A), the diamine compound (B), and the diamine compound (C) as a diamine component to be reacted with tetracarboxylic dianhydride. An acid or a polyimide is mentioned.
  • 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.
  • the liquid crystal aligning agent of this invention may contain components other than the above.
  • examples thereof include a solvent or compound that improves the film thickness uniformity and surface smoothness when a liquid crystal alignment treatment agent is applied, and a compound that improves the adhesion between the liquid crystal alignment film and the substrate.
  • Specific examples of the solvent for improving the film thickness uniformity and surface smoothness include the following.
  • solvents may be used alone or in combination.
  • it is preferably 5 to 80% by mass, more preferably 20 to 60% by mass, based on the total amount of the solvent contained in the liquid crystal aligning agent.
  • the compound that improves the uniformity of the film thickness and the surface smoothness include a fluorine-based surfactant, a silicone-based surfactant, and a nonionic surfactant.
  • 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 (manufactured by 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 is preferably 0.1 to 30 parts by mass, more preferably 1 to 30 parts by mass with respect to 100 parts by mass of the resin component contained in the liquid crystal aligning agent. 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.
  • the liquid crystal alignment treatment agent of the present invention is a dielectric or conductive material for the purpose of changing the electrical properties such as the dielectric constant and conductivity of the liquid crystal alignment film as long as the effects of the present invention are not impaired.
  • a crosslinkable compound for the purpose of increasing the hardness and density of the liquid crystal alignment film may be added.
  • the liquid crystal alignment treatment agent of the present invention can be used as a liquid crystal alignment film without applying an alignment treatment after being applied and baked on a substrate and then subjected to an alignment treatment by rubbing treatment, light irradiation, or the like.
  • the substrate to be used is not particularly limited as long as it is a highly transparent substrate, and a glass substrate or a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used.
  • a substrate on which an ITO electrode or the like for driving liquid crystal is formed from the viewpoint of simplifying the process.
  • 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.
  • a method for applying the liquid crystal alignment treatment agent is not particularly limited, but industrially, a method of performing 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.
  • Firing 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. If it is too thin, the reliability of the liquid crystal display element may be lowered. 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, spray spacers on the liquid crystal alignment film of one substrate, and make the liquid crystal alignment film surface inside. Examples include a method of bonding the other substrate and injecting the liquid crystal under reduced pressure, or a method of sealing the liquid crystal after dropping the liquid crystal on the liquid crystal alignment film surface on which the spacers are dispersed, and the like. .
  • the thickness of the spacer at this time is preferably 1-30 ⁇ m, more preferably 2-10 ⁇ m.
  • the liquid crystal display device manufactured using the liquid crystal alignment treatment agent of the present invention has excellent reliability and can be suitably used for a large-screen, high-definition liquid crystal television.
  • PBCH5DAB 1,3-diamino-4- ⁇ 4- [trans-4- (trans-4-n-pentylcyclohexyl) cyclohexyl] phenoxy ⁇ benzene
  • PBCH7DAB 1,3-diamino-4- ⁇ 4- [trans-4 -(Trans-4-n-heptylcyclohexyl) cyclohexyl] phenoxy ⁇ benzene
  • BPCH5DAB 1,3-diamino-4- ⁇ 4- [4- (trans-4-n-pentylcyclohexyl) phenyl] phenoxy ⁇ benzene
  • p-PDA p-phenylenediamine
  • m-PBCH5DABEs 3,5-diamino- ⁇ 4- [trans-4- (trans-4-n-pentylcyclohexyl) cyclohexyl] phenyl ⁇ benzoate
  • PBP5DABz 1,3-diamino- 4-[(4-n-pentylphenyl) phenoxymethyl] benzene
  • PCH7DAB 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxy] benzene
  • PBP5DAB 1,3-diamino-4 -[(4-n-pentylphenyl) phenoxy] benzenediamine (S1)
  • 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 manufactured by Shodex (KD-803, KD-805).
  • 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 liquid crystal aligning agent [1] obtained above was spin-coated on the ITO surface of the 3 cm ⁇ 4 cm ITO electrode substrate, and baked at 80 ° C. for 5 minutes in a 210 ° C. hot air circulating oven for 1 hour. A polyimide coating was prepared.
  • This substrate with a liquid crystal alignment film is subjected to a rubbing treatment with a roll diameter 120 mm, a rayon cloth rubbing device under the conditions of a rotation speed of 300 rpm, a roll traveling speed of 20 mm / sec, and an indentation amount of 0.3 mm.
  • a rubbing treatment with a roll diameter 120 mm, a rayon cloth rubbing device under the conditions of a rotation speed of 300 rpm, a roll traveling speed of 20 mm / sec, and an indentation amount of 0.3 mm.
  • pretilt angle of the liquid crystal cell produced as described above was measured at room temperature using a pretilt angle measuring device (ELSICON model: PAS-301). The results are shown in Table 11. Moreover, when the liquid crystal cell produced similarly to the above except having not rubbed was observed with the polarization microscope, it was confirmed that the liquid crystal was uniformly vertically aligned.
  • ⁇ Evaluation of voltage holding ratio> A voltage of 4 V was applied to the liquid crystal cell after the pretilt angle measurement at a temperature of 80 ° C. at 60 ⁇ m, the voltage after 16.67 ms and 1667 ms was measured, and the voltage holding ratio was calculated as the voltage holding ratio. . The results are shown in Table 12.
  • ⁇ Evaluation of relaxation of residual charge> A DC voltage of 10 V was applied to the liquid crystal cell after measuring the voltage holding ratio for 30 minutes and short-circuited for 1 second, and then the potential generated in the liquid crystal cell was measured for 1800 seconds. Then, the residual charges after 50 seconds and 1000 seconds were measured. For measurement, a 6254 type liquid crystal physical property evaluation apparatus manufactured by Toyo Technica Co., Ltd. was used.
  • liquid crystal aligning agent [3] was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
  • a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 11 described later. In addition, when the liquid crystal cell produced like Example 1 was observed with the polarizing microscope except not having rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned. Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 12 and Table 13.
  • NMP (22.7g) and BCS (25.8g) were added to this polyimide powder (3.10g), and liquid crystal aligning agent [5] was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
  • Example 11 Using the obtained liquid crystal aligning agent [5], a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 11. In addition, when the liquid crystal cell produced like Example 1 was observed with the polarizing microscope except not having rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned. Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 12 and Table 13.
  • liquid crystal aligning agent [6] was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
  • a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 11. In addition, when the liquid crystal cell produced like Example 1 was observed with the polarizing microscope except not having rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned. Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 12 and Table 13.
  • liquid crystal aligning agent [8] was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
  • a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 11. In addition, when the liquid crystal cell produced like Example 1 was observed with the polarizing microscope except not having rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned. Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 12 and Table 13.
  • NMP (10.0 g) and BCS (36.5 g) were added to the obtained polyamic acid solution (20.0 g) to obtain a liquid crystal aligning agent [9]. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
  • Example 11 Using the obtained liquid crystal aligning agent [9], a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 11. In addition, when the liquid crystal cell produced like Example 1 was observed with the polarizing microscope except not having rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned. Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 12 and Table 13.
  • Example 11 Using the obtained liquid crystal aligning agent [10], a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 11. In addition, when the liquid crystal cell produced like Example 1 was observed with the polarizing microscope except not having rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned. Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 12 and Table 13.
  • NMP (13.3 g) and BCS (33.4 g) were added to the obtained polyamic acid solution (20.0 g) to obtain a liquid crystal aligning agent [11]. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
  • Example 11 Using the obtained liquid crystal aligning agent [11], a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 11. In addition, when the liquid crystal cell produced like Example 1 was observed with the polarizing microscope except not having rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned. Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 12 and Table 13.
  • Example 12 Using the obtained liquid crystal aligning agent [12], a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 11. In addition, when the liquid crystal cell produced like Example 1 was observed with the polarizing microscope except not having rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned. Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 12 and Table 13.
  • NMP (20.8g) and BCS (29.3g) were added to this polyimide powder (3.21g), and liquid crystal aligning agent [13] was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
  • Example 11 Using the obtained liquid crystal aligning agent [13], a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 11. In addition, when the liquid crystal cell produced like Example 1 was observed with the polarizing microscope except not having rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned. Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 12 and Table 13.
  • NMP was added to this polyamic acid solution (20.2 g) to dilute the polyamic acid content to 6% by mass, and then acetic anhydride (4.30 g) and pyridine (3.33 g) as an imidization catalyst. And reacted at 90 ° C. for 3.5 hours.
  • This reaction solution was put into methanol (270 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder.
  • the imidation ratio of this polyimide was 80%, the number average molecular weight was 17,900, and the weight average molecular weight was 47,300.
  • Example 11 Using the obtained liquid crystal aligning agent [14], a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 11. In addition, when the liquid crystal cell produced like Example 1 was observed with the polarizing microscope except not having rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned. Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 12 and Table 13.
  • Example 15 ⁇ Example 15> BODA (3.50 g, 14.0 mol), m-BPCH5DABz (3.98 g, 8.39 mmol), diamine (B1) (2.03 g, 8.39 mmol), and DBA (1.70 g, 11.2 mmol). After mixing in NMP (23.2 g) and reacting at 80 ° C. for 5 hours, CBDA (2.74 g, 14.0 mmol) and NMP (18.5 g) were added and reacted at 40 ° C. for 6 hours. A solution was obtained.
  • NMP was added to this polyamic acid solution (20.0 g) to dilute the polyamic acid content to 6% by mass, and then acetic anhydride (4.29 g) and pyridine (3.35 g) as an imidization catalyst. And reacted at 80 ° C. for 4 hours.
  • This reaction solution was put into methanol (290 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder.
  • the imidation ratio of this polyimide was 54%, the number average molecular weight was 17,800, and the weight average molecular weight was 48,100.
  • Example 11 Using the obtained liquid crystal aligning agent [15], a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 11. In addition, when the liquid crystal cell produced like Example 1 was observed with the polarizing microscope except not having rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned. Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 12 and Table 13.
  • NMP (22.7g) and BCS (25.8g) were added to this polyimide powder (3.30g), and liquid crystal aligning agent [16] was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
  • Example 11 Using the obtained liquid crystal aligning agent [16], a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 11. In addition, when the liquid crystal cell produced like Example 1 was observed with the polarizing microscope except not having rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned. Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 12 and Table 13.
  • Example 11 Using the obtained liquid crystal aligning agent [17], a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 11. In addition, when the liquid crystal cell produced like Example 1 was observed with the polarizing microscope except not having rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned. Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 12 and Table 13.
  • Example 11 Using the obtained liquid crystal aligning agent [18], a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 11. In addition, when the liquid crystal cell produced like Example 1 was observed with the polarizing microscope except not having rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned. Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 12 and Table 13.
  • NMP (22.1g) and BCS (25.0g) were added to this polyimide powder (3.20g), and the liquid-crystal aligning agent [19] was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
  • Example 11 Using the obtained liquid crystal aligning agent [19], a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 11. In addition, when the liquid crystal cell produced like Example 1 was observed with the polarizing microscope except not having rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned. Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 12 and Table 13.
  • NMP was added to this polyamic acid solution (20.1 g) to dilute the polyamic acid content to 6% by mass, and then acetic anhydride (2.50 g) and pyridine (1.95 g) as an imidization catalyst. And reacted at 80 ° C. for 4 hours.
  • This reaction solution was put into methanol (290 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder.
  • the imidation ratio of this polyimide was 54%, the number average molecular weight was 18,100, and the weight average molecular weight was 47,800.
  • NMP (22.7g) and BCS (25.8g) were added to this polyimide powder (3.11g), and liquid crystal aligning agent [20] was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
  • Example 11 Using the obtained liquid crystal aligning agent [20], a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 11. In addition, when the liquid crystal cell produced like Example 1 was observed with the polarizing microscope except not having rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned. Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 12 and Table 13.
  • the liquid crystal aligning agent [21] obtained above was spin-coated on the ITO surface of the 3 cm ⁇ 4 cm ITO electrode substrate, and baked at 80 ° C. for 5 minutes in a 210 ° C. hot air circulating oven for 1 hour. A polyimide coating was prepared.
  • This substrate with a liquid crystal alignment film is subjected to a rubbing treatment with a roll diameter 120 mm, a rayon cloth rubbing device under the conditions of a rotation speed of 300 rpm, a roll traveling speed of 20 mm / sec, and an indentation amount of 0.3 mm.
  • a rubbing treatment with a roll diameter 120 mm, a rayon cloth rubbing device under the conditions of a rotation speed of 300 rpm, a roll traveling speed of 20 mm / sec, and an indentation amount of 0.3 mm.
  • ⁇ Evaluation of pretilt angle> The pretilt angle of the liquid crystal cell produced as described above was measured at room temperature using a pretilt angle measuring device (ELSICON model: PAS-301). The results are shown in Table 15. Moreover, when the liquid crystal cell produced similarly to the above except having not rubbed was observed with the polarization microscope, it was confirmed that the liquid crystal was uniformly vertically aligned.
  • ⁇ Evaluation of voltage holding ratio> A voltage of 4 V was applied to the liquid crystal cell after the pretilt angle measurement at a temperature of 80 ° C. at 60 ⁇ m, the voltage after 16.67 ms and 1667 ms was measured, and the voltage holding ratio was calculated as the voltage holding ratio. . The results are shown in Table 16.
  • Example 21 Using the obtained liquid crystal aligning agent [22], a liquid crystal cell was produced in the same manner as in Example 21, and the pretilt angle was evaluated. The results are shown in Table 15. In addition, when the liquid crystal cell produced like Example 21 was observed with the polarizing microscope except not having rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned. Further, using the liquid crystal cell manufactured in the same manner as in Example 21, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 16 and Table 17.
  • Example 21 Using the obtained liquid crystal aligning agent [23], a liquid crystal cell was produced in the same manner as in Example 21, and the pretilt angle was evaluated. The results are shown in Table 15. In addition, when the liquid crystal cell produced like Example 21 was observed with the polarizing microscope except not having rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned. Further, using the liquid crystal cell manufactured in the same manner as in Example 21, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 16 and Table 17.
  • NMP (22.1g) and BCS (25.3g) were added to this polyimide powder (3.00g), and liquid crystal aligning agent [25] was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
  • Example 21 Using the obtained liquid crystal aligning agent [25], a liquid crystal cell was produced in the same manner as in Example 21, and the pretilt angle was evaluated. The results are shown in Table 15. In addition, when the liquid crystal cell produced like Example 21 was observed with the polarizing microscope except not having rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned. Further, using the liquid crystal cell manufactured in the same manner as in Example 21, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 16 and Table 17.
  • NMP (29.3g) and BCS (33.3g) were added to this polyimide powder (4.01g), and the liquid-crystal aligning agent [26] was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
  • Example 21 Using the obtained liquid crystal aligning agent [26], a liquid crystal cell was produced in the same manner as in Example 21, and the pretilt angle was evaluated. The results are shown in Table 15. In addition, when the liquid crystal cell produced like Example 21 was observed with the polarizing microscope except not having rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned. Further, using the liquid crystal cell manufactured in the same manner as in Example 21, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 16 and Table 17.
  • Example 21 Using the obtained liquid crystal aligning agent [27], a liquid crystal cell was produced in the same manner as in Example 21, and the pretilt angle was evaluated. The results are shown in Table 15. In addition, when the liquid crystal cell produced like Example 1 was observed with the polarizing microscope except not having rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned. Further, using the liquid crystal cell manufactured in the same manner as in Example 21, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 16 and Table 17.
  • Example 21 Using the obtained liquid crystal aligning agent [28], a liquid crystal cell was produced in the same manner as in Example 21, and the pretilt angle was evaluated. The results are shown in Table 15. In addition, when the liquid crystal cell produced like Example 21 was observed with the polarizing microscope except not having rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned. Further, using the liquid crystal cell manufactured in the same manner as in Example 21, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 16 and Table 17.
  • a liquid crystal aligning agent [29] NMP (10.0 g) and BCS (36.7 g) were added to the obtained polyamic acid solution (20.1 g) to obtain a liquid crystal aligning agent [29]. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
  • a liquid crystal aligning agent [29] Using the obtained liquid crystal aligning agent [29], a liquid crystal cell was produced in the same manner as in Example 21, and the pretilt angle was evaluated. The results are shown in Table 15. In addition, when the liquid crystal cell produced like Example 21 was observed with the polarizing microscope except not having rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned. Further, using the liquid crystal cell manufactured in the same manner as in Example 21, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 16 and Table 17.
  • NMP (20.8 g) and BCS (29.3 g) were added to this polyimide powder (3.20 g) to obtain a liquid crystal aligning agent [30]. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
  • Example 21 Using the obtained liquid crystal aligning agent [30], a liquid crystal cell was produced in the same manner as in Example 21, and the pretilt angle was evaluated. The results are shown in Table 15. In addition, when the liquid crystal cell produced like Example 21 was observed with the polarizing microscope except not having rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned. Further, using the liquid crystal cell manufactured in the same manner as in Example 21, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 16 and Table 17.
  • NMP (21.5g) and BCS (30.3g) were added to this polyimide powder (3.31g), and liquid crystal aligning agent [32] was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
  • Example 21 Using the obtained liquid crystal aligning agent [32], a liquid crystal cell was produced in the same manner as in Example 21, and the pretilt angle was evaluated. The results are shown in Table 15. In addition, when the liquid crystal cell produced like Example 21 was observed with the polarizing microscope except not having rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned. Further, using the liquid crystal cell manufactured in the same manner as in Example 21, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 16 and Table 17.
  • Example 21 Using the obtained liquid crystal aligning agent [33], a liquid crystal cell was produced in the same manner as in Example 21, and the pretilt angle was evaluated. The results are shown in Table 15. In addition, when the liquid crystal cell produced like Example 21 was observed with the polarizing microscope except not having rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned. Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 16 and Table 17.
  • NMP (20.2g) and BCS (28.4g) were added to this polyimide powder (3.11g), and the liquid-crystal aligning agent [34] was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
  • Example 21 Using the obtained liquid crystal aligning agent [34], a liquid crystal cell was produced in the same manner as in Example 21, and the pretilt angle was evaluated. The results are shown in Table 15. In addition, when the liquid crystal cell produced like Example 21 was observed with the polarizing microscope except not having rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned. Further, using the liquid crystal cell manufactured in the same manner as in Example 21, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 16 and Table 17.
  • Example 21 Using the obtained liquid crystal aligning agent [35], a liquid crystal cell was produced in the same manner as in Example 21, and the pretilt angle was evaluated. The results are shown in Table 15. In addition, when the liquid crystal cell produced like Example 21 was observed with the polarizing microscope except not having rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned. Further, using the liquid crystal cell manufactured in the same manner as in Example 21, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 16 and Table 17.
  • Example 21 Using the obtained liquid crystal aligning agent [36], a liquid crystal cell was produced in the same manner as in Example 21, and the pretilt angle was evaluated. The results are shown in Table 15. In addition, when the liquid crystal cell produced like Example 21 was observed with the polarizing microscope except not having rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned. Further, using the liquid crystal cell manufactured in the same manner as in Example 21, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 16 and Table 17.
  • Printing was performed using the liquid crystal alignment treatment agents obtained in Examples 1 to 16, 21 to 36, and Comparative Examples 1, 2, 5, and 6.
  • a simple printing machine (S15 type) manufactured by Nissha Printing Co., Ltd. was used as the printing machine. Printing was performed on a cleaned chromium vapor deposition substrate at a printing area of 8 cm ⁇ 8 cm, a printing pressure of 0.2 mm, five discarded substrates, a time from printing to temporary drying of 90 seconds, and a temporary drying temperature of 70 ° C. for 5 minutes. .
  • the pinholes were confirmed by visual observation under a sodium lamp. Tables 11 and 15 show the number of pinholes as printability.
  • a liquid crystal display element produced using a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention has excellent reliability, and can be suitably used for a large-screen, high-definition liquid crystal television, etc. Useful.

Landscapes

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

Abstract

L'invention concerne un agent d'alignement de cristaux liquides qui est caractérisé en ce qu'il comporte un copolymère produit en faisant réagir un composant de diamine avec un dianhydride tétracarboxylique, ledit composant de diamine comportant un composé de diamine (A) représenté par la formule [1], un composé de diamine (B) représenté par la formule [2] et un composé de diamine (C) possédant un groupe carboxy dans la molécule. [Dans la formule [1], p représente un nombre entier valant 0 ou 1; X1 représente un groupe phénylène; X2 représente un groupe phénylène ou cyclohexylène; X3 représente un groupe cyclohexylène; et X4 représente un groupe alkyle possédant de 3 à 12 atomes de carbone, un groupe fluoroalkyle possédant de 3 à 12 atomes de carbone, un groupe alcoxy possédant de 3 à 12 atomes de carbone ou un groupe fluoroalcoxy possédant de 3 à 12 atomes de carbone. Dans la formule [2], Y1 représente -O-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -CH2O-, -OCO-, -CON(CH3)- ou -N(CH3)CO-; Y2 représente une liaison simple, un groupe hydrocarboné aliphatique possédant de 1 à 20 atomes de carbone, un groupe hydrocarboné cyclique non aromatique ou un groupe hydrocarboné aromatique; Y3 représente une liaison simple, -O-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -COO-, -OCO-, -CON(CH3)-, -N(CH3)CO- ou -O(CH2)m- (où m représente un nombre entier valant de 1 à 5); Y4 représente un noyau hétérocyclique aromatique azoté; et n représente un nombre entier valant de 1 à 4.]
PCT/JP2009/066422 2008-09-24 2009-09-18 Agent d'alignement de cristaux liquides et élément d'affichage à cristaux liquides l'utilisant Ceased WO2010035719A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2010530837A JP5382372B2 (ja) 2008-09-24 2009-09-18 液晶配向処理剤及びそれを用いた液晶表示素子
CN2009801383003A CN102165365B (zh) 2008-09-24 2009-09-18 液晶取向处理剂以及利用该处理剂的液晶显示元件

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2008245037 2008-09-24
JP2008-245038 2008-09-24
JP2008-245037 2008-09-24
JP2008245038 2008-09-24

Publications (1)

Publication Number Publication Date
WO2010035719A1 true WO2010035719A1 (fr) 2010-04-01

Family

ID=42059718

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2009/066422 Ceased WO2010035719A1 (fr) 2008-09-24 2009-09-18 Agent d'alignement de cristaux liquides et élément d'affichage à cristaux liquides l'utilisant

Country Status (5)

Country Link
JP (1) JP5382372B2 (fr)
KR (1) KR101613751B1 (fr)
CN (1) CN102165365B (fr)
TW (1) TWI457368B (fr)
WO (1) WO2010035719A1 (fr)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2005219450B2 (en) * 2004-03-02 2011-08-04 Poly Coat Pty Ltd Paintable primer system
JP2012042694A (ja) * 2010-08-19 2012-03-01 Jnc Corp ジアミン、液晶配向剤、液晶配向膜および液晶表示素子
US20120057115A1 (en) * 2010-09-03 2012-03-08 Panasonic Liquid Crystal Display Co., Ltd. Liquid crystal display device
WO2012121257A1 (fr) * 2011-03-07 2012-09-13 日産化学工業株式会社 Composition, agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides
WO2012121259A1 (fr) * 2011-03-07 2012-09-13 日産化学工業株式会社 Composition, agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
WO2012165355A1 (fr) * 2011-05-27 2012-12-06 日産化学工業株式会社 Composition, agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
CN103026291A (zh) * 2010-06-10 2013-04-03 日产化学工业株式会社 液晶取向处理剂、液晶取向膜及液晶显示元件
KR20130112742A (ko) 2012-04-03 2013-10-14 제이에스알 가부시끼가이샤 액정 배향제, 액정 배향막, 액정 표시 소자, 중합체 및 화합물
JP2015106156A (ja) * 2013-11-29 2015-06-08 達興材料股▲ふん▼有限公司 液晶配向剤、液晶配向膜および液晶表示素子
JP5936000B2 (ja) * 2010-04-22 2016-06-15 日産化学工業株式会社 液晶表示素子の製造方法
KR20180061414A (ko) * 2011-07-12 2018-06-07 닛산 가가쿠 고교 가부시키 가이샤 조성물, 액정 배향 처리제, 액정 배향막 및 액정 표시 소자
KR20210116592A (ko) 2019-01-22 2021-09-27 닛산 가가쿠 가부시키가이샤 액정 배향제, 액정 배향막 및 액정 표시 소자
US20220169789A1 (en) * 2020-11-27 2022-06-02 Zhen Ding Technology Co., Ltd. Polymer dispersion, method for manufacturing the polymer dispersion, and method for manufacturing polymer composite film

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101951501B1 (ko) * 2011-09-08 2019-02-22 닛산 가가쿠 가부시키가이샤 액정 배향 처리제, 액정 배향막 및 액정 표시 소자
TWI522392B (zh) * 2013-05-22 2016-02-21 奇美實業股份有限公司 液晶配向劑、液晶配向膜及液晶顯示元件
CN103305236B (zh) * 2013-06-25 2015-07-08 深圳市华星光电技术有限公司 一种液晶面板及其配向膜被用于形成液晶面板的用途
TWI482801B (zh) * 2013-09-18 2015-05-01 Chi Mei Corp 液晶配向劑、液晶配向膜及液晶顯示元件
CN107407839B (zh) * 2014-12-25 2020-09-18 日产化学工业株式会社 液晶取向处理剂、液晶取向膜及液晶表示元件
CN107250899B (zh) * 2014-12-25 2020-10-09 日产化学工业株式会社 液晶取向处理剂、液晶取向膜及液晶表示元件

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005097377A (ja) * 2003-09-24 2005-04-14 Fuji Photo Film Co Ltd 配向膜、重合体、それを用いた位相差板およびその作製方法、ならびに液晶表示装置

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW548491B (en) * 2000-07-07 2003-08-21 Nissan Chemical Ind Ltd Liquid crystal orientating agent and liquid crystal display element using the same
JP4228614B2 (ja) * 2002-08-06 2009-02-25 チッソ株式会社 エステル結合を有するフェニレンジアミン
CN101490188B (zh) 2006-07-18 2012-07-04 日产化学工业株式会社 液晶定向剂、使用了该定向剂的液晶定向膜及液晶显示元件

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005097377A (ja) * 2003-09-24 2005-04-14 Fuji Photo Film Co Ltd 配向膜、重合体、それを用いた位相差板およびその作製方法、ならびに液晶表示装置

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2005219450B2 (en) * 2004-03-02 2011-08-04 Poly Coat Pty Ltd Paintable primer system
KR101775182B1 (ko) 2010-04-22 2017-09-05 닛산 가가쿠 고교 가부시키 가이샤 액정 배향 처리제, 액정 배향막 및 액정 표시 소자
JP5936000B2 (ja) * 2010-04-22 2016-06-15 日産化学工業株式会社 液晶表示素子の製造方法
CN103026291A (zh) * 2010-06-10 2013-04-03 日产化学工业株式会社 液晶取向处理剂、液晶取向膜及液晶显示元件
CN103026291B (zh) * 2010-06-10 2015-08-19 日产化学工业株式会社 液晶取向处理剂、液晶取向膜及液晶显示元件
JP2012042694A (ja) * 2010-08-19 2012-03-01 Jnc Corp ジアミン、液晶配向剤、液晶配向膜および液晶表示素子
US20120057115A1 (en) * 2010-09-03 2012-03-08 Panasonic Liquid Crystal Display Co., Ltd. Liquid crystal display device
CN103502312A (zh) * 2011-03-07 2014-01-08 日产化学工业株式会社 组合物、液晶取向处理剂、液晶取向膜及液晶显示元件
CN103502312B (zh) * 2011-03-07 2015-07-29 日产化学工业株式会社 组合物、液晶取向处理剂、液晶取向膜及液晶显示元件
WO2012121259A1 (fr) * 2011-03-07 2012-09-13 日産化学工業株式会社 Composition, agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
WO2012121257A1 (fr) * 2011-03-07 2012-09-13 日産化学工業株式会社 Composition, agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides
CN103492462A (zh) * 2011-03-07 2014-01-01 日产化学工业株式会社 组合物、液晶取向处理剂、液晶取向膜及液晶显示元件
JPWO2012121259A1 (ja) * 2011-03-07 2014-07-17 日産化学工業株式会社 組成物、液晶配向処理剤、液晶配向膜、及び液晶表示素子
JPWO2012121257A1 (ja) * 2011-03-07 2014-07-17 日産化学工業株式会社 組成物、液晶配向処理剤、液晶配向膜、及び液晶表示素子
CN103687911B (zh) * 2011-05-27 2018-04-24 日产化学工业株式会社 组合物、液晶取向处理剂、液晶取向膜及液晶显示元件
JPWO2012165355A1 (ja) * 2011-05-27 2015-02-23 日産化学工業株式会社 組成物、液晶配向処理剤、液晶配向膜及び液晶表示素子
CN103687911A (zh) * 2011-05-27 2014-03-26 日产化学工业株式会社 组合物、液晶取向处理剂、液晶取向膜及液晶显示元件
KR101897846B1 (ko) * 2011-05-27 2018-09-12 닛산 가가쿠 가부시키가이샤 조성물, 액정 배향 처리제, 액정 배향막 및 액정 표시 소자
KR20140033434A (ko) * 2011-05-27 2014-03-18 닛산 가가쿠 고교 가부시키 가이샤 조성물, 액정 배향 처리제, 액정 배향막 및 액정 표시 소자
WO2012165355A1 (fr) * 2011-05-27 2012-12-06 日産化学工業株式会社 Composition, agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
KR102026039B1 (ko) * 2011-07-12 2019-09-26 닛산 가가쿠 가부시키가이샤 조성물, 액정 배향 처리제, 액정 배향막 및 액정 표시 소자
KR20180061414A (ko) * 2011-07-12 2018-06-07 닛산 가가쿠 고교 가부시키 가이샤 조성물, 액정 배향 처리제, 액정 배향막 및 액정 표시 소자
KR20130112742A (ko) 2012-04-03 2013-10-14 제이에스알 가부시끼가이샤 액정 배향제, 액정 배향막, 액정 표시 소자, 중합체 및 화합물
JP2015106156A (ja) * 2013-11-29 2015-06-08 達興材料股▲ふん▼有限公司 液晶配向剤、液晶配向膜および液晶表示素子
KR20210116592A (ko) 2019-01-22 2021-09-27 닛산 가가쿠 가부시키가이샤 액정 배향제, 액정 배향막 및 액정 표시 소자
US20220169789A1 (en) * 2020-11-27 2022-06-02 Zhen Ding Technology Co., Ltd. Polymer dispersion, method for manufacturing the polymer dispersion, and method for manufacturing polymer composite film
US11680138B2 (en) * 2020-11-27 2023-06-20 Zhen Ding Technology Co., Ltd. Polymer dispersion, method for manufacturing the polymer dispersion, and method for manufacturing polymer composite film

Also Published As

Publication number Publication date
JPWO2010035719A1 (ja) 2012-02-23
KR101613751B1 (ko) 2016-04-19
KR20110056523A (ko) 2011-05-30
CN102165365B (zh) 2013-11-06
CN102165365A (zh) 2011-08-24
TW201030055A (en) 2010-08-16
JP5382372B2 (ja) 2014-01-08
TWI457368B (zh) 2014-10-21

Similar Documents

Publication Publication Date Title
JP5382372B2 (ja) 液晶配向処理剤及びそれを用いた液晶表示素子
JP5177150B2 (ja) 液晶配向剤、液晶配向膜及び液晶表示素子
JP5729299B2 (ja) ジアミン化合物、ポリアミド酸、ポリイミド及び液晶配向処理剤
JP5240207B2 (ja) 液晶配向処理剤、及びそれを用いた液晶表示素子
JP5663876B2 (ja) 液晶配向処理剤、及びそれを用いた液晶表示素子
KR101826380B1 (ko) 액정 배향 처리제, 액정 배향막 및 액정 표시 소자
JP5651953B2 (ja) 液晶配向剤、及び液晶表示素子
KR102125106B1 (ko) 액정 배향제, 액정 배향막, 및 액정 표시 소자
JP5999107B2 (ja) 液晶配向剤、液晶配向膜及び液晶表示素子
JP6183616B2 (ja) 液晶配向剤、液晶配向膜及び液晶表示素子
JP5218062B2 (ja) 液晶配向処理剤及びそれを用いた液晶表示素子
JPWO2014024893A1 (ja) 液晶配向剤、液晶配向膜及び液晶表示素子
JP5614412B2 (ja) 液晶配向処理剤、液晶配向膜、及びそれを用いた液晶表示素子

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200980138300.3

Country of ref document: CN

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

Ref document number: 09816134

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2010530837

Country of ref document: JP

ENP Entry into the national phase

Ref document number: 20117006555

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 09816134

Country of ref document: EP

Kind code of ref document: A1