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WO2012121259A1 - Composition, agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides - Google Patents

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

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Publication number
WO2012121259A1
WO2012121259A1 PCT/JP2012/055712 JP2012055712W WO2012121259A1 WO 2012121259 A1 WO2012121259 A1 WO 2012121259A1 JP 2012055712 W JP2012055712 W JP 2012055712W WO 2012121259 A1 WO2012121259 A1 WO 2012121259A1
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Prior art keywords
liquid crystal
group
polyimide
carbon atoms
formula
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PCT/JP2012/055712
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English (en)
Japanese (ja)
Inventor
徳俊 三木
耕平 後藤
幸司 園山
保坂　和義
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Nissan Chemical Corp
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Nissan Chemical Corp
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Priority to JP2013503561A priority Critical patent/JP6075286B2/ja
Priority to KR1020137026224A priority patent/KR101878522B1/ko
Priority to CN201280020095.2A priority patent/CN103492462B/zh
Publication of WO2012121259A1 publication Critical patent/WO2012121259A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
    • C08G73/1032—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous characterised by the solvent(s) used
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/07—Aldehydes; Ketones
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723—Polyimide, polyamide-imide

Definitions

  • the present invention relates to a composition used for forming a film, in particular, a liquid crystal alignment treatment agent used for forming a liquid crystal alignment film, a liquid crystal alignment film to be obtained, and a liquid crystal display element using the liquid crystal alignment film.
  • a film made of an organic material such as a polymer material has been widely used as an interlayer insulating film, a protective film, and the like in electronic devices because of its ease of formation and insulation performance.
  • an organic film made of an organic material is used as a liquid crystal alignment film.
  • the liquid crystal alignment film is formed on the surface of the substrate that sandwiches the liquid crystal, and plays a role of aligning the liquid crystal in a certain direction. Further, the liquid crystal alignment film has a role of controlling the pretilt angle of the liquid crystal in addition to the role of aligning the liquid crystal in a certain direction.
  • liquid crystal display elements have become highly functional, and the range of use of these liquid crystal display elements has expanded, and the liquid crystal alignment film has performance and reliability for achieving high display quality by suppressing display defects of the liquid crystal display elements. Is also sought.
  • the liquid crystal alignment film made of this polyimide organic film is composed of a polyamic acid (also called polyamic acid) which is a polyimide precursor and / or a liquid crystal aligning agent which is a composition containing a polyimide solution imidized with polyamic acid. It is formed. That is, the polyimide-based liquid crystal alignment film is obtained by applying a liquid crystal alignment treatment agent comprising a polyimide solution or a polyamic acid solution, which is a polyimide precursor, to a substrate and firing it at a high temperature of about 200 to 300 ° C. (For example, refer patent document 1).
  • a liquid crystal alignment treatment agent comprising a polyimide solution or a polyamic acid solution, which is a polyimide precursor
  • the baking process for forming the polyimide-based liquid crystal alignment film requires a particularly high temperature in the process of manufacturing a liquid crystal display element. Therefore, in the case where a thin and lightweight plastic substrate having a low heat resistance is used instead of a normal glass substrate as a substrate for a liquid crystal display element, it is required to enable firing at a lower temperature. Similarly, low-temperature firing of the liquid crystal alignment film is also required in order to suppress deterioration such as a decrease in color characteristics in the color filter and to reduce energy costs in manufacturing the liquid crystal display element. Furthermore, the temperature of the baking process is also required to be lowered from the viewpoint of suppressing a decrease in reliability of the liquid crystal display element (such as a decrease in characteristics during long-term use).
  • the present invention provides a composition capable of forming a polyimide organic film formed by heating at a low temperature, particularly a liquid crystal alignment treatment agent capable of forming a liquid crystal alignment film by heating at a low temperature, and the liquid crystal alignment treatment agent.
  • An object is to provide a liquid crystal alignment film and a liquid crystal display element using the liquid crystal alignment film.
  • a polyimide-based film for example, a liquid crystal alignment film is formed using a polyimide solution obtained by dissolving polyimide or a polyimide precursor in a solvent, or a polyimide precursor solution, as described above.
  • the solution is applied to the substrate and is usually heat-treated at a high temperature of about 200 to 300 ° C.
  • a film is formed by performing a dehydration ring-closing reaction (thermal imidization) of polyamic acid and simultaneously removing the solvent.
  • a polyimide solution is used for film formation, the main purpose of the heat treatment is to remove the solvent.
  • the heat treatment temperature in the case of using the polyimide solution is usually lower than that in the case of using polyamic acid, although it is affected by the boiling point of the solvent used.
  • a film can be formed at a heat treatment temperature of about 200 ° C. Therefore, it is more preferable to use a polyimide solution at a low heat treatment temperature.
  • a highly polar solvent such as N-methyl-2-pyrrolidone (hereinafter also referred to as NMP) has been used.
  • NMP N-methyl-2-pyrrolidone
  • the boiling point of the highly polar solvent is high such that, for example, the boiling point of NMP is 200 ° C. or higher.
  • a high heat treatment temperature of about 200 ° C. near the boiling point of NMP is required.
  • the solvent (NMP) remains in the resulting film.
  • the characteristics are degraded, and the characteristics of the liquid crystal display element are degraded.
  • NMP which is a highly polar solvent
  • NMP has a relatively high surface tension characteristic
  • the wetting and spreading characteristics on the substrate are not good.
  • the surface tension of the solvent used can be made lower, the coating property to the substrate becomes better.
  • lowering the heat treatment and improving the coatability during film formation are important in the formation of polyimide films for the purpose of insulating films and protective films for electronic devices, especially liquid crystal alignment films. Become.
  • the present inventor conducted research to reduce the heat treatment temperature and improve the coating property in the formation of polyimide-based films, particularly polyimide-based liquid crystal alignment films, and found that a diamine component having a specific structure and tetracarboxylic dianhydride.
  • a polyimide precursor obtained from a raw material and / or a polyimide obtained by imidizing the polyimide precursor dissolves well in a solvent containing a cyclic ketone having a low boiling point and a low surface tension characteristic, and as a result
  • the inventors have found that such an object can be sufficiently achieved.
  • a polyimide precursor obtained by reacting a diamine component containing one or more selected from the group consisting of unsubstituted metaphenylenediamine and substituted metaphenylenediamine with a tetracarboxylic dianhydride component and / or A composition comprising a polyimide obtained by imidizing a polyimide precursor, and a cyclic ketone solvent that dissolves the polyimide precursor and / or polyimide.
  • X in the formula [1] is a — (CH 2 ) a —COOH group (a is an integer of 0 to 4), — (CH 2 ) b —OH group (b is 0 to 4) An integer), a hydrocarbon group having 8 to 22 carbon atoms, a disubstituted amino group substituted with a hydrocarbon group having 1 to 6 carbon atoms, or a group represented by the following formula [2]: The composition as described. (In the formula [2], Y 1 is a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or —OCO—.
  • Y 2 is a single bond or — (CH 2 ) b — (b is an integer of 1 to 15), Y 3 is a single bond, — (CH 2 ) c — (c is an integer of 1 to 15) Is —O—, —CH 2 O—, —COO— or —OCO—.
  • Y 4 is a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring (an arbitrary hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, an alkoxyl having 1 to 3 carbon atoms) Or a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom, or an organic group having 12 to 25 carbon atoms having a steroid skeleton.
  • Y 5 is a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocyclic ring (any hydrogen atom on these cyclic groups has 1 to 3 carbon atoms). And an alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom.
  • composition according to any one of (1) to (6), wherein the tetracarboxylic dianhydride is a compound represented by the following formula [3].
  • Z 1 is a tetravalent organic group having 4 to 13 carbon atoms and contains a non-aromatic cyclic hydrocarbon group having 4 to 10 carbon atoms.
  • Z 1 in the formula [3] has a structure represented by the following formulas [3a] to [3j].
  • Z 2 to Z 5 are a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and may be the same or different.
  • Z 6 and Z 7 are hydrogen atoms or methyl groups, which may be the same or different.
  • a liquid crystal aligning agent comprising the composition according to any one of (1) to (9) above.
  • a liquid crystal alignment film obtained from the liquid crystal aligning agent according to (10).
  • a liquid crystal composition having a liquid crystal layer between a pair of substrates provided with electrodes and including a polymerizable compound that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates.
  • the liquid crystal alignment film according to (11) which is used for a liquid crystal display device manufactured through a step of polymerizing the polymerizable compound while applying a voltage between the electrodes.
  • a liquid crystal display device having the liquid crystal alignment film according to (11).
  • a polymerizable compound having a liquid crystal layer between a pair of substrates provided with an electrode and the liquid crystal alignment film, and polymerized by at least one of active energy rays and heat between the pair of substrates.
  • membrane of a more uniform characteristic by low heat processing temperature is provided.
  • a liquid crystal aligning agent capable of forming a liquid crystal alignment film having excellent electrical properties without defects because it has excellent coating properties and can be fired at a low temperature. From the liquid crystal alignment film obtained by using the liquid crystal aligning agent of the present invention, a liquid crystal display element having high reliability can be obtained because of excellent electrical characteristics.
  • the diamine component and tetracarboxylic dianhydride used to obtain the polyimide precursor and / or polyimide imidized with the polyimide precursor used in the present invention (hereinafter collectively referred to as the polyimide of the present invention).
  • the components will be described.
  • the metaphenylene diamine of the present invention includes unsubstituted metaphenylene diamine and substituted metaphenylene diamine.
  • the metaphenylenediamine used in the present invention is a diamine represented by the following formula [1].
  • X is a substituent
  • n is an integer of 0-4.
  • the formula [1] is metaphenylenediamine.
  • the substituent represented by X is a — (CH 2 ) a —COOH group (a is an integer of 0 to 4), a — (CH 2 ) b —OH group. (B is an integer of 0 to 4), a hydrocarbon group having 8 to 22 carbon atoms, a disubstituted amino group substituted with a hydrocarbon group having 1 to 6 carbon atoms, or a group represented by the following formula [2] It is.
  • Y 1 is a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or —OCO—. .
  • a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O— or —COO— is a viewpoint that facilitates the synthesis of the side chain structure.
  • a single bond, — (CH 2 ) a — (a is an integer of 1 to 10), —O—, —CH 2 O— or —COO— is more preferable.
  • Y 2 is a single bond or — (CH 2 ) b — (b is an integer of 1 to 15). Among these, a single bond or — (CH 2 ) b — (b is an integer of 1 to 10) is preferable.
  • Y 3 is a single bond, — (CH 2 ) c — (c is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or —OCO—. is there.
  • a single bond, — (CH 2 ) c — (c is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or —OCO— is used to synthesize a side chain structure. It is preferable from the viewpoint of facilitating. Further, a single bond, — (CH 2 ) c — (c is an integer of 1 to 10), —O—, —CH 2 O—, —COO— or —OCO— is more preferable.
  • Y 4 represents a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring (an arbitrary hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, Carbon atoms having 1 to 3 carbon atoms, fluorine-containing alkyl groups having 1 to 3 carbon atoms, fluorine-containing alkoxyl groups having 1 to 3 carbon atoms, or fluorine atoms), or carbon having a steroid skeleton
  • Y 5 is a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocyclic ring, and any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms.
  • the group may be substituted with any one of a group, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, and a fluorine atom.
  • n is an integer of 0-4.
  • it is an integer of 0-2.
  • Y 6 represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms.
  • a fluorine-containing alkyl group having 1 to 18 carbon atoms is one of an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, and a fluorine-containing alkoxyl group having 1 to 10 carbon atoms. Is preferred.
  • it is any one of an alkyl group having 1 to 12 carbon atoms and an alkoxyl group having 1 to 12 carbon atoms. More preferably, it is any one of an alkyl group having 1 to 9 carbon atoms and an alkoxyl group having 1 to 9 carbon atoms.
  • substituted metaphenylenediamine is preferred compared to unsubstituted metaphenylenediamine (hereinafter sometimes referred to as metaphenylenediamine).
  • a substituted metaphenylenediamine in which X is a disubstituted amino group substituted with a hydrocarbon group having 1 to 6 carbon atoms in the formula [1] is represented by the following formula [1A]. (In the formula [1A], R 1 and R 2 are each independently a hydrocarbon group having 1 to 6 carbon atoms.)
  • R 1 represents a hydrocarbon group having 1 to 6 carbon atoms.
  • the hydrocarbon group for R 1 preferably contains a carbon-carbon double bond, and this double bond is more preferably between the second and third carbons from the nitrogen atom.
  • the number of carbon atoms of R 1 is preferably 4 or less, more preferably 3 or less, from the viewpoint of the printability of the composition or the liquid crystal alignment treatment agent using the composition.
  • R 3 , R 4 and R 5 are each independently a hydrogen atom or a methyl group.
  • preferred positions of the two amino groups are the 2,4 position, the 2,5 position, or the 3,5 position on the benzene ring with respect to the N-allyl group.
  • Preferable examples of the diamine represented by the formula [1B] include a compound represented by the following formula [1C].
  • Preferred specific examples of the compound represented by the formula [1C] are represented by the following formulas [1C-1] to [1C-6]. Of these, diamines of the formula [1C-1] are particularly preferred.
  • the diamine having the structure represented by the formula [1C] is not limited to these examples.
  • diamine represented by the formula [1A] is a diamine having the structure of the following formula [1D]. More specifically, it is a compound represented by the following formulas [1D-1] to [1D-6]. Of these, diamines of the formula [1D-1] are particularly preferred. The diamine represented by the formula [1D] is not limited to these examples.
  • the substituted metaphenylenediamine represented by the formula [1A] depends on the solubility in a solvent when used as a polyimide, and characteristics such as liquid crystal alignment, voltage holding ratio, and accumulated charge when used as a liquid crystal alignment film. In addition, one type or a mixture of two or more types can be used.
  • substituted metaphenylenediamine shown by Formula [1] below is given, it is not limited to these examples. That is, m-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 2,6-diaminotoluene, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4 In addition to diaminobenzyl alcohol, 4,6-diaminoresorcinol, 3,5-diaminobenzoic acid, 2,4-diaminobenzoic acid and the like, metas represented by the following formulas [1-1] to [1-35] Mention may be made of phenylenediamine. (In the formulas [1-1] to [1-4], A 1 is an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group.)
  • R 1 is —O—, —OCH 2 —, —CH 2 O—, —COOCH 2 — or —CH 2 OCO—
  • R 2 is (It is an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group.)
  • R 3 represents —COO—, —OCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, —OCH 2 — or CH 2-
  • R 4 is an alkyl group, alkoxy group, fluorine-containing alkyl group or fluorine-containing alkoxy group having 1 to 22 carbon atoms.
  • R 5 represents —COO—, —OCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, —OCH 2 —, — CH 2 — or O—
  • R 6 is a fluorine group, cyano group, trifluoromethane group, nitro group, azo group, formyl group, acetyl group, acetoxy group or hydroxyl group.
  • R 7 is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer.
  • R 8 is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer. .
  • B 4 is an alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom
  • B 3 is a 1,4-cyclohexylene group or a 1,4-phenylene group.
  • B 2 is an oxygen atom or COO- * (where a bond marked with "*" is bonded to B 3 )
  • B 1 is an oxygen atom or COO- * (where "*" is The bond attached is bonded to (CH 2 ) a 2 ).
  • a 1 is an integer of 0 or 1
  • a 2 is an integer of 2 to 10
  • a 3 is an integer of 0 or 1.
  • the above-mentioned metaphenylenediamine has one kind or two or more kinds according to properties such as solubility in a solvent when it is made polyimide, liquid crystal orientation when it is made a liquid crystal alignment film, voltage holding ratio, accumulated charge, etc. It can also be used by mixing.
  • the method for producing metaphenylenediamine represented by the formula [1] is not particularly limited, but preferred methods include those shown below.
  • the metaphenylenediamine of the present invention can be obtained by synthesizing a dinitro compound represented by the following formula [1E] and further reducing the nitro group to convert it to an amino group.
  • the method for reducing the two nitro groups is not particularly limited, and usually palladium-carbon, platinum oxide, Raney nickel, platinum black, rhodium-alumina, platinum sulfide carbon, etc. are used as a catalyst, ethyl acetate, toluene, tetrahydrofuran, There is a method in which hydrogen gas, hydrazine, hydrogen chloride, or the like is used in a solvent such as dioxane or an alcohol solvent.
  • X and n in Formula [1E] are the same meaning as the definition in Formula [1] in the above-mentioned metaphenylenediamine.
  • diamines include, for example, p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, 2,5-diaminotoluene, 2,5 -Diaminophenol, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4 , 4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-biphenyl, 3,3'-trifluoromethyl-4,4 ' -Diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphen
  • diamines examples include those having an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring or a heterocyclic ring in the diamine side chain, or those having a macrocyclic substituent composed of these. .
  • diamines represented by the following formulas [DA1] to [DA8] can be exemplified.
  • a 1 is an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group.
  • a 2 is —COO—, —OCO—, —CONH—, —NHCO—, —CH 2 —, —O—, —CO— or —NH—
  • 3 is an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group.
  • n is an integer of 1 to 5.
  • a diamine having a carboxyl group in the molecule represented by the following formulas [DA17] to [DA21] can also be used.
  • m 1 is an integer of 1 to 4
  • a 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—, each of m 2 and m 3 is an integer of 0 to 4, and m 2 + m 3 is an integer of 1 to 4.
  • m 4 and m 5 are each an integer of 1 to 5.
  • a 5 is a linear or branched alkyl group having 1 to 5 carbon atoms
  • m 6 is an integer of 1 to 5.
  • a 6 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 is an integer of 1 to 4.
  • diamines represented by the following formulas [DA22] and [DA23] can also be used.
  • diamines mentioned above may be used alone or in combination of two or more depending on the solubility of the polymer in the solvent and the properties of the liquid crystal alignment, voltage holding ratio, accumulated charge, etc. Can also be used.
  • a tetracarboxylic dianhydride having an alicyclic structure (also referred to as a specific tetracarboxylic dianhydride) is used as a tetracarboxylic dianhydride component.
  • a specific tetracarboxylic dianhydride a tetracarboxylic dianhydride having an alicyclic structure represented by the following formula [3] is preferable.
  • Z 1 is a tetravalent organic group having 4 to 13 carbon atoms, and contains a non-aromatic cyclic hydrocarbon group having 4 to 10 carbon atoms. Specifically, Z 1 is a structure represented by the following formulas [3a] to [3j].
  • Z 2 to Z 5 are groups selected from the group consisting of a hydrogen atom, a methyl group, a chlorine atom and a benzene ring, and may be the same or different.
  • Z 6 and Z 7 are a hydrogen atom or a methyl group, and may be the same or different.
  • particularly preferred structure of Z 1 is the formula [3a], the formula [3c], the formula [3d], the formula [3e], the formula [3f] or the formula from the viewpoint of polymerization reactivity and ease of synthesis. It is a structure shown by [3g]. Especially, the structure shown by Formula [3e], Formula [3f], or Formula [3g] is preferable.
  • the amount used is 20% by mass or more of the total tetracarboxylic dianhydride component.
  • the desired effect is obtained, and it is more preferably 25% by mass or more.
  • tetracarboxylic dianhydrides other than specific tetracarboxylic dianhydride can be used.
  • Specific examples thereof include, for example, pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid.
  • composition of the present invention among the above-mentioned other tetracarboxylic dianhydrides, for example, in the case of a liquid crystal alignment film, in consideration of characteristics such as liquid crystal alignment properties, voltage holding characteristics, and accumulated charges, one kind is used. Alternatively, two or more types can be selected and used.
  • polyimide precursor and polyimide used in the composition of the present invention are preferably obtained as follows.
  • the polyimide precursor represents polyimide acid (also referred to as polyamic acid). That is, the polyimide precursor used by this invention is obtained by making the diamine component containing the above-mentioned metaphenylenediamine react with the tetracarboxylic dianhydride component which has an above-described alicyclic structure.
  • dehydrating and ring-closing a polyimide precursor is manufactured from the diamine component containing a metaphenylenediamine, so that the solubility to a solvent improves and low temperature baking is attained so that it may mention later. .
  • the amount of the above-mentioned metaphenylenediamine in the diamine component used as a raw material is preferably 40 mol% or more, and more preferably 45 mol% or more.
  • the amount used is preferably 15 mol% or more, more preferably 30 mol% or more in the diamine component.
  • said metaphenylenediamine may be sufficient as 100 mol% in a diamine component.
  • a known synthesis method can be used as a method for obtaining a polyimide precursor by a reaction between a diamine component and tetracarboxylic dianhydride.
  • a known synthesis method can be used.
  • the organic solvent used for the reaction between the diamine component and tetracarboxylic dianhydride is not particularly limited as long as the produced polyamic acid is soluble. Specific examples thereof include, for example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, ⁇ -butyrolactone, 1,3-dimethyl. -Imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone or 4-hydroxy-4-methyl-2-pentanone. These may be used alone or in combination. These may be used alone or in combination.
  • a solvent that does not dissolve the polyimide precursor can be used by mixing with the above solvent as long as the produced polyamic acid does not precipitate.
  • moisture content in an organic solvent inhibits a polymerization reaction and causes the produced
  • 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 the organic solvent. It is possible to use a method of adding it after being dispersed or dissolved. Conversely, a method of adding a diamine component to a solution in which tetracarboxylic dianhydride is dispersed or dissolved in an organic solvent, a method of adding tetracarboxylic dianhydride and a diamine component alternately, etc. Can do. In the present invention, any of these methods may be used.
  • the diamine component or tetracarboxylic dianhydride 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. It is good also as a high molecular weight body by carrying out a mixing reaction.
  • the temperature at which the diamine component and tetracarboxylic dianhydride are reacted can be arbitrarily selected within the range of ⁇ 20 to 150 ° C., but in the range of ⁇ 5 to 100 ° C. in consideration of the reaction efficiency. It is preferable.
  • reaction can be performed by arbitrary density
  • the ratio between the total number of moles of the diamine component and the total number of moles of the tetracarboxylic dianhydride 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 polymer produced. Therefore, it is possible to determine the total molar ratio by appropriately selecting depending on the case.
  • the polyimide used in the present invention is obtained by dehydrating and ring-closing the above polyimide precursor.
  • the polyimide can be used as a polymer for obtaining a liquid crystal alignment film.
  • the dehydration cyclization rate (imidation rate) of the polyimide precursor does not necessarily need to be 100%. For example, in the range of 35 to 95%, depending on the application and purpose, More preferably, it can be adjusted in the range of 50 to 80%.
  • Examples of the method for imidizing the polyimide precursor include thermal imidization in which the polyimide precursor solution is heated as it is, and catalyst imidization in which a catalyst is added to the polyimide precursor solution.
  • the temperature when the polyimide precursor is thermally imidized in the solution is 100 to 400 ° C., preferably 120 to 250 ° C.
  • the imidization of the polyimide precursor is preferably performed while removing water generated by the imidization reaction from the reaction system.
  • the catalyst imidation of the polyimide precursor can be performed by adding a basic catalyst and an acid anhydride to the polyimide precursor solution and stirring at -20 to 250 ° C, preferably 0 to 180 ° C.
  • the amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times the amidic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol times the amido group. 30 mole times.
  • Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Among them, pyridine is preferable in that 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, acetic anhydride is preferable because purification after the completion of the reaction is easy.
  • the imidization rate by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.
  • 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 deposited in a poor solvent and precipitated can be recovered by filtration and then dried at normal temperature or under reduced pressure at room temperature or by heating.
  • impurities in the polymer 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 weight of the polymer (polyimide precursor or polyimide) contained in the composition of the present invention is in consideration of the strength of the coating film obtained using this, the workability during coating film formation, and the uniformity of the coating film,
  • the weight average molecular weight measured by GPC (Gel Permeation Chromatography) method is preferably 5,000 to 1,000,000, and more preferably 10,000 to 150,000.
  • the film-forming composition of the present invention for example, a liquid crystal alignment treatment agent is a composition containing the imide polymer of the present invention obtained as described above and a solvent in which the polyimide polymer is dissolved, A coating liquid for forming a liquid crystal alignment film.
  • the content of the polyimide polymer of the present invention contained in the composition is preferably 1 to 20% by mass, more preferably 3 to 15% by mass, and particularly preferably 3 to 10% by mass.
  • all of the polymer components contained in the composition may be the polyimide of the present invention.
  • the polyimide of the other structure manufactured without using metaphenylenediamine other than the polyimide of this invention may be mixed.
  • the content of the polyimide having another structure in the polymer component can be 0.5 to 15% by mass, preferably 1 to 10% by mass.
  • the polymer component containing the polyimide of the present invention is contained in a dissolved state.
  • a cyclic ketone which is a solvent that dissolves the polyimide of the present invention and has a lower boiling point and lower surface tension than NMP, is used.
  • cyclic ketones include cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, cyclononanone, and cyclodecanone.
  • any of cyclohexanone and cyclopentanone, or a mixture thereof is preferable.
  • the composition of the present invention for example, the liquid crystal aligning agent, preferably has an organic solvent content of 70 to 99% by mass from the viewpoint of forming a uniform film by coating. This content can be appropriately changed depending on the film thickness of the target liquid crystal alignment film.
  • a solvent in that case, it is possible to use only a cyclic ketone solvent, but other organic solvents are appropriately mixed and contained within a range that does not hinder low-temperature baking and improvement of coating properties. It is also possible.
  • organic solvents include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, ⁇ -butyrolactone, , 3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone or 4-hydroxy-4-methyl-2-pentanone. These may be used alone or in combination. Even when these other organic solvents are contained, the content of the cyclic ketone solvent is preferably 50% by mass or more, more preferably 60% by mass or more, and most preferably 70% by mass or more in the total solvent. is there.
  • composition of the present invention for example, the liquid crystal aligning agent is used for improving the coating properties for the purpose of further improving the film thickness uniformity and surface smoothness of the film formed as long as the effects of the present invention are not impaired.
  • Organic solvent hereinafter also referred to as a poor solvent.
  • the content of the cyclic ketone solvent is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.
  • the composition of the present invention includes a compound for improving the thickness uniformity and surface smoothness of the film when the composition or the liquid crystal aligning agent is applied, and a film to be formed, as long as the effects of the present invention are not impaired.
  • substrate can be included.
  • Examples of compounds that improve the uniformity of the film thickness and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.
  • fluorine-based surfactants silicone-based surfactants
  • nonionic surfactants examples include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.
  • F-top EF301, EF303, EF352 manufactured by Tochem Products
  • MegaFuck F171, F173, R-30 manufactured by Dainippon Ink
  • Florard FC430, FC431 manufactured by Sumitomo 3M
  • Asahi Guard AG710 And 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 composition.
  • the compound that improves the adhesion between the formed film and the substrate include the following functional silane-containing compounds and epoxy group-containing compounds.
  • the amount of the compound added is 0.1 to 30 parts by mass with respect to 100 parts by mass of the polymer component contained in the composition. It is preferably 1 to 20 parts by mass. If the amount is less than 0.1 part by mass, the effect of improving the adhesion cannot be expected, and if it exceeds 30 parts by mass, the orientation of the liquid crystal may deteriorate.
  • composition of the present invention for example, is a crosslinkable compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group, and a lower group, unless the effects of the present invention are impaired.
  • a crosslinkable compound having at least one substituent selected from the group consisting of alkoxyalkyl groups or a crosslinkable compound having a polymerizable unsaturated bond can also be contained.
  • crosslinkable compound having an epoxy group or an isocyanate group examples include bisphenolacetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, tetraglycidylaminodiphenylene, tetraglycidyl-m-xylenediamine, tetra Glycidyl-1,3-bis (aminoethyl) cyclohexane, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether ethane, bisphenol hexafluoroacetodiglycidyl ether, 1,3-bis (1- (2,3-epoxypropoxy)- 1-trifluoromethyl-2,2,2-trifluoromethyl) benzene, 4,4-bis (2,3-epoxypropoxy) octafluorobiphenyl Triglycidyl-p-amin
  • the crosslinkable compound having an oxetane group is a crosslinkable compound having at least two oxetane groups represented by the following formula [4].
  • the crosslinkable compound having a cyclocarbonate group is a crosslinkable compound having at least two cyclocarbonate groups represented by the following formula [5].
  • n is an integer of 1 to 5
  • n is an integer of 1 to 5
  • n is 1 to 100
  • n is an integer of 1 to 10.
  • polysiloxanes having at least one structure represented by the following formulas [5-38] to [5-40] can also be mentioned.
  • R 1 , R 2 , R 3 , R 4 and R 5 each independently represents a structure represented by the formula [5], a hydrogen atom, a hydroxyl group, An alkyl group having 1 to 10 carbon atoms, an alkoxyl group, an aliphatic ring or an aromatic ring, at least one of which is a structure represented by the formula [5]).
  • each R 6 independently represents a structure represented by the formula [5], a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group, an aliphatic ring or an aromatic group. And at least one is a structure represented by the formula [5].
  • n is an integer of 1 to 10.
  • Examples of the crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxyl group include an amino resin having a hydroxyl group or an alkoxyl group, such as a melamine resin, a urea resin, a guanamine resin, and a glycoluril.
  • a melamine resin, a urea resin, a guanamine resin, and a glycoluril such as a melamine resin, a urea resin, a guanamine resin, and a glycoluril.
  • a melamine derivative, a benzoguanamine derivative, or glycoluril in which a hydrogen atom of an amino group is substituted with a methylol group and / or an alkoxymethyl group can be used.
  • the melamine derivative or benzoguanamine derivative can exist as a dimer or a trimer. These preferably have an average of 3 to 6 methylol groups or alkoxymethyl groups
  • Examples of melamine derivatives or benzoguanamine derivatives include MX-750 with an average of 3.7 substituted methoxymethyl groups per triazine ring, and an average of 5.8 substituted methoxymethyl groups per triazine ring.
  • MW-30 manufactured by Sanwa Chemical Co., Ltd.
  • glycoluril examples include butoxymethylated glycoluril such as Cymel 1170, methylolated glycoluril such as Cymel 1172, methoxymethylolated glycoluril such as Powderlink 1174, and the like.
  • benzene or phenolic compound having a hydroxyl group or an alkoxyl group examples include 1,3,5-tris (methoxymethyl) benzene, 1,2,4-tris (isopropoxymethyl) benzene, 1,4-bis ( sec-butoxymethyl) benzene, 2,6-dihydroxymethyl-p-tert-butylphenol and the like. Specifically, it is a crosslinkable compound represented by the following formulas [6-1] to [6-48].
  • crosslinkable compound having a polymerizable unsaturated bond examples include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and tri (meth) acryloyloxyethoxytrimethylol.
  • Crosslinkable compounds having three polymerizable unsaturated groups in the molecule such as propane and glycerin polyglycidyl ether poly (meth) acrylate; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) ) Acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (me ) Acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide bisphenol A type di (meth) acrylate, propylene oxide bisphenol type di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) ) Acrylate, pentaerythritol di (meth) acrylate, ethylene glycol digly
  • E 1 is a group selected from the group consisting of a cyclohexane ring, a bicyclohexane ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, a fluorene ring, an anthracene ring, and a phenanthrene ring
  • E 2 Is a group selected from the following formulas [7a] and [7b], and n is an integer of 1 to 4.
  • the said compound is an example of a crosslinkable compound, It is not limited to these.
  • the crosslinkable compound contained in the composition of the present invention may be one kind or a combination of two or more kinds.
  • the content of the crosslinkable compound in the composition of the present invention is preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of the polymer component.
  • the amount is more preferably 0.1 to 100 parts by weight, particularly 1 to 50 parts by weight, based on 100 parts by weight of the polymer component. Part is most preferred.
  • the composition of the present invention is a dielectric 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.
  • Body or conductive material may be added.
  • composition of the present invention is a liquid crystal alignment treatment agent
  • the following formula is used as a compound that promotes charge transfer in the liquid crystal alignment film to be formed and promotes charge release of a liquid crystal cell using the liquid crystal alignment film.
  • Nitrogen-containing heterocyclic amine compounds represented by [M1] to [M156] can also be added.
  • the amine compound may be added directly to the polymer solution, but it is preferably added after a solution having a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass with an appropriate solvent.
  • the solvent is not particularly limited as long as it is an organic solvent that dissolves polyimide in addition to the cyclic ketone solvent described above.
  • a liquid crystal aligning agent is formed from a liquid crystal aligning agent
  • the liquid crystal alignment treatment agent is applied onto a substrate, fired by heat treatment, and then subjected to alignment treatment by rubbing treatment or light irradiation to form a liquid crystal alignment film.
  • a liquid crystal alignment film can be formed without alignment treatment.
  • the substrate is not particularly limited as long as it is a highly transparent substrate. In addition to a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate can also be used.
  • a substrate on which an ITO electrode for driving a liquid crystal is formed.
  • an opaque substrate such as a silicon wafer can be used if only one substrate is used, and a material that reflects light such as aluminum can be used as an electrode in this case.
  • the method for applying the liquid crystal aligning agent is not particularly limited, but industrially, methods such as screen printing, offset printing, flexographic printing, and ink jet methods are generally used. Other coating methods include a dipping method, a roll coater method, a slit coater method, a spinner method, and a spray method, and these may be used depending on the purpose.
  • the liquid crystal aligning agent of the present invention has good coating properties even when the above coating method is used.
  • the solvent is evaporated at 50 to 180 ° C., preferably 80 to 150 ° C. by a heating means such as a hot plate, a heat circulation oven, or an IR (infrared) oven. It can be a membrane. If the thickness of the coating film after baking is too thick, it is not preferable in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered. Therefore, the thickness of the coating after baking is preferably 5 to 300 nm, more preferably 10 to 100 nm. When the liquid crystal is horizontally or tilted, the baked coating film is treated by rubbing or irradiation with polarized ultraviolet rays.
  • the liquid crystal display element is a liquid crystal display element obtained by obtaining a substrate with a liquid crystal alignment film from the liquid crystal alignment treatment agent of the present embodiment by the method described above, and then manufacturing a liquid crystal cell by a known method.
  • a liquid crystal cell manufacturing method a pair of substrates on which a liquid crystal alignment film is formed are prepared, spacers are dispersed on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is on the inside, so that the other Examples include a method in which substrates are attached and liquid crystal is injected under reduced pressure, or a method in which liquid crystal is dropped onto a liquid crystal alignment film surface on which spacers are dispersed and then a substrate is attached and sealed.
  • the liquid crystal alignment film has a liquid crystal layer between a pair of substrates provided with electrodes, and a liquid crystal composition containing a polymerizable compound that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates. And it is preferably used also for the liquid crystal display element manufactured through the process of superposing
  • ultraviolet rays are suitable as the active energy ray.
  • the above liquid crystal display element controls the pretilt of liquid crystal molecules by a PSA (Polymer Sustained Alignment) method.
  • a PSA method a small amount of a photopolymerizable compound, for example, a photopolymerizable monomer is mixed in a liquid crystal material, and after assembling a liquid crystal cell, a predetermined voltage is applied to the liquid crystal layer and an ultraviolet ray is applied to the photopolymerizable compound.
  • the pretilt of the liquid crystal molecules is controlled by the produced polymer. Since the alignment state of the liquid crystal molecules when the polymer is formed is stored even after the voltage is removed, the pretilt of the liquid crystal molecules can be adjusted by controlling the electric field formed in the liquid crystal layer.
  • the PSA method does not require a rubbing process and is suitable for forming a vertical alignment type liquid crystal layer in which it is difficult to control the pretilt by the rubbing process.
  • a liquid crystal cell is prepared, and a polymerizable compound is polymerized by at least one of ultraviolet irradiation and heating.
  • the alignment of liquid crystal molecules can be controlled.
  • a pair of substrates on which a liquid crystal alignment film is formed is prepared, spacers are dispersed on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is on the inside. Then, the other substrate is bonded, the liquid crystal is injected under reduced pressure and sealed, the liquid crystal is dropped on the liquid crystal alignment film surface on which the spacers are dispersed, and then the substrate is bonded and sealed.
  • a polymerizable compound that is polymerized by heat or ultraviolet irradiation is mixed.
  • the polymerizable compound include compounds having at least one polymerizable unsaturated group such as an acrylate group or a methacrylate group in the molecule.
  • the polymerizable compound is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the liquid crystal component.
  • the polymerizable compound When the polymerizable compound is less than 0.01 part by mass, the polymerizable compound is not polymerized and the alignment of the liquid crystal cannot be controlled, and when it exceeds 10 parts by mass, the amount of the unreacted polymerizable compound increases and the liquid crystal display The burn-in characteristic of the element is deteriorated.
  • the polymerizable compound After producing the liquid crystal cell, the polymerizable compound is polymerized by irradiating with heat or ultraviolet rays while applying an AC or DC voltage to the liquid crystal cell. Thereby, the alignment of the liquid crystal molecules can be controlled.
  • the liquid crystal aligning agent of the present invention has a liquid crystal layer between a pair of substrates provided with electrodes, and is polymerized by at least one of active energy rays and heat between the pair of substrates. It is also preferably used for a liquid crystal display device manufactured through a step of disposing a liquid crystal alignment film containing a group and applying a voltage between the electrodes.
  • ultraviolet rays are suitable as the active energy ray.
  • the wavelength of ultraviolet rays is 300 to 400 nm, preferably 310 to 360 nm. In the case of polymerization by heating, the heating temperature is 40 to 120 ° C, preferably 60 to 80 ° C.
  • liquid crystal alignment treatment agent of the present invention contains a specific compound having a double bond site that reacts by irradiation with heat or ultraviolet rays, the alignment of liquid crystal molecules can be controlled by at least one of ultraviolet irradiation and heating. it can.
  • liquid crystal cell production prepare a pair of substrates on which a liquid crystal alignment film is formed, spread spacers on the liquid crystal alignment film of one substrate, and make the liquid crystal alignment film surface inside.
  • Examples include a method in which the other substrate is bonded and liquid crystal is injected under reduced pressure to seal, and a method in which the liquid crystal is dropped on the liquid crystal alignment film surface on which spacers are dispersed and then the substrate is bonded and sealed.
  • a liquid crystal display element is obtained through the above steps. Since these liquid crystal display elements use the liquid crystal alignment film of the present invention as the liquid crystal alignment film, the manufacturing process becomes lower temperature, excellent in reliability, and suitable for a large-screen, high-definition liquid crystal television. Is available.
  • the molecular weight of polyimide in the synthesis example is as follows using a normal temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko KK) and columns (KD-803, KD-805) (manufactured by Shodex). The measurement was performed as described above.
  • GPC normal temperature gel permeation chromatography
  • the imidation ratio of polyimide in the synthesis example was measured as follows. Polyimide powder (20 mg) is put into an NMR sample tube (NMR sampling tube standard ⁇ 5 (manufactured by Kusano Kagaku)) and deuterated dimethyl sulfoxide (DMSO-d6, 0.05 mass% TMS (tetramethylsilane) mixture) ( 0.53 ml) was added and completely dissolved by applying ultrasonic waves. This solution was measured for proton NMR at 500 MHz with an NMR (nuclear magnetic resonance) measuring instrument (JNW-ECA500) (manufactured by JEOL Datum).
  • the imidation rate is determined based on protons derived from structures that do not change before and after imidation as reference protons, and the peak integrated value of these protons and proton peaks derived from NH groups of amic acid appearing in the vicinity of 9.5 to 10.0 ppm. It calculated
  • Imidization rate (%) (1 ⁇ ⁇ x / y) ⁇ 100
  • x is a proton peak integrated value derived from NH group of amic acid
  • y is a peak integrated value of reference proton
  • ⁇ is one NH group proton of amic acid in the case of polyamic acid (imidation rate is 0%) Is the number ratio of the reference proton to.
  • This deposit was wash
  • the imidation ratio of this polyimide was 76%, the number average molecular weight was 17,200, and the weight average molecular weight was 51,100.
  • This reaction solution was put into methanol (378 ml), and the resulting precipitate was separated by filtration. This deposit was wash
  • the imidation ratio of this polyimide was 50%, the number average molecular weight was 17,600, and the weight average molecular weight was 52,000.
  • This deposit was wash
  • the imidation ratio of this polyimide was 75%, the number average molecular weight was 14,500, and the weight average molecular weight was 41,200.
  • This deposit was wash
  • the imidation ratio of this polyimide was 53%, the number average molecular weight was 19,800, and the weight average molecular weight was 55,900.
  • This deposit was wash
  • the imidation ratio of this polyimide was 80%, the number average molecular weight was 11,900, and the weight average molecular weight was 28,100.
  • This deposit was wash
  • the imidation ratio of this polyimide was 60%, the number average molecular weight was 14,800, and the weight average molecular weight was 30,500.
  • This deposit was wash
  • the imidation ratio of this polyimide was 77%, the number average molecular weight was 14,200, and the weight average molecular weight was 30,000.
  • This deposit was wash
  • the imidation ratio of this polyimide was 82%, the number average molecular weight was 11,000, and the weight average molecular weight was 22,100.
  • Examples 45 to 66> CPN (27.6 g) was added to each of the polyimide powders (A) to (V) (1.0 g each) of Synthesis Examples 1 to 22, and stirred at 50 ° C. for 24 hours to dissolve each polyimide.
  • any of the polyimide solutions no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was uniform.
  • the obtained polyimide solutions were subjected to pressure filtration through a membrane filter having a pore diameter of 1 ⁇ m to obtain liquid crystal aligning agents (23) to (44) having a polyimide component content of 3.5% by mass.
  • each solution containing CHN and NMP is filtered under pressure through a membrane filter having a pore diameter of 1 ⁇ m, and liquid crystal alignment treatment agents (45) to (48) having a polyimide component content of 3.5% by mass are added. Obtained.
  • Examples 71 to 74> CHN (13.3 g) was added to each of the polyimide powder (E) of Synthesis Example 5 and the polyimide powders (O) to (Q) (1.0 g of each) of Synthesis Examples 15 to 17, and 24 hours at 50 ° C. Stir to dissolve each polyimide. Then, NMP (5.71g) and BCS (8.57g) were further added to each obtained solution, and it stirred, and obtained each polyimide solution containing CHN, NMP, and BCS. In any of the polyimide solutions, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was uniform.
  • each polyimide solution containing CHN, NMP and BCS is pressure filtered through a membrane filter having a pore diameter of 1 ⁇ m, and the liquid crystal alignment treatment agent (49) to (52) having a polyimide component content of 3.5% by mass. )
  • each polyimide solution containing CPN and NMP is subjected to pressure filtration with a membrane filter having a pore diameter of 1 ⁇ m, and the liquid crystal aligning agent (53) to (56) having a polyimide component content of 3.5% by mass.
  • each polyimide solution containing CPN, NMP and BCS is pressure filtered through a membrane filter having a pore diameter of 1 ⁇ m, and the liquid crystal alignment treatment agent (57) to (60) having a polyimide component content of 3.5% by mass. )
  • each polyimide solution containing CHN and PGME is subjected to pressure filtration with a membrane filter having a pore diameter of 1 ⁇ m, and the liquid crystal aligning agents (61) to (64) having a polyimide component content of 3.5% by mass.
  • Examples 87 to 90> CPN (19.0 g) was added to each of the polyimide powder (E) of Synthesis Example 5 and the polyimide powders (O) to (Q) (1.0 g of each) of Synthesis Examples 15 to 17, and the mixture was added at 50 ° C. for 24 hours. Stir to dissolve each polyimide. Then, PGME (8.57g) was further added to each obtained solution, it stirred, and each polyimide solution containing CPN and PGME was obtained. In any of the polyimide solutions, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was uniform.
  • each polyimide solution containing CPN and PGME is subjected to pressure filtration with a membrane filter having a pore size of 1 ⁇ m, and the liquid crystal aligning agent (65) to (68) having a polyimide component content of 3.5% by mass.
  • a liquid crystal alignment film was prepared using the liquid crystal alignment treatment agents obtained in Examples 23 to 66, and a liquid crystal surface element using the liquid crystal alignment film was prepared.
  • a liquid crystal display element a liquid crystal cell with parallel alignment or a liquid crystal cell with vertical alignment was prepared according to the characteristics of the liquid crystal alignment film.
  • a liquid crystal cell was prepared by spin-coating a liquid crystal aligning agent on a glass substrate with an ITO electrode (length 40 mm ⁇ width 30 mm, thickness 0.7 mm), and heat-circulating clean for 5 minutes on a hot plate at 80 ° C. After heat-treating at 220 ° C. for 30 minutes in an oven, a liquid crystal alignment film was formed as a coating film having a thickness of 100 nm to obtain a substrate with a liquid crystal alignment film. It was found that all the liquid crystal alignment films formed on the substrate were excellent in film thickness uniformity, and the liquid crystal alignment treatment agent showed excellent coating properties.
  • the obtained substrate with the liquid crystal alignment film was subjected to a known rubbing treatment. Further, the rubbing treatment was not performed on the substrate with a liquid crystal alignment film for vertical alignment.
  • a liquid crystal for parallel alignment (MLC-2003, manufactured by Merck) is used for the liquid crystal cell for parallel alignment
  • a liquid crystal for vertical alignment (MLC-6608, manufactured by Merck) is used for the liquid crystal cell for vertical alignment. ) was used.
  • the alignment state of the liquid crystal was observed with a polarizing microscope (ECLIPSE E600WPOL, manufactured by Nikon Corp.), and it was confirmed that uniform liquid crystal parallel alignment or vertical alignment without defects was formed.
  • Table 49 and Table 50 show the results of the alignment state of the liquid crystal of the liquid crystal display element.
  • Example 26 Example 27, Examples 37 to 39, Example 48, Example 49, Examples 59 to 61, Example 83, Example 86, Example 87, Example 90, and Comparative Example
  • a liquid crystal display device was produced using a liquid crystal cell produced using 2 to 6 liquid crystal alignment treatment agents.
  • the liquid crystal display element was produced by the method described above. A voltage of 1 V was applied to these liquid crystal display elements at a temperature of 80 ° C. at 60 ⁇ m, the voltage after 50 ms was measured, and how much the voltage was held compared to immediately after the application was shown as a voltage holding ratio.
  • the measurement was performed using a VHR-1 voltage holding ratio measuring device (manufactured by Toyo Technica Co., Ltd.) with settings of Voltage: ⁇ 1 V, Pulse Width: 60 ⁇ s, and Frame Period: 50 ms.
  • the results of the voltage holding ratio of the liquid crystal display element are shown in the table.
  • the liquid crystal aligning agent of the present invention can be obtained from the polyimide obtained using the diamine component containing metaphenylenediamine, and the liquid crystal aligning agent is excellent in coatability. Moreover, it turns out that preparation of the liquid crystal aligning film using the liquid-crystal aligning agent of this invention is possible by low-temperature baking.
  • the composition of the present invention can be widely used for the formation of films such as interlayer insulating films and protective films in electronic devices and the like, and in particular, as a liquid crystal alignment treatment agent, it has excellent coating properties and can be fired at a low temperature. It is used for forming a liquid crystal alignment film used for a highly reliable liquid crystal display element.

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Abstract

La composition, en particulier, l'agent d'alignement de cristaux liquides ci-décrit, peut former un film polyimide de qualité élevée ayant des caractéristiques uniformes, en particulier, un film d'alignement de cristaux liquides, à l'aide d'une basse température de traitement thermique. Ladite composition est caractérisée en ce qu'elle comprend : un précurseur de polyimide obtenu par réaction d'un composant de diamine comprenant un ou plusieurs types de diamine choisis dans le groupe constitué par une phénylènediamine non substituée et une phénylènediamine substituée avec un composant dianhydride d'acide tétracarboxylique ; et/ou un polyimide obtenu par imidation du précurseur de polyimide ; et un solvant de type cétone cyclique qui dissout le précurseur de polyimide et/ou le polyimide. (Dans la formule [1], X est un groupe substitué et n est un entier entre 0 et 4).
PCT/JP2012/055712 2011-03-07 2012-03-06 Composition, agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides Ceased WO2012121259A1 (fr)

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JP2013503561A JP6075286B2 (ja) 2011-03-07 2012-03-06 組成物、液晶配向処理剤、液晶配向膜、及び液晶表示素子
KR1020137026224A KR101878522B1 (ko) 2011-03-07 2012-03-06 조성물, 액정 배향 처리제, 액정 배향막, 및 액정 표시 소자
CN201280020095.2A CN103492462B (zh) 2011-03-07 2012-03-06 组合物、液晶取向处理剂、液晶取向膜及液晶显示元件

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WO2014208704A1 (fr) * 2013-06-27 2014-12-31 宇部興産株式会社 Précurseur de polyimide et polyimide
KR20190094247A (ko) 2016-12-28 2019-08-12 닛산 가가쿠 가부시키가이샤 액정 배향제, 액정 배향막, 및 액정 표시 소자
KR20190095473A (ko) 2016-12-28 2019-08-14 닛산 가가쿠 가부시키가이샤 액정 배향제, 액정 배향막, 및 액정 표시 소자
KR20190100958A (ko) 2016-12-28 2019-08-29 닛산 가가쿠 가부시키가이샤 액정 배향제, 액정 배향막, 및 액정 표시 소자

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KR102345961B1 (ko) * 2014-03-27 2021-12-30 닛산 가가쿠 가부시키가이샤 액정 표시 소자, 액정 배향막 및 액정 배향 처리제

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WO2006077964A2 (fr) * 2005-01-21 2006-07-27 Mitsubishi Gas Chemical Co Résine de polyimide, film de polyimide et stratifié de polyimide
WO2008146637A1 (fr) * 2007-05-24 2008-12-04 Mitsubishi Gas Chemical Company, Inc. Procédé et appareil de production de film de résine transparent incolore
JP2010002880A (ja) * 2008-03-18 2010-01-07 Jsr Corp 液晶配向剤および液晶表示素子
JP2010039032A (ja) * 2008-08-01 2010-02-18 Kaneka Corp 新規な塗布型光学補償フィルムおよびその製造方法
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014208704A1 (fr) * 2013-06-27 2014-12-31 宇部興産株式会社 Précurseur de polyimide et polyimide
KR20190094247A (ko) 2016-12-28 2019-08-12 닛산 가가쿠 가부시키가이샤 액정 배향제, 액정 배향막, 및 액정 표시 소자
KR20190095473A (ko) 2016-12-28 2019-08-14 닛산 가가쿠 가부시키가이샤 액정 배향제, 액정 배향막, 및 액정 표시 소자
KR20190100958A (ko) 2016-12-28 2019-08-29 닛산 가가쿠 가부시키가이샤 액정 배향제, 액정 배향막, 및 액정 표시 소자

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TW201302855A (zh) 2013-01-16
KR20140009447A (ko) 2014-01-22
TWI624494B (zh) 2018-05-21
JP6075286B2 (ja) 2017-02-08
CN103492462A (zh) 2014-01-01
KR101878522B1 (ko) 2018-07-13
CN103492462B (zh) 2016-01-20

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