WO2014092126A1 - Composition, agent de traitement d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides - Google Patents

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

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WO2014092126A1
WO2014092126A1 PCT/JP2013/083230 JP2013083230W WO2014092126A1 WO 2014092126 A1 WO2014092126 A1 WO 2014092126A1 JP 2013083230 W JP2013083230 W JP 2013083230W WO 2014092126 A1 WO2014092126 A1 WO 2014092126A1
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liquid crystal
formula
group
composition
carbon atoms
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PCT/JP2013/083230
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English (en)
Japanese (ja)
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保坂　和義
徳俊 三木
雅章 片山
幸司 巴
奈穂 菊池
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日産化学工業株式会社
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Priority to JP2014552070A priority Critical patent/JP6299977B2/ja
Priority to KR1020157017643A priority patent/KR102283305B1/ko
Priority to CN201380072403.0A priority patent/CN104968722B/zh
Publication of WO2014092126A1 publication Critical patent/WO2014092126A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/10—Esters of organic acids, i.e. acylates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/26—Cellulose ethers
    • C08L1/28—Alkyl ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/26—Cellulose ethers
    • C08L1/28—Alkyl ethers
    • C08L1/284—Alkyl ethers with hydroxylated hydrocarbon radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/26—Cellulose ethers
    • C08L1/28—Alkyl ethers
    • C08L1/286—Alkyl ethers substituted with acid radicals, e.g. carboxymethyl cellulose [CMC]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/26—Cellulose ethers
    • C08L1/28—Alkyl ethers
    • C08L1/288—Alkyl ethers substituted with nitrogen-containing radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/26—Cellulose ethers
    • C08L1/30—Aryl ethers; Aralkyl ethers
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use 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 C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • the present invention relates to a composition used for forming a resin film, a liquid crystal alignment treatment agent used in the production of a liquid crystal display element, a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent, and a liquid crystal display element using the liquid crystal alignment film. Is.
  • a resin film made of an organic material such as a polymer material is widely used as an interlayer insulating film or a protective film in an electronic device because of its ease of formation and insulation performance.
  • a resin film made of an organic material is used as a liquid crystal alignment film.
  • polyimide-based organic films with excellent durability are used as resin films used industrially.
  • this polyimide organic film is also used as a liquid crystal alignment film of a liquid crystal display element.
  • the polyimide organic film is formed from a composition containing a polyimide precursor, polyamic acid or polyimide. That is, the polyimide organic film is formed by applying a composition containing polyamic acid or polyimide onto a substrate and performing a baking process (see, for example, Patent Document 1).
  • the liquid crystal alignment film is used for the purpose of controlling the alignment state of the liquid crystal.
  • the liquid crystal alignment film used in the liquid crystal alignment film has a high voltage holding ratio and a direct current voltage from the viewpoint of suppressing the decrease in contrast of the liquid crystal display elements and reducing the afterimage phenomenon.
  • the characteristic that the accumulated charge when applied is small or the relaxation of the accumulated charge by the DC voltage is fast has become important.
  • one carboxylic acid is included in the molecule.
  • Liquid crystal aligning agent containing a very small amount of a compound selected from a compound containing an acid group, a compound containing one carboxylic anhydride group in the molecule, and a compound containing one tertiary amino group in the molecule (For example, see Patent Document 2) is known.
  • JP 09-278724 A Japanese Patent Laid-Open No. 08-76128
  • liquid crystal display elements are being used for in-vehicle applications such as car navigation systems and meter panels, as well as smartphones and tablet computers.
  • in-vehicle applications such as car navigation systems and meter panels, as well as smartphones and tablet computers.
  • the backlight is used with a high light amount or a backlight with a high calorific value.
  • the liquid crystal display element is likely to receive a lot of external light such as sunlight including ultraviolet rays.
  • peripheral members in the liquid crystal display element for example, organic members such as color filters and column spacers may be decomposed.
  • the voltage holding ratio characteristic is lowered, and line burn-in, which is a display defect of the liquid crystal display element, occurs, and the reliability of the liquid crystal display element is lowered.
  • the liquid crystal alignment film is required to have a good voltage holding ratio even when the peripheral member of the liquid crystal display element is decomposed by light irradiation to the liquid crystal display element.
  • the liquid crystal alignment film is required that this characteristic be good.
  • a composition composed of a normal polyimide polymer has low transparency of the resin film, and accordingly, the resin film is easily decomposed when exposed to light such as ultraviolet rays. Therefore, it is necessary to increase the transparency of the resin film and suppress decomposition.
  • an object of the present invention is to provide a composition having the above characteristics. That is, an object of the present invention is to provide a composition in which the resin film has high transparency and can suppress the decomposition of the resin film by light such as ultraviolet rays.
  • the present invention provides a liquid crystal alignment film using the above-described composition, wherein the liquid crystal alignment film has an excellent voltage holding ratio even when light is irradiated in a state where an insulating film made of an organic member is present under the liquid crystal alignment film. It aims at providing the liquid-crystal aligning agent used as this.
  • an object of the present invention is to provide a liquid crystal display element provided with a liquid crystal alignment film that meets the above-mentioned requirements.
  • the present inventor has at least one polymer selected from a cellulose-based polymer having a specific structure and a polyimide precursor obtained by reacting a diamine component with a tetracarboxylic acid component or a polyimide.
  • the present invention has been completed by finding that a composition containing a salt is extremely effective for achieving the above object.
  • the present invention has the following gist.
  • Component (A) a polymer having a structure represented by the following formula [1].
  • X 1 , X 2 , X 3 , X 4 , X 5 and X 6 each independently represent a group having a structure selected from the following formulas [1a] to [1m].
  • N represents an integer of 100 to 1000000).
  • X 7 , X 8 , X 9 , X 10 , X 11 , X 12 , X 13 and X 14 are each independently a benzene ring, methyl group, or ethyl group. , N-propyl group, isopropyl group or butyl group, in formula [1h], n represents an integer of 0 to 3, and in formula [1i], m represents an integer of 0 to 3.
  • Component (B) At least one polymer selected from a polyimide precursor and a polyimide obtained by reacting a diamine component and a tetracarboxylic acid component.
  • a represents an integer of 0 to 4.
  • a represents an integer of 0 to 4 and n represents an integer of 1 to 4).
  • Y has a structure selected from the following formula [2b-1], formula [2b-2], formula [2b-3], formula [2b-4], or formula [2b-5].
  • a represents an integer of 0 to 4
  • 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 represents a single bond or — (CH 2 ) b — (b is an integer of 1 to 15)
  • Y 3 represents a single bond, — (CH 2 ) c — (c is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or —OCO—
  • Y 4 represents a benzene ring, A divalent cyclic group selected from a cyclohexane ring or a heterocyclic ring, or a divalent organic group having 12 to 25 carbon atoms having a steroid skeleton, wherein any hydrogen atom on the cyclic group has 1 to 3 carbon atoms
  • Y 5 represents a divalent cyclic group selected from benzene ring, cyclohexane ring or a heterocyclic ring, any hydrogen atom on these cyclic group
  • carbon atoms 1 May be substituted with an alkyl group having 1 to 3, 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, or a fluorine atom
  • n is 0
  • 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.
  • Y 7 represents —O—, —CH 2 O—, —COO—, —OCO—, —CONH— or —NHCO—
  • Y 8 has 8 to 22 carbon atoms.
  • Y 9 and Y 10 each independently represent a hydrocarbon group having 1 to 12 carbon atoms
  • Y 11 represents an alkyl group having 1 to 5 carbon atoms. Show).
  • Z 1 is a group having a structure selected from the following formulas [3a] to [3j]).
  • Z 2 to Z 5 represent 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 A hydrogen atom or a methyl group, which may be the same or different.
  • the component (D) contains at least one solvent selected from the solvents represented by the following formulas [D-1] to [D-3]: A composition according to claim 1.
  • D 1 represents an alkyl group having 1 to 3 carbon atoms
  • D 2 represents an alkyl group having 1 to 3 carbon atoms
  • D 3 represents an alkyl group having 1 to 4 carbon atoms
  • the component (E) contains at least one solvent selected from 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether or ethylene glycol monobutyl ether.
  • solvent selected from 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether or ethylene glycol monobutyl ether.
  • 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.
  • a liquid crystal display device comprising the liquid crystal alignment film according to (14).
  • a liquid crystal alignment film having a liquid crystal layer between a pair of substrates provided with electrodes and including a polymerizable group that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates.
  • a liquid crystal display device comprising the liquid crystal alignment film according to (16).
  • a composition containing at least one polymer selected from a cellulose-based polymer having a specific structure of the present invention and a polyimide precursor or polyimide obtained by reacting a diamine component and a tetracarboxylic acid component is a resin film.
  • the transparency of the resin is high, and decomposition of the resin film accompanying light irradiation can be suppressed.
  • the liquid crystal alignment treatment agent comprising the composition of the present invention forms a liquid crystal alignment film having an excellent voltage holding ratio even when irradiated with light in the presence of an insulating film made of an organic member under the liquid crystal alignment film. Can do. Therefore, the liquid crystal display element having the liquid crystal alignment film obtained thereby can have high reliability.
  • the present invention relates to a composition containing the following components (A) and (B), a liquid crystal alignment treatment agent, a resin film obtained using the composition, and a liquid crystal alignment film obtained using the liquid crystal alignment treatment agent. Furthermore, the present invention relates to a liquid crystal display element having the liquid crystal alignment film.
  • Component (A) a polymer having a structure represented by the following formula [1] (also referred to as a specific cellulose polymer).
  • X 1 , X 2 , X 3 , X 4 , X 5 and X 6 are each independently at least one structure selected from the following formulas [1a] to [1m]. And n represents an integer of 100 to 1,000,000).
  • X 7 , X 8 , X 9 , X 10 , X 11 , X 12 , X 13 and X 14 are each independently a benzene ring, methyl group, or ethyl group. , N-propyl group, isopropyl group or butyl group, in formula [1h], n represents an integer of 0 to 3, and in formula [1i], m represents an integer of 0 to 3.
  • Component (B) At least one polymer selected from a polyimide precursor or polyimide obtained by reacting a diamine component and a tetracarboxylic acid component (also referred to as a specific polyimide polymer).
  • the specific cellulose polymer of the present invention has higher transparency than the polyimide polymer. Therefore, the resin film obtained from the composition of the present invention is less likely to absorb light such as ultraviolet rays than that obtained from a normal polyimide polymer, and accordingly, the resin film is less likely to be decomposed.
  • composition of the present invention contains a specific polyimide polymer excellent in light resistance and heat resistance together with the specific cellulose polymer, the stability of the resin film against light and heat becomes higher.
  • the specific cellulose polymer of the present invention has many OH groups (hydroxyl groups) and COOH groups (carboxylic acid groups), it can trap ionic impurities such as metals and low molecular weight organic compounds. Therefore, the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention becomes a liquid crystal alignment film having an excellent voltage holding ratio even when light is irradiated in a state where an insulating film made of an organic member is present under the liquid crystal alignment film. .
  • liquid-crystal aligning agent of this invention contains the specific polyimide type polymer, the ability to orient a liquid crystal (it is also called liquid crystal orientation) and a pretilt angle are provided with the characteristic of the voltage retention mentioned above.
  • a liquid crystal alignment film having excellent characteristics can also be formed.
  • the composition of the present invention can form a highly transparent resin film.
  • the liquid-crystal aligning agent obtained from the composition of this invention is excellent in a voltage holding
  • the specific cellulose polymer as the component (A) of the present invention is a polymer having a structure represented by the following formula [1].
  • X 1 , X 2 , X 3 , X 4 , X 5 and X 6 each independently have at least one structure selected from the following formulas [1a] to [1m] Indicates a group.
  • X 7 , X 8 , X 9 , X 10 , X 11 , X 12 , X 13 and X 14 are each independently a benzene ring, methyl group, ethyl group, n -Represents propyl, isopropyl or butyl.
  • n represents an integer of 0 to 3. Of these, an integer of 0 or 1 is preferable.
  • m represents an integer of 0 to 3. Of these, an integer of 0 or 1 is preferable.
  • X 1 , X 2 , X 3 , X 4 , X 5 and X 6 each independently represent a structure selected from formula [1a] to formula [1m]. May be one type or two or more types. In particular, it is preferable to use two or more types from the viewpoints of solubility of a specific cellulose polymer in a solvent and applicability of a composition or a liquid crystal aligning agent. It is particularly preferable to use the structure of the formula [1a] and the structures of the formulas [1b] to [1m]. Furthermore, it is preferable to use the structure of formula [1a] and the structure of formula [1c], the structure of formula [1d], the structure of formula [1e], the structure of formula [1h], or the structure of formula [1i].
  • n represents an integer of 100 to 1,000,000.
  • 100 to 500,000 is preferable from the viewpoint of the solubility of the specific cellulose polymer in a solvent and the handleability when adjusted as a composition or a liquid crystal aligning agent. More preferred is 100 to 100,000.
  • Specific examples of the specific cellulose-based polymer of the present invention include the following, but are not limited to these examples.
  • cellulose methylcellulose, ethylcellulose, propylcellulose, butylcellulose, methylethylcellulose, acetylcellulose, cellulose propionate, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, ethylhydroxyethylcellulose, hydroxybutylmethylcellulose, hydroxypropylmethylcellulose Phthalate, methylaminocellulose, ethylaminocellulose, propylaminocellulose, benzylcellulose, tribenzoylcellulose, cellulose acetate butyrate, cellulose acetate propionate, carboxymethylcellulose, carboxymethylethylcellulose or carboxy Include the chill hydroxyethyl cellulose.
  • Particularly preferred are methylcellulose, ethylcellulose, acetylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, ethylhydroxyethylcellulose or hydroxypropylmethylcellulose phthalate.
  • a method of reacting in the presence of an alkali to cellulose and benzyl chloride to introduce the structure of formula [1c] is a halogen compound having a cellulose and X 7 a method of reacting in the presence of an alkali
  • a method of reacting the method and cellulose and acetic anhydride is reacted with an acid chloride compound having the structure of cellulose and X 8 in the presence of an alkali
  • a method in which cellulose and a halogen compound having a structure of X 9 —OH are reacted in the presence of an alkali.
  • cellulose and X a method of reacting in the presence of an alkali and a halogen compound having the structure 10 -COOH, the case of introducing the structure of formula [1 g], the cellulose A method of reacting in the presence of an alkali and a halogen compound having the structure 11 -NH 2, the case of introducing the structure of formula [1h], a method of reacting a cellulose with phthalic acid, introducing the structure of formula [1i] If you are a method of reacting a halogen compound having a cellulose and X 12 and phthalic acid skeleton in the presence of an alkali, to introduce the structure of formula [1k] can include a method of reacting a cellulose with maleic anhydride It is done.
  • These specific cellulosic polymers represented by the formula [1] are the solubility and coating properties of the specific cellulosic polymer of the present invention in a solvent, the orientation of liquid crystals when used as a liquid crystal alignment film, the voltage holding ratio, One type or a mixture of two or more types can be used in accordance with characteristics such as accumulated charge.
  • the specific polyimide polymer which is the component (B) of the present invention is a polymer selected from a polyimide precursor or a polyimide obtained by reacting a diamine component and a tetracarboxylic acid component.
  • the polyimide precursor has a structure represented by the following formula [A].
  • R 1 is a tetravalent organic group
  • R 2 is a divalent organic group
  • a 1 and A 2 represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • a 3 and A 4 each represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an acetyl group, which may be the same or different
  • n represents a positive integer. Show).
  • the diamine component is a diamine compound having two primary or secondary amino groups in the molecule
  • the tetracarboxylic acid component is a tetracarboxylic acid compound, tetracarboxylic dianhydride, or tetracarboxylic acid dihalide compound.
  • tetracarboxylic acid dialkyl ester compounds or tetracarboxylic acid dialkyl ester dihalide compounds are examples of the tetracarboxylic acid dialkyl ester compounds.
  • R 1 and R 2 are as defined in formula [A]).
  • the polymer of the formula [D] obtained above is added to the alkyl group having 1 to 8 carbon atoms of A 1 and A 2 represented by the formula [A] and the formula [A] by a usual synthesis method. It is also possible to introduce an alkyl group having 1 to 5 carbon atoms or an acetyl group of A 3 and A 4 shown.
  • a known diamine compound can be used as the diamine component for producing the specific polyimide polymer that is the component (B) of the present invention.
  • a represents an integer of 0 to 4. Especially, the integer of 0 or 1 is preferable from the point of the availability of a raw material or the ease of a synthesis
  • diamine compound having a structure represented by the formula [2a] include a diamine compound represented by the following formula [2a-1].
  • a represents an integer of 0 to 4. Among these, 0 or 1 is preferable from the viewpoint of availability of raw materials and ease of synthesis.
  • n represents an integer of 1 to 4. Among these, 1 is preferable from the viewpoint of ease of synthesis.
  • the method for producing the diamine compound represented by the formula [2a] of the present invention is not particularly limited, but preferred methods include those shown below.
  • a diamine compound represented by the formula [2a-1] is obtained by synthesizing a dinitro compound represented by the following formula [2a-A], and further reducing the nitro group to convert it to an amino group. It is done.
  • a represents an integer of 0 to 4 and n represents an integer of 1 to 4).
  • the method for reducing the dinitro group of the dinitro compound represented by the formula [2a-A] is not particularly limited, and is usually palladium-carbon in a solvent such as ethyl acetate, toluene, tetrahydrofuran, dioxane or an alcohol solvent, There is a method in which platinum oxide, Raney nickel, platinum black, rhodium-alumina, platinum sulfide carbon, or the like is used as a catalyst and reacted in hydrogen gas, hydrazine, or hydrogen chloride.
  • Examples of the diamine compound represented by the formula [2a] of the present invention further include diamine compounds represented by the following formulas [2a-2] to [2a-5].
  • a 1 is a single bond, —CH 2 —, —C 2 H 4 —, —C (CH 3 ) 2 —, —CF 2 —, —C (CF 3 ) 2 —, — O—, —CO—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —CH 2 O—, —OCH 2 —, —COO—, —OCO—, —CON (CH 3 ) — or —N (CH 3 ) CO—.
  • a single bond —CH 2 —, —C (CH 3 ) 2 —, —O—, —CO—, —NH—, —N (CH 3 ) —, —CONH —, —NHCO—, —COO— or —OCO— is preferred. More preferred is a single bond, —CH 2 —, —C (CH 3 ) 2 —, —O—, —CO—, —NH— or —N (CH 3 ) —.
  • n 1 and m 2 each represent an integer of 0 to 4, and m 1 + m 2 represents an integer of 1 to 4. Among them, m 1 + m 2 is 1 or 2 are preferred.
  • n 3 and m 4 each represent an integer of 1 to 5. Of these, 1 or 2 is preferable from the viewpoint of ease of synthesis.
  • a 2 represents a linear or branched alkyl group having 1 to 5 carbon atoms. Of these, a linear alkyl group having 1 to 3 carbon atoms is preferable.
  • m 5 represents an integer of 1 to 5. Of these, 1 or 2 is preferable.
  • a 3 is a single bond, —CH 2 —, —C 2 H 4 —, —C (CH 3 ) 2 —, —CF 2 —, —C (CF 3 ) 2 —, — O—, —CO—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —CH 2 O—, —OCH 2 —, —COO—, —OCO—, —CON (CH 3 ) — or —N (CH 3 ) CO—.
  • a single bond —CH 2 —, —C (CH 3 ) 2 —, —O—, —CO—, —NH—, —CONH—, —NHCO—, —CH 2 O—, —OCH 2 — , —COO— or —OCO— is preferable. More preferred is —O—, —CO—, —NH—, —CONH—, —NHCO—, —CH 2 O—, —OCH 2 —, —COO— or —OCO—.
  • m 6 represents an integer of 1 to 4. Of these, 1 is preferable from the viewpoint of ease of synthesis.
  • the diamine compounds represented by the formulas [2a-1] to [2a-5] are preferably 20 mol% to 100 mol%, more preferably 30 mol% to 80 mol%, based on the total diamine component. It is preferable that
  • the diamine compound represented by the formula [2a-1] to the formula [2a-5] is a liquid crystal in the case where the specific polyimide polymer of the present invention is dissolved in a solvent, the coating property of the composition, or a liquid crystal alignment film.
  • One kind or a mixture of two or more kinds can be used according to the properties such as the orientation, voltage holding ratio, and accumulated charge.
  • a diamine compound represented by the following formula [2b] is preferably used as the diamine component for producing the specific polyimide polymer of the present invention.
  • Y represents at least one selected from the following formula [2b-1], formula [2b-2], formula [2b-3], formula [2b-4], or formula [2b-5].
  • a represents an integer of 0 to 4. Especially, the integer of 0 or 1 is preferable from the point of the availability of a raw material or the ease of a synthesis
  • 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 preferred.
  • More preferred is a single bond, — (CH 2 ) a — (a is an integer of 1 to 10), —O—, —CH 2 O— or —COO—.
  • Y 2 represents a single bond or — (CH 2 ) b — (b is an integer of 1 to 15).
  • 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—.
  • a single bond, — (CH 2 ) c — (c is an integer of 1 to 15), —O—, —CH 2 O— or —COO— is preferable from the viewpoint of ease of synthesis. More preferred is a single bond, — (CH 2 ) c — (c is an integer of 1 to 10), —O—, —CH 2 O— or —COO—.
  • Y 4 is a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, and any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms. And 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, or a fluorine atom. Furthermore, Y 4 may be a divalent organic group selected from organic groups having 12 to 25 carbon atoms having a steroid skeleton. Of these, an organic group having 12 to 25 carbon atoms having a benzene ring, a cyclohexane ring or a steroid skeleton is preferable from the viewpoint of ease of synthesis.
  • Y 5 represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, and any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms. And 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, or a fluorine atom. Of these, a benzene ring or a cyclohexane ring is preferable.
  • n represents an integer of 0 to 4.
  • 0 to 3 are preferable from the viewpoint of availability of raw materials and ease of synthesis. More preferred is 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. Indicates. Of these, 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, or a fluorine-containing alkoxyl group having 1 to 10 carbon atoms is preferable.
  • it is an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms. Particularly preferred is an alkyl group having 1 to 9 carbon atoms or an alkoxyl group having 1 to 9 carbon atoms.
  • Y 7 represents —O—, —CH 2 O—, —COO—, —OCO—, —CONH— or —NHCO—.
  • —O—, —CH 2 O—, —COO— or —CONH— is preferable. More preferred is —O—, —COO— or —CONH—.
  • Y 8 represents an alkyl group having 8 to 22 carbon atoms.
  • Y 9 and Y 10 each independently represent a hydrocarbon group having 1 to 12 carbon atoms.
  • Y 11 represents an alkyl group having 1 to 5 carbon atoms.
  • the method for producing the diamine compound represented by the formula [2b] of the present invention is not particularly limited, but preferred methods include those shown below.
  • a diamine compound represented by the formula [2b] can be obtained by synthesizing a dinitro compound represented by the following formula [2b-A], further reducing the nitro group and converting it to an amino group.
  • Y is at least selected from Formula [2b-1], Formula [2b-2], Formula [2b-3], Formula [2b-4], or Formula [2b-5].
  • 1 represents a substituent of one structure, and m represents an integer of 0 to 4.
  • the method for reducing the dinitro group of the dinitro compound represented by the formula [2b-A] is not particularly limited, and is usually palladium-carbon in a solvent such as ethyl acetate, toluene, tetrahydrofuran, dioxane or an alcohol solvent.
  • a solvent such as ethyl acetate, toluene, tetrahydrofuran, dioxane or an alcohol solvent.
  • platinum oxide, Raney nickel, platinum black, rhodium-alumina, platinum sulfide carbon, or the like is used as a catalyst and reacted in hydrogen gas, hydrazine, or hydrogen chloride.
  • the diamine compound represented by the formula [2b] includes m-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 2,6-diaminotoluene, 2,4-diaminophenol, 3,5-diaminophenol.
  • diamine compounds having structures represented by the following formulas [2b-6] to [2b-46] are exemplified. be able to.
  • a 1 represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group).
  • R 1 represents —O—, —OCH 2 —, —CH 2 O—, —COOCH 2 — or CH 2 OCO—
  • R 2 represents carbon An alkyl group, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group represented by formulas 1 to 22).
  • R 3 represents —COO—, —OCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, —OCH 2 — or — CH 2 - indicates
  • R 4 represents an alkyl group, alkoxy group, fluorine-containing alkyl group or fluorine-containing alkoxy group of 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, a cyano group, a trifluoromethane group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group or a hydroxyl group).
  • R 7 represents an alkyl group having 3 to 12 carbon atoms. Note that the cis-trans isomerism of 1,4-cyclohexylene is the trans isomer. preferable).
  • R 8 represents an alkyl group having 3 to 12 carbon atoms.
  • the cis-trans isomerism of 1,4-cyclohexylene is the trans isomer. preferable).
  • B 4 represents an alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom
  • B 3 represents a 1,4-cyclohexylene group or a 1,4-phenylene group
  • B 2 represents an oxygen atom or —COO— * (where a bond marked with “*” binds to B 3 )
  • B 1 represents an oxygen atom or —COO— * (where “*” bond marked with represents a (CH 2) bind to a 2).
  • a 1 represents an integer of 0 or 1
  • a 2 represents an integer of 2 ⁇ 10
  • a 3 is 0 or 1 Indicates an integer).
  • the composition using the diamine compound in which the substituent Y in the formula [2b] is represented by the formula [2b-2] has a hydrophobic property of the resin film. Can be high. Further, when the liquid crystal alignment film is used, the pretilt angle of the liquid crystal can be increased. At that time, for the purpose of enhancing these effects, among the above diamine compounds, diamines represented by the formula [2b-28] to the formula [2b-39] or the formula [2b-42] to the formula [2b-46] are used. It is preferable to use a compound.
  • diamine compounds represented by the formulas [2b-24] to [2b-39] or the formulas [2b-42] to [2b-46].
  • these diamine compounds are 5 mol% or more and 80 mol% or less of the whole diamine component. More preferably, these diamine compounds are 5 mol% or more and 60 mol% of the whole diamine component from the viewpoint of the applicability of the composition and the liquid crystal alignment treatment agent and the electric characteristics as the liquid crystal alignment film.
  • the diamine compound represented by the formula [2b] is used for the solubility and coating property of the specific polyimide polymer of the present invention in a solvent, liquid crystal alignment in the case of forming a liquid crystal alignment film, voltage holding ratio, accumulated charge, etc. Depending on the characteristics, one kind or a mixture of two or more kinds can be used.
  • diamine component for producing the specific polyimide polymer of the present invention examples include diamine compounds represented by the formulas [2a-1] to [2a-5] and diamine compounds other than the diamine compounds represented by the formula [2b]. (Also referred to as other diamine compounds) can be used as the diamine component. Specific examples of other diamine compounds are shown below, but are not limited to these examples.
  • diamine compounds 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, and those having a macrocyclic substituent composed of these. .
  • diamine compounds represented by the following formulas [DA1] to [DA13] can be exemplified.
  • a 1 represents —COO—, —OCO—, —CONH—, —NHCO—, —CH 2 —, —O—, —CO— or —NH—
  • a 2 represents a linear or branched alkyl group having 1 to 22 carbon atoms or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms).
  • p represents an integer of 1 to 10).
  • diamine compounds represented by the following formulas [DA8] to [DA13] can also be used as other diamine compounds.
  • n represents an integer of 1 to 5
  • a diamine compound represented by the following formula [DA14] can also be used as long as the effects of the present invention are not impaired.
  • a 1 represents —O—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —CH 2 O—, —OCO—, —CON (CH 3 ).
  • a 3 is a hydrocarbon group, A 3 is a single bond, —O—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —COO—, —OCO—, —CON (CH 3 ) —, —N (CH 3 ) CO— or —O (CH 2 ) m — (m is an integer of 1 to 5), A 4 is a nitrogen-containing aromatic heterocycle, and n is 1 to 4 is an integer).
  • diamine compounds represented by the following formulas [DA15] and [DA16] can also be used.
  • the above-mentioned other diamine compounds have characteristics such as the solubility of the specific polyimide polymer of the present invention in a solvent, the coating property of the composition, the orientation of the liquid crystal when it is used as a liquid crystal alignment film, the voltage holding ratio, and the accumulated charge. Depending on the case, one kind or a mixture of two or more kinds may be used.
  • tetracarboxylic acid component As the tetracarboxylic acid component for producing the specific polyimide polymer which is the component (B) of the present invention, tetracarboxylic dianhydride represented by the following formula [3] or tetracarboxylic acid derivative tetra It is preferable to use a carboxylic acid, a tetracarboxylic acid dihalide compound, a tetracarboxylic acid dialkyl ester compound or a tetracarboxylic acid dialkyl ester dihalide compound (all are collectively referred to as a specific tetracarboxylic acid component).
  • Z 1 is a group having a structure selected from the following formulas [3a] to [3j].
  • Z 2 to Z 5 represent 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 represent a hydrogen atom or a methyl group, and may be the same or different.
  • Z 1 is represented by the formula [3a], from the viewpoint of ease of synthesis and polymerization reactivity when producing a polymer.
  • a structure represented by Formula [3c], Formula [3d], Formula [3e], Formula [3f], or Formula [3g] is preferable. More preferred is a structure represented by formula [3a], formula [3e], formula [3f] or formula [3g], and particularly preferred is formula [3e], formula [3f] or formula [3g]. It is.
  • the specific tetracarboxylic acid component of the present invention is preferably 1 mol% or more of the total tetracarboxylic acid component. More preferred is 5 mol% or more, and particularly preferred is 10 mol% or more.
  • the usage-amount is made into 20 mol% or more of the whole tetracarboxylic acid component, and it is desired An effect is obtained. Preferably, it is 30 mol% or more.
  • all of the tetracarboxylic acid component may be a tetracarboxylic acid component having a structure of the formula [3e], the formula [3f], or the formula [3g].
  • tetracarboxylic acid components other than the specific tetracarboxylic acid component can be used as long as the effects of the present invention are not impaired.
  • examples of other tetracarboxylic acid components include the following tetracarboxylic acid compounds, tetracarboxylic dianhydrides, tetracarboxylic acid dihalide compounds, tetracarboxylic acid dialkyl ester compounds, and tetracarboxylic acid dialkyl ester dihalide compounds.
  • tetracarboxylic acid components include pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalene.
  • Tetracarboxylic acid 2,3,6,7-anthracenetetracarboxylic acid, 1,2,5,6-anthracenetetracarboxylic 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-dicarboxyphenyl) sulfone, bis ( 3,4-dicarboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, 1,1,1,3,3,3-hexafluoro- , 2-bis (3,4-dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) diphenylsilane, 2,3,4,5-pyridine Te
  • the specific tetracarboxylic acid component and other tetracarboxylic acid components are the solubility of the specific polyimide polymer of the present invention in the solvent, the coating property of the composition, the alignment property of the liquid crystal when used as a liquid crystal alignment film, and the voltage holding ratio. Depending on the characteristics such as accumulated charge, one kind or a mixture of two or more kinds may be used.
  • the method for synthesizing the specific polyimide polymer is not particularly limited. Usually, it is obtained by reacting a diamine component and a tetracarboxylic acid component. Generally, at least one tetracarboxylic acid component selected from the group consisting of tetracarboxylic acids and derivatives thereof is reacted with a diamine component consisting of one or more diamine compounds to obtain a polyamic acid.
  • a method of obtaining polyamic acid by polycondensation of tetracarboxylic dianhydride and primary or secondary diamine compound, dehydration polycondensation reaction of tetracarboxylic acid and primary or secondary diamine compound A method of obtaining polyamic acid by polycondensation of a tetracarboxylic acid dihalide and a primary or secondary diamine compound is used.
  • a method of polycondensing a tetracarboxylic acid obtained by dialkyl esterifying a carboxylic acid group with a primary or secondary diamine compound, a tetracarboxylic acid dihalide obtained by dialkyl esterifying a carboxylic acid group and 1 A method of polycondensation with a secondary or secondary diamine compound or a method of converting a carboxyl group of a polyamic acid into an ester is used.
  • polyimide In order to obtain polyimide, a method is used in which the polyamic acid or polyamic acid alkyl ester is cyclized to form polyimide.
  • the reaction between the diamine component and the tetracarboxylic acid component is usually carried out with the diamine component and the tetracarboxylic acid component in an organic solvent.
  • the organic solvent used at that time is not particularly limited as long as the produced polyimide precursor is dissolved. Although the specific example of the organic solvent used for reaction below is given, it is not limited to these examples.
  • D 1 represents an alkyl group having 1 to 3 carbon atoms
  • D 2 represents an alkyl group having 1 to 3 carbon atoms
  • D 3 represents an alkyl group having 1 to 4 carbon atoms
  • the solution in which the diamine component is dispersed or dissolved in the organic solvent is stirred, and the tetracarboxylic acid component is dispersed or dissolved in the organic solvent as it is.
  • a method of adding a diamine component to a solution obtained by dispersing or dissolving a tetracarboxylic acid component in an organic solvent a method of alternately adding a diamine component and a tetracarboxylic acid component, etc. Any of these methods may be used.
  • the polymerization temperature can be selected from -20 ° C to 150 ° C, but is preferably in the range of -5 ° C to 100 ° C.
  • the reaction can be carried out at any concentration, but if the concentration is too low, it 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. It becomes. Therefore, it is preferably 1 to 50% by mass, more preferably 5 to 30% 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 the diamine component to the total number of moles of the tetracarboxylic acid component is preferably 0.8 to 1.2. Similar to a normal polycondensation reaction, the molecular weight of the polyimide precursor produced increases as the molar ratio approaches 1.0.
  • the polyimide of the present invention is a polyimide obtained by ring closure of the polyimide precursor, and in this polyimide, the ring closure rate of the amic acid group (also referred to as imidization rate) is not necessarily 100%. It can be arbitrarily adjusted according to the purpose.
  • Examples of the method for imidizing the polyimide precursor include thermal imidization in which the polyimide precursor solution is heated as it is or catalytic imidization in which a catalyst is added to the polyimide precursor solution.
  • the temperature is 100 ° C. to 400 ° C., preferably 120 ° C. to 250 ° C., and it is preferable to carry out while removing water generated by the imidation reaction from the system.
  • 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 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, and trioctylamine. Among them, pyridine is preferable because it has a basicity appropriate for advancing 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 solvent and precipitated.
  • the solvent used for precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, and water.
  • the polymer precipitated in the solvent can be collected by filtration, and then dried by normal temperature or reduced pressure at room temperature or by heating.
  • the solvent at this time include alcohols, ketones, and hydrocarbons, and it is preferable to use three or more kinds of solvents selected from these because purification efficiency is further increased.
  • the molecular weight of the specific polyimide polymer of the present invention was measured by a GPC (Gel Permeation Chromatography) method in consideration of the strength of the resin film or liquid crystal alignment film obtained therefrom, workability at the time of film formation, and coating properties.
  • the weight average molecular weight is preferably 5,000 to 1,000,000, and more preferably 10,000 to 150,000.
  • composition or liquid crystal alignment treatment agent of the present invention is a coating solution for forming a resin film or a liquid crystal alignment film (also collectively referred to as a resin film), and is a specific cellulose polymer, a specific polyimide polymer, and a solvent. It is the application
  • the ratio of the specific cellulose polymer and the specific polyimide polymer in the composition or the liquid crystal aligning agent of the present invention is such that when the ratio of the specific polyimide polymer is 1, the ratio of the specific cellulose polymer is 0. 1-9. Particularly preferred is 0.2-4.
  • All the polymer components in the composition or the liquid crystal aligning agent of the present invention may all be the specific cellulose polymer and the specific polyimide polymer of the present invention, and other polymers are mixed. May be. In that case, the content of the other polymer is 0.5 to 15% by mass, preferably 1 to 10% by mass, of the specific polymer of the present invention.
  • Other polymers include diamine compounds represented by the above formulas [2a-1] to [2a-5], diamine compounds represented by the formula [2b], and polyimides not using the specific tetracarboxylic acid component System polymers.
  • polymers other than a cellulose polymer and a polyimide polymer, specifically, an acrylic polymer, a methacrylic polymer, polystyrene, polyamide, or polysiloxane may be used.
  • the organic solvent in the composition or the liquid crystal aligning agent of the present invention preferably has an organic solvent content of 70 to 99.9% by mass from the viewpoint of forming a uniform resin film by coating. This content can be appropriately changed depending on the film thickness of the target resin film or liquid crystal alignment film.
  • the organic solvent used in the composition or the liquid crystal aligning agent of the present invention is not particularly limited as long as it is an organic solvent (also referred to as a good solvent) that dissolves the specific cellulose polymer and the specific polyimide polymer.
  • an organic solvent also referred to as a good solvent
  • a good solvent is given to the following, it is not limited to these examples.
  • N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, ⁇ -butyrolactone, the solvents represented by the above formulas [D-1] to [D-3], and the like can be given. These may be used alone or in combination.
  • N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and ⁇ -butyrolactone are preferably used.
  • component (C) ⁇ -butyrolactone
  • the specific cellulose polymer and the specific polyimide polymer are highly soluble in the solvent, the solvents represented by the above formulas [D-1] to [D-3] It is preferable to use
  • the good solvent in the composition or liquid crystal aligning agent of the present invention is preferably 10 to 100% by mass of the total solvent contained in the composition or liquid crystal aligning agent. Of these, 20 to 90% by mass is preferable. More preferred is 30 to 80% by mass.
  • composition or liquid-crystal aligning agent of this invention improves the coating property and surface smoothness of the resin film or liquid crystal aligning film at the time of apply
  • An organic solvent also referred to as a poor solvent
  • a poor solvent can be used. Although the specific example of a poor solvent is given to the following, it is not limited to these examples.
  • ethanol isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isopentyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 1,2- Ethane All, 1,2-propanediol, 1,3-propan
  • 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether or ethylene glycol monobutyl ether (also referred to as component (E) above), or the above-described formula [D -1] to a solvent represented by the formula [D-3] are preferably used.
  • These poor solvents are preferably 1 to 70% by mass of the whole organic solvent contained in the composition or the liquid crystal aligning agent. Among these, 1 to 60% by mass is preferable. More preferred is 5 to 60% by mass.
  • the composition or liquid crystal aligning agent of the present invention includes 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 alkoxyalkyl as long as the effects of the present invention are not impaired.
  • a crosslinkable compound having at least one substituent selected from the group consisting of groups or a crosslinkable compound having a polymerizable unsaturated bond can also be introduced. It is necessary to have two or more of these substituents and polymerizable unsaturated bonds in the crosslinkable compound.
  • 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-
  • the crosslinkable compound having an oxetane group is a crosslinkable compound having at least two oxetane groups represented by the following formula [4].
  • n represents an integer of 1 to 3).
  • n represents an integer of 1 to 3
  • n represents an integer of 1 to 3
  • n represents 1 to 100 Indicates an integer
  • n represents an integer of 1 to 10).
  • the crosslinkable compound having a cyclocarbonate group is a crosslinkable compound having at least two cyclocarbonate groups represented by the following formula [5].
  • n represents an integer of 1 to 10
  • n represents an integer of 1 to 10
  • n represents an integer of 1 to 100, and in the formula [5-37], n represents 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 represents a structure represented by the formula [5].
  • n represents 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 or an alkoxymethyl group or both 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 per
  • Examples of such melamine derivatives or benzoguanamine derivatives include MX-750, which has an average of 3.7 substituted methoxymethyl groups per triazine ring, and an average of 5. methoxymethyl groups per triazine ring.
  • Examples of the benzene or phenolic compound having a hydroxyl group or an alkoxyl group include 1,3,5-tris (methoxymethyl) benzene, 1,2,4-tris (isopropoxymethyl) benzene, 1,4-bis ( sec-butoxymethyl) benzene or 2,6-dihydroxymethyl-p-tert-butylphenol.
  • 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 or 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 (meth) 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 diglycidyl
  • E 1 represents 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 or a phenanthrene ring; 2 represents a group selected from the following formula [7a] or [7b], and n represents an integer of 1 to 4.
  • crosslinkable compound used for the composition or liquid crystal aligning agent 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 or the liquid crystal aligning agent of the present invention is preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of all the polymer components.
  • the amount is more preferably 0.1 to 100 parts by weight, and most preferably 1 to 50 parts by weight, based on 100 parts by weight of all polymer components.
  • a compound that promotes charge transfer in a liquid crystal alignment film and promotes charge release of a liquid crystal cell using the liquid crystal alignment film when a liquid crystal alignment film using the liquid crystal alignment treatment agent using the composition of the present invention is formed. It is preferable to add nitrogen-containing heterocyclic amine compounds represented by the formulas [M1] to [M156], which are described on pages 69 to 73 of International Publication No. WO2011 / 132751 (published 2011.10.27). .
  • This amine compound may be added directly to the composition, but it may be added after a solution having a concentration of 0.1% by mass to 10% by mass, preferably 1% by mass to 7% by mass with an appropriate solvent.
  • the solvent is not particularly limited as long as it is an organic solvent that dissolves the specific polyimide polymer described above.
  • the composition or the liquid crystal alignment treatment agent of the present invention has a uniform film thickness or surface smoothness of the resin film or the liquid crystal alignment film when the composition or the liquid crystal alignment treatment agent is applied.
  • Compounds that improve can be used.
  • a compound that improves the adhesion between the resin coating or the liquid crystal alignment film and the substrate can also be used.
  • Examples of compounds that improve the film thickness uniformity and surface smoothness of the resin coating or the liquid crystal alignment film include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.
  • F-top EF301, EF303, EF352 (above, manufactured by Tochem Products), MegaFuck F171, F173, R-30 (above, manufactured by Dainippon Ink), Florard FC430, FC431 (or more) And Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (above, 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 2 parts by mass with respect to 100 parts by mass of all the polymer components contained in the composition or the liquid crystal aligning agent. 1 part by mass.
  • the compound that improves the adhesion between the resin coating or the liquid crystal alignment film and the substrate include the functional silane-containing compounds and epoxy group-containing compounds shown below.
  • the amount of improving the adhesion cannot be expected, and if it exceeds 30 parts by mass, the storage stability of the composition or the liquid crystal aligning agent may be deteriorated.
  • composition or the liquid crystal alignment treatment agent of the present invention includes the above-mentioned poor solvent, crosslinkable compound, compound that improves the uniformity of film thickness and surface smoothness of the resin film or liquid crystal alignment film, and the compound that adheres to the substrate.
  • a dielectric material or a conductive material for the purpose of changing electrical characteristics such as dielectric constant or conductivity of the resin film or the liquid crystal alignment film may be added.
  • the composition of the present invention can be used as a resin film after coating and baking on a substrate.
  • a substrate used in this case a glass substrate, a silicon wafer, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like can be used depending on a target device.
  • the coating method of the composition is not particularly limited, but industrially, there are methods such as a dipping method, a roll coater method, a slit coater method, a spinner method, a spray method, screen printing, offset printing, flexographic printing, or an inkjet method. It is common. These can be appropriately selected according to the purpose.
  • the composition After the composition is applied onto the substrate, it is heated at 30 to 300 ° C., preferably 30 to 250, depending on the solvent used in the composition by a heating means such as a hot plate, a thermal circulation oven or an IR (infrared) oven.
  • the solvent can be evaporated at a temperature of 0 ° C. to form a resin film.
  • the thickness of the resin film after firing can be adjusted to 0.01 to 100 ⁇ m depending on the purpose.
  • the liquid crystal alignment treatment agent using the composition of the present invention can be used as a liquid crystal alignment film by applying alignment treatment by rubbing treatment or light irradiation after coating and baking on a substrate.
  • it can be used as a liquid crystal alignment film without alignment treatment.
  • the substrate used at this time is not particularly limited as long as it is a highly transparent substrate.
  • a plastic substrate such as an acrylic substrate or a polycarbonate substrate can also be used. From the viewpoint of simplification of the process, it is preferable to use 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, a method of screen printing, offset printing, flexographic printing, an inkjet method, or the like is generally used.
  • Examples of 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 After applying the liquid crystal aligning agent on the substrate, it is preferably 30 to 300 ° C., depending on the solvent used for the liquid crystal aligning agent, by a heating means such as a hot plate, a thermal circulation oven or an IR (infrared) oven.
  • the liquid crystal alignment film can be obtained by evaporating the solvent at a temperature of 30 to 250 ° C. If the thickness of the liquid crystal alignment film after baking is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered. Is 10 to 100 nm.
  • the fired liquid crystal alignment 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 alignment treatment agent of the present invention by the above-described method and then preparing a liquid crystal cell by a known method.
  • a method for manufacturing a liquid crystal cell 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 place the other side of the liquid crystal alignment film on the other side. And a method of sealing the substrate by injecting liquid crystal under reduced pressure, or a method of bonding the substrate after dropping the liquid crystal on the surface of the liquid crystal alignment film on which the spacers are dispersed, and the like.
  • the liquid-crystal aligning agent of this invention has a liquid-crystal layer between a pair of board
  • the liquid crystal composition is also preferably used for a liquid crystal display device produced through a step of polymerizing a polymerizable compound by at least one of irradiation with active energy rays and heating while applying a voltage between 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. Further, ultraviolet irradiation and heating may be performed simultaneously.
  • 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 after obtaining a substrate with a liquid crystal alignment film from the liquid crystal alignment treatment agent of the present invention by the above-described method, and a polymerizable compound is produced by at least one of irradiation with ultraviolet rays and heating.
  • the orientation of the liquid crystal molecules can be controlled by polymerizing.
  • 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 and the liquid crystal is injected under reduced pressure, or 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.
  • 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 is less than 0.01 part by mass, the polymerizable compound is not polymerized and the orientation of the liquid crystal cannot be controlled, and when it exceeds 10 parts by mass, the amount of unreacted polymerizable compound increases and the liquid crystal display element. The seizure characteristics of the steel deteriorate.
  • the polymerizable compound After producing the liquid crystal cell, the polymerizable compound is polymerized by heating or irradiating with 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.
  • the heating temperature is 40 to 120 ° C, preferably 60 to 80 ° C. Further, ultraviolet irradiation and heating may be performed simultaneously.
  • liquid crystal aligning agent of the present invention contains a specific compound having a double bond site that reacts by heat or ultraviolet irradiation, 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 attached and liquid crystal is injected under reduced pressure and sealing is performed, or a method in which the substrate is attached and sealed after the liquid crystal is dropped on the liquid crystal alignment film surface on which the spacers are dispersed.
  • the orientation of the liquid crystal molecules can be controlled by irradiating with heat or ultraviolet rays while applying an AC or DC voltage to the liquid crystal cell.
  • the liquid crystal display device manufactured using the liquid crystal aligning agent of the present invention has excellent reliability and can be suitably used for a large-screen, high-definition liquid crystal television.
  • A1 3,5-Diaminobenzoic acid (diamine compound represented by the following formula [A1])
  • A2 2,5-diaminobenzoic acid (diamine compound represented by the following formula [A2])
  • B1 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxy] benzene (diamine compound represented by the following formula [B1])
  • B2 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxymethyl] benzene (diamine compound represented by the following formula [B2])
  • B3 1,3-diamino-4- ⁇ 4- [trans-4- (trans-4-n-pentylcyclohexyl) cyclohexyl] phenoxy ⁇ benzene (diamine compound represented by the following formula [B3])
  • B4 Diamine compound represented by the following formula [B4]
  • B5 1,3-diamino-4-octadecyloxybenzene (diamine compound represented by the following formula [B5])
  • B5 Diamine compound represented by the following formula [B
  • NMP N-methyl-2-pyrrolidone
  • NEP N-ethyl-2-pyrrolidone
  • ⁇ -BL ⁇ -butyrolactone
  • the molecular weights of the polyimide precursor and the polyimide in the synthesis example are determined using a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko KK) and a column (KD-803, KD-805) (manufactured by Shodex). The measurement was performed as follows.
  • the imidation ratio of polyimide in the synthesis example was measured as follows. 20 mg of polyimide powder was put into an NMR (nuclear magnetic resonance) sample tube (NMR sampling tube standard, ⁇ 5 (manufactured by Kusano Kagaku)), and deuterated dimethyl sulfoxide (DMSO-d6, 0.05 mass% TMS (tetramethylsilane)). (Mixed product) (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 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 ppm 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.
  • the specific polyimide polymer of the present invention is shown in Table 1.
  • Tables 2 to 4 show the compositions and liquid crystal aligning agents of the present invention.
  • compositions or liquid crystal alignment treatment agents obtained in the examples and comparative examples of the present invention “Evaluation of transparency of resin film”, “Evaluation of ink jet coatability of liquid crystal alignment treatment agent”, “Preparation of liquid crystal cell” And “Evaluation of liquid crystal alignment (ordinary cell)”, “Preparation of liquid crystal cell and evaluation of liquid crystal alignment (PSA cell)” and “Evaluation of voltage holding ratio on insulating film coated substrate”.
  • the conditions are as follows.
  • an ultraviolet-visible absorption spectrum with a wavelength of 300 to 750 nm was measured with an ultraviolet-visible spectrophotometer (UV-2550) (manufactured by Shimadzu Corporation).
  • UV-2550 ultraviolet-visible spectrophotometer
  • Tables 5 to 7 show the results of the transparency of the resin films obtained in the examples and comparative examples.
  • Example 7 of the present invention The liquid crystal aligning agent (7) obtained in Example 7 of the present invention and the liquid crystal aligning agent (13) obtained in Example 13 were subjected to pressure filtration with a membrane filter having a pore diameter of 1 ⁇ m, and evaluation of ink jet coatability was performed. Went.
  • As the ink jet coater HIS-200 (manufactured by Hitachi Plant Technology) was used. Application is on an ITO (indium tin oxide) vapor-deposited substrate cleaned with pure water and IPA (isopropyl alcohol), the application area is 70 ⁇ 70 mm, the nozzle pitch is 0.423 mm, and the scan pitch is 0.5 mm. The speed was 40 mm / second, the time from application to temporary drying was 60 seconds, and temporary drying was performed on a hot plate at 70 ° C. for 5 minutes.
  • the surface of the ITO substrate was rubbed using a rayon cloth with a rubbing apparatus having a roll diameter of 120 mm under the conditions of a roll rotation speed of 1000 rpm, a roll traveling speed of 50 mm / sec, and an indentation amount of 0.1 mm.
  • liquid crystal aligning agent (1) and liquid crystal aligning agent (2) obtained in Example 1 and Example 2 obtained in Example 1 and Example 2
  • the liquid crystal aligning agent In the liquid crystal cell using the treating agent (21) and the liquid crystal aligning agent (24) obtained in Comparative Example 5 nematic liquid crystal (MLC-2003) (manufactured by Merck Japan) was used as the liquid crystal.
  • MLC-2003 nematic liquid crystal
  • a liquid crystal cell using the liquid crystal aligning agent (23), nematic liquid crystal (MLC-6608) manufactured by Merck Japan
  • the liquid crystal alignment was evaluated using the liquid crystal cell obtained above.
  • the liquid crystal alignment was confirmed by observing the liquid crystal cell with a polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon Corporation) to check for the presence of alignment defects. Specifically, those in which no alignment defect was observed were considered excellent in this evaluation (shown as good in Tables 8 to 10).
  • Tables 8 to 10 show the liquid crystal orientation results obtained in the examples and comparative examples.
  • This solution was washed with pure water and IPA at the center with a 10 ⁇ 10 mm ITO electrode substrate with a pattern spacing of 20 ⁇ m (vertical 40 mm ⁇ width 30 mm, thickness 0.7 mm) and at the center with a 10 ⁇ 40 mm ITO electrode substrate
  • Spin coating was performed on the ITO surface (length 40 mm ⁇ width 30 mm, thickness 0.7 mm), and heat treatment was performed on a hot plate at 100 ° C. for 5 minutes to obtain a polyimide coating film having a thickness of 100 nm.
  • After the coated surface was washed with pure water, it was heat-treated at 100 ° C. for 15 minutes in a heat circulation type clean oven to obtain a substrate with a liquid crystal alignment film.
  • This substrate with a liquid crystal alignment film was combined with a liquid crystal alignment film surface inside, with a 6 ⁇ m spacer in between, and the periphery was adhered with a sealant to produce an empty cell.
  • a nematic liquid crystal (MLC-6608) (manufactured by Merck Japan) was added to the empty cell by a reduced pressure injection method, and a polymerizable compound (1) represented by the following formula was added to 100% by mass of the nematic liquid crystal (MLC-6608). Liquid crystal mixed with 0.3% by mass of the polymerizable compound (1) was injected, and the injection port was sealed to obtain a liquid crystal cell.
  • the response speed of the liquid crystal before and after UV irradiation of this liquid crystal cell was measured.
  • T90 ⁇ T10 from 90% transmittance to 10% transmittance was measured.
  • the response speed of the liquid crystal cell after the ultraviolet irradiation was faster than that of the liquid crystal cell before the ultraviolet irradiation, so that it was confirmed that the alignment direction of the liquid crystal was controlled. Further, in any liquid crystal cell, it was confirmed by observation with a polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon Corporation) that the liquid crystal was uniformly aligned.
  • ECLIPSE E600WPOL polarizing microscope
  • the insulating film composition obtained above was filtered using a 0.2 ⁇ m filter. Thereafter, this composition was washed with pure water and IPA, and a 10 ⁇ 10 mm substrate with an ITO electrode having a pattern spacing of 20 ⁇ m (length 40 mm ⁇ width 30 mm, thickness 0.7 mm) and a center 10 ⁇ 40 mm ITO It spin-coated on the ITO surface of the board
  • This coating film was irradiated with ultraviolet rays having an irradiation amount at 365 nm of 500 mJ / cm 2 by an ultraviolet irradiation apparatus PLA-501 (F) (manufactured by Canon Inc.) and subjected to heat treatment at 120 ° C. for 1 minute on a hot plate. did. Thereafter, a heat treatment was further performed on a hot plate at 200 ° C. for 60 minutes to obtain a substrate coated with an insulating film having a thickness of 1.12 ⁇ m.
  • a liquid crystal cell was prepared using a solution obtained by pressure-filtering the liquid crystal aligning agents obtained in Examples and Comparative Examples of the present invention through a membrane filter having a pore diameter of 1 ⁇ m and storing at ⁇ 15 ° C. for 48 hours. This solution is spin-coated on the insulating film-coated surface of the insulating film-coated substrate obtained above, and heat-treated on a hot plate at 100 ° C. for 5 minutes to provide an ITO substrate with a polyimide liquid crystal alignment film having a thickness of 100 nm Got.
  • the surface of the ITO substrate was rubbed using a rayon cloth with a rubbing apparatus having a roll diameter of 120 mm under the conditions of a roll rotation speed of 1000 rpm, a roll traveling speed of 50 mm / sec, and an indentation amount of 0.1 mm.
  • VHR voltage holding ratio measuring device
  • the liquid crystal cell for which the measurement of the voltage holding ratio was completed was irradiated with ultraviolet rays of 10 J / cm 2 in terms of 365 nm, and then VHR was measured under the same conditions.
  • the ultraviolet irradiation was performed using a desktop UV curing device (HCT3B28HEX-1) (manufactured by SEN LIGHT CORPORATION).
  • Tables 8 to 10 show the evaluation results of the voltage holding ratios of the insulating film coated substrates obtained in the examples and comparative examples.
  • Example 1 To the polyamic acid solution (1) (11.5 g) and CE-2 (0.72 g) having a resin solid content concentration of 25 mass% obtained by the synthesis method of Synthesis Example 1, NMP (27.0 g) and BCS (26 2 g) was added and stirred at 50 ° C. for 6 hours to obtain a composition (1). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (1) was used for evaluation also as a liquid-crystal aligning agent (1).
  • composition (1) and liquid crystal aligning agent (1) under the above-mentioned conditions, “Evaluation of transparency of resin film”, “Preparation of liquid crystal cell and evaluation of liquid crystal alignment (normal cell)” And “Evaluation of voltage holding ratio on insulating film coated substrate”.
  • Example 2 Polyimide powder (2) (2.33 g) and CE-1 (1.00 g) obtained by the synthesis method of Synthesis Example 2 were added to NEP (32.7 g), PCS (5.70 g) and BCS (21.2 g). ) And stirred at 70 ° C. for 24 hours to obtain a composition (2).
  • this composition no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution.
  • this composition (2) was used for evaluation also as a liquid-crystal aligning agent (2).
  • composition (2) and liquid crystal aligning agent (2) under the above-mentioned conditions, “Evaluation of transparency of resin film”, “Preparation of liquid crystal cell and evaluation of liquid crystal alignment (normal cell)” And “Evaluation of voltage holding ratio on insulating film coated substrate”.
  • Example 3 Polyamide acid solution (3) (12.6 g) having a solid content concentration of 25% by mass obtained by the synthesis method of Synthesis Example 3 and CE-1, NMP (15.7 g), BCS (15.9 g) and PB (19.1 g) was added, and the mixture was stirred at 50 ° C. for 6 hours to obtain a composition (3). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (3) was used for evaluation also as a liquid-crystal aligning agent (3).
  • Example 4 The polyamic acid solution (3) (7.80 g) having a solid content concentration of 25 mass% obtained by the synthesis method of Synthesis Example 3 and CE-2 were mixed with NMP (26.7 g), PCS (5.61 g) and BCS. (17.7g) was added and it stirred at 50 degreeC for 6 hours, and obtained the composition (4). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (4) was used for evaluation also as a liquid-crystal aligning agent (4).
  • Example 5 Polyimide powder (4) (2.45 g) and CE-2 (1.05 g) obtained by the synthesis method of Synthesis Example 4 were added to NMP (9.27 g), NEP (24.7 g) and PB (28.6 g). ) And stirred at 70 ° C. for 24 hours to obtain a composition (5).
  • this composition no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution.
  • this composition (5) was used for evaluation also as a liquid-crystal aligning agent (5).
  • Example 6 Polyimide powder (5) (2.00 g) and CE-2 (1.33 g) obtained by the synthesis method of Synthesis Example 5 were added to NMP (11.6 g), NEP (17.3 g) and PB (30.2 g). ) And stirred at 70 ° C. for 24 hours to obtain a composition (6). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (6) was used for evaluation also as a liquid-crystal aligning agent (6).
  • Example 7 Polyimide powder (5) (1.08 g) and CE-2 (0.72 g) obtained by the synthesis method of Synthesis Example 5 were added to NMP (11.7 g), NEP (17.6 g) and PB (30.0 g). ) And stirred at 70 ° C. for 24 hours to obtain a composition (7).
  • this composition no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution.
  • this composition (7) was used for evaluation also as a liquid-crystal aligning agent (7).
  • Example 8 Polyimide powder (5) (2.15 g) and CE-2 (0.92 g) obtained by the synthesis method of Synthesis Example 5 were added to ⁇ -BL (24.2 g), DEEE (11.7 g) and BCS (24 0.5 g) and stirred at 70 ° C. for 24 hours to obtain a composition (8).
  • this composition no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution.
  • this composition (8) was used for evaluation also as a liquid-crystal aligning agent (8).
  • composition (8) and the liquid crystal aligning agent (8) obtained, "Evaluation of transparency of resin film”, “Preparation of liquid crystal cell and evaluation of liquid crystal alignment (ordinary cell)” And “Evaluation of voltage holding ratio on insulating film coated substrate”.
  • NEP (35.9 g) and BCS (24.2 g) were added to polyimide powder (6) (2.83 g) and CE-1 (0.50 g) obtained by the synthesis method of Synthesis Example 6, and the mixture was heated to 70 ° C. The mixture was stirred for 24 hours to obtain a composition (9). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (9) was used for evaluation also as a liquid-crystal aligning agent (9).
  • Example 10 Polyimide powder (7) (1.89 g) and CE-2 (1.55 g) obtained by the synthesis method of Synthesis Example 7 were added to NEP (26.6 g), BCS (12.5 g) and PB (21.9 g). ) And stirred at 70 ° C. for 24 hours to obtain a composition (10). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (10) was used for evaluation also as a liquid-crystal aligning agent (10).
  • Example 11 Polyimide powder (8) (1.53 g) and CE-2 (1.87 g) obtained by the synthesis method of Synthesis Example 8 were added to NMP (14.5 g), NEP (14.5 g) and PB (30.9 g). ) And stirred at 70 ° C. for 24 hours to obtain a composition (11). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (11) was used for evaluation also as a liquid-crystal aligning agent (11).
  • Example 12 Polyimide powder (8) (1.88 g) and CE-2 (1.25 g) obtained by the synthesis method of Synthesis Example 8 were added to ⁇ -BL (24.7 g), PGME (17.8 g) and PB (18 8 g), and the mixture was stirred at 70 ° C. for 24 hours to obtain a composition (12). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (12) was used for evaluation also as a liquid-crystal aligning agent (12).
  • Example 13 ⁇ -BL (22.3 g) and PGME (39.4 g) were added to polyimide powder (8) (1.08 g) and CE-2 (0.75 g) obtained by the synthesis method of Synthesis Example 8, and 70 It stirred at 24 degreeC for 24 hours and obtained the composition (13). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (13) was used for evaluation also as a liquid-crystal aligning agent (13).
  • Example 14 Polyimide powder (9) (2.80 g) and CE-1 (0.70 g) obtained by the synthesis method of Synthesis Example 9 were added to NMP (35.0 g), DEEE (12.0 g) and BCS (15.9 g). ) And stirred at 70 ° C. for 24 hours to obtain a composition (14). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (14) was used for evaluation also as a liquid-crystal aligning agent (14).
  • composition (14) and liquid crystal aligning agent (14) “Evaluation of transparency of resin film”, “Preparation of liquid crystal cell and evaluation of liquid crystal alignment (ordinary cell)” And “Evaluation of voltage holding ratio on insulating film coated substrate”.
  • Example 15 Polyimide powder (10) (2.38 g) and CE-2 (1.02 g) obtained by the synthesis method of Synthesis Example 10 were added to NEP (26.8 g), BCS (24.7 g) and PB (9.27 g). ) And stirred at 70 ° C. for 24 hours to obtain a composition (15). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (15) was used for evaluation also as a liquid-crystal aligning agent (15).
  • Example 16 Polyimide powder (11) (2.45 g) and CE-2 (1.05 g) obtained by the synthesis method of Synthesis Example 11 were added to NEP (37.5 g), DEEE (6.02 g) and BCS (19.1 g). ) And stirred at 70 ° C. for 24 hours to obtain a composition (16). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (16) was used for evaluation also as a liquid-crystal aligning agent (16).
  • Example 17 The polyamic acid solution (12) (11.2 g) having a resin solid content concentration of 25% by mass obtained by the synthesis method of Synthesis Example 12 and CE-2 were mixed with NMP (26.3 g), BCS (12.8 g) and PB. (12.8 g) was added and stirred at 50 ° C. for 6 hours to obtain a composition (17). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (17) was used for evaluation also as a liquid-crystal aligning agent (17).
  • Example 18 Polyimide powder (13) (2.23 g) and CE-2 (1.20 g) obtained by the synthesis method of Synthesis Example 13 were added to NMP (30.8 g), PCS (14.7 g) and BCS (15.6 g). ) And stirred at 70 ° C. for 24 hours to obtain a composition (18). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (18) was used for evaluation also as a liquid-crystal aligning agent (18).
  • composition (21) and the liquid crystal aligning agent (21) obtained, "Evaluation of transparency of resin film”, “Preparation of liquid crystal cell and evaluation of liquid crystal alignment (ordinary cell)” And “Evaluation of voltage holding ratio on insulating film coated substrate”.
  • * 3 Indicates the proportion of the polymer in the composition (liquid crystal aligning agent).
  • * 4 Indicates the proportion of the polymer in the composition (liquid crystal aligning agent).
  • the composition of the example of the present invention obtained a resin film having higher transparency than the composition of the comparative example.
  • the composition using the specific cellulose polymer as the component (A) of the present invention and the specific cellulose system Comparison with a composition not using a polymer, that is, comparison between Example 1 and Comparative Example 1, comparison between Example 2 and Comparative Example 2, comparison between Example 3 and Comparative Example 3, and Example 6 And Comparison with Comparative Example 4.
  • the liquid crystal alignment treatment agent obtained from the composition of the present invention is more liquid crystal alignment treatment agent than the liquid crystal alignment treatment agent obtained from the composition of the comparative example. Even when light was irradiated in a state where there was an insulating film made of an organic member, a result with excellent voltage holding ratio was obtained (from evaluation of the voltage holding ratio on the insulating film coated substrate in Examples and Comparative Examples).
  • the composition using the specific cellulose polymer as the component (A) of the present invention and the specific cellulose system Comparison with a composition not using a polymer, that is, comparison between Example 1 and Comparative Example 1, comparison between Example 2 and Comparative Example 2, comparison between Example 3 and Comparative Example 3, and Example 6 And Comparison with Comparative Example 4. Furthermore, the result excellent in the said voltage retention was obtained also with the comparative example 5 which does not contain a specific polyimide-type polymer.
  • composition of the present invention has high transparency of the resin film, and can suppress decomposition of the resin film by light such as ultraviolet rays.
  • the liquid crystal aligning agent of the present invention becomes a liquid crystal alignment film having an excellent voltage holding ratio even when light is irradiated in a state where an insulating film made of an organic member is present under the liquid crystal alignment film.
  • the liquid crystal display element having the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention has excellent reliability, and can be suitably used for a large-screen, high-definition liquid crystal television, etc. It is useful for a device, a TFT liquid crystal device, particularly a vertical alignment type liquid crystal display device.
  • the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention is also useful for a liquid crystal display element that needs to be irradiated with ultraviolet rays when producing a liquid crystal display element. That is, a liquid crystal composition comprising a liquid crystal layer between a pair of substrates provided with electrodes, and containing a polymerizable compound that is polymerized by at least one of active energy rays and heat between the pair of substrates, A liquid crystal display element manufactured through a step of polymerizing the polymerizable compound while applying a voltage between the electrodes, and further comprising a liquid crystal layer between a pair of substrates provided with electrodes, A liquid crystal produced by placing a liquid crystal alignment film containing a polymerizable group that polymerizes at least one of active energy rays and heat between substrates and polymerizing the polymerizable group while applying a voltage between the electrodes. It is also useful for display elements.

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  • Chemical & Material Sciences (AREA)
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  • Medicinal Chemistry (AREA)
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  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
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Abstract

L'invention concerne un agent de traitement d'alignement de cristaux liquides contenant une composition qui contient au moins un type de polymère choisi parmi des polymères à base de cellulose de structure spécifique et des polyimides ou des précurseurs de polyimides obtenus par réaction d'un constituant diamine et d'un constituant acide tétracarboxylique.
PCT/JP2013/083230 2012-12-12 2013-12-11 Composition, agent de traitement d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides WO2014092126A1 (fr)

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JP2014552070A JP6299977B2 (ja) 2012-12-12 2013-12-11 液晶配向処理剤、液晶配向膜および液晶表示素子
KR1020157017643A KR102283305B1 (ko) 2012-12-12 2013-12-11 조성물, 액정 배향 처리제, 액정 배향막 및 액정 표시 소자
CN201380072403.0A CN104968722B (zh) 2012-12-12 2013-12-11 组合物、液晶取向处理剂、液晶取向膜和液晶显示元件

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JP2012271187 2012-12-12
JP2012-271187 2012-12-12

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WO2015012368A1 (fr) * 2013-07-25 2015-01-29 日産化学工業株式会社 Élément d'affichage à cristaux liquides, agent d'alignement de cristaux liquides, et film d'alignement de cristaux liquides
JP2016200698A (ja) * 2015-04-09 2016-12-01 Jsr株式会社 液晶表示素子、感放射線性樹脂組成物、層間絶縁膜、層間絶縁膜の製造方法および液晶表示素子の製造方法
JP2019133015A (ja) * 2018-01-31 2019-08-08 Jsr株式会社 液晶配向剤、液晶配向膜及び液晶素子
US11260635B2 (en) * 2017-02-13 2022-03-01 Tokyo Ohka Kogyo Co., Ltd. Resin composition, method for producing cured article, cured article, flexible substrate, and flexible display
TWI827467B (zh) * 2022-03-18 2023-12-21 日商日產化學股份有限公司 絕緣膜形成用感光性樹脂組成物

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WO2023149435A1 (fr) * 2022-02-03 2023-08-10 株式会社カネカ Composition de résine, objet moulé et film
CN117099046A (zh) * 2022-03-18 2023-11-21 日产化学株式会社 绝缘膜形成用感光性树脂组合物

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JP6299977B2 (ja) 2018-03-28
JP2018028694A (ja) 2018-02-22
JPWO2014092126A1 (ja) 2017-01-12
CN104968722B (zh) 2017-08-25
TW201439166A (zh) 2014-10-16
KR20150093735A (ko) 2015-08-18
CN104968722A (zh) 2015-10-07

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