WO2021070714A1 - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents
Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element Download PDFInfo
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- WO2021070714A1 WO2021070714A1 PCT/JP2020/037265 JP2020037265W WO2021070714A1 WO 2021070714 A1 WO2021070714 A1 WO 2021070714A1 JP 2020037265 W JP2020037265 W JP 2020037265W WO 2021070714 A1 WO2021070714 A1 WO 2021070714A1
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- 0 *C(CCc1ccccc1)=C Chemical compound *C(CCc1ccccc1)=C 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
- C09K19/56—Aligning agents
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
- C07C15/40—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals
- C07C15/50—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals polycyclic non-condensed
- C07C15/52—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals polycyclic non-condensed containing a group with formula
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/215—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring having unsaturation outside the six-membered aromatic rings
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
- C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
- C09K19/542—Macromolecular compounds
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- 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
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- 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
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- 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
- G02F1/1343—Electrodes
- G02F1/134309—Electrodes characterised by their geometrical arrangement
- G02F1/134363—Electrodes characterised by their geometrical arrangement for applying an electric field parallel to the substrate, i.e. in-plane switching [IPS]
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- 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
- G02F1/1343—Electrodes
- G02F1/134309—Electrodes characterised by their geometrical arrangement
- G02F1/134372—Electrodes characterised by their geometrical arrangement for fringe field switching [FFS] where the common electrode is not patterned
Definitions
- the present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film obtained from the liquid crystal alignment agent, a liquid crystal display element using the liquid crystal alignment film, and a novel compound used for the liquid crystal alignment agent.
- liquid crystal display element As a liquid crystal display element, various drive methods having different electrode structures and physical properties of liquid crystal molecules used have been developed. For example, TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, and VA (Vertical) have been developed. Various display elements such as Alignment type, IPS (In-Plane Switching) type, and FFS (Finge Field Switching) type are known. These liquid crystal display elements generally have a liquid crystal alignment film for orienting liquid crystal molecules.
- liquid crystal alignment film As a material for the liquid crystal alignment film, for example, polymers such as polyamic acid, polyamic acid ester, polyimide, and polyamide are known.
- polymers such as polyamic acid, polyamic acid ester, polyimide, and polyamide are known.
- the most widely used liquid crystal alignment film in industry is a film formed on an electrode substrate using a polymerizable composition containing the above polymer, and the surface of the film is unidirectionally covered with a cloth such as cotton, nylon, or polyester. It is manufactured by performing a so-called rubbing process of rubbing against.
- the rubbing process is a simple and highly productive industrially useful method.
- the surface of the alignment film generated by the rubbing process is scratched, dusted, affected by mechanical force or static electricity, and in-plane of the alignment process.
- There are various problems such as non-uniformity.
- Patent Document 1 proposes to use a polyimide film having an alicyclic structure such as a cyclobutane ring in the main chain for the photoalignment method.
- the above-mentioned photo-alignment method can be produced by an industrially simple manufacturing process as a rubbing-less alignment treatment method, and can be obtained by the rubbing treatment method for IPS-driven and FFS-driven liquid crystal display elements. Since it can be expected to improve the contrast and viewing angle characteristics of the liquid crystal display element as compared with the liquid crystal alignment film, it is attracting attention as a promising liquid crystal alignment processing method.
- liquid crystal display elements may be used for a long time in an environment of high temperature and high humidity or in an environment exposed to light irradiation.
- the liquid crystal alignment film is required to withstand use in such a harsh environment, and particularly high voltage retention is one of the important characteristics.
- the voltage retention rate tends to decrease in the case of the photo-alignment method in which a chemical change is caused by irradiation with radiation or the like.
- the liquid crystal orientation is not sufficient when the orientation ability is imparted by the photo-alignment method, and that seizure becomes a problem in, for example, IPS-driven or FFS-driven liquid crystal display elements. became.
- the present invention has a high voltage retention rate in a harsh environment, good liquid crystal orientation, and an IPS drive method even in the case of alignment treatment by a photoalignment method that causes a chemical change by irradiation with radiation or the like.
- An object of the present invention is to provide a novel compound used as a liquid crystal aligning agent.
- the present invention comprises a liquid crystal alignment agent containing two or more aromatic compounds having two or more structures represented by the following formula (1), a liquid crystal alignment film obtained from the liquid crystal alignment agent, and the liquid crystal alignment film. It is a liquid crystal display element having a liquid crystal display element, and further, a novel compound used for the liquid crystal alignment agent.
- R is a hydrogen atom or a methyl group.
- Any hydrogen atom on the benzene ring can be a hydroxy group, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a monovalent organic having 1 to 6 carbon atoms containing a fluorine atom. It may be substituted by a group.
- the voltage retention rate is high and the liquid crystal orientation is good even in the case of the orientation treatment by the photoalignment method in which a chemical change is caused by irradiation with radiation or the like, particularly in the IPS drive method and FFS.
- the liquid crystal alignment agent of the present invention is characterized by containing an aromatic compound having two or more structures represented by the following formula (1) (hereinafter, may be referred to as an aromatic compound of the formula (1)). To do.
- R in the above formula (1) represents a hydrogen atom or a methyl group.
- Any hydrogen atom on the benzene ring may be a hydroxy group, a halogen atom, an alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms.
- it may be substituted with a monovalent organic group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms having a fluorine atom.
- examples of the monovalent organic group having a fluorine atom include a trifluoromethyl group, a trifluoroethyl group, a trifluoromethoxy group, and a trifluoroethoxy group.
- liquid crystal alignment agent of the present invention by containing the aromatic compound of the above formula (1) as an additive, a photoalignment that causes a chemical change by irradiation with radiation or the like is caused as specifically illustrated in the examples described later. Even in the case of alignment treatment by the method, it is possible to obtain a liquid crystal alignment film in a liquid crystal display element having a high voltage retention rate and good liquid crystal alignment under a harsh environment.
- the mechanism is not always clear, but it can be considered as follows.
- the alignment treatment by the photo-alignment method for example, the surface of a film-like material formed from a liquid crystal alignment agent formed on the surface of a substrate is irradiated with high-energy UV light polarized in a substantially linear manner.
- the liquid crystal alignment agent of the present invention when the impurities are generated by irradiation with UV light, the aromatic compound of the above formula (1) has a functional group capable of reacting with the impurities, which lowers the voltage retention rate. By reacting with the impurities that bring about the above, the impurities contained in the obtained liquid crystal alignment film can be reduced. Therefore, the liquid crystal alignment film obtained from the liquid crystal alignment agent of the present invention is considered to maintain a high voltage retention rate.
- the aromatic compound of the above formula (1) contained in the liquid crystal alignment agent of the present invention has a highly flat structure, the liquid crystal orientation of the obtained liquid crystal alignment film is not hindered and the liquid crystal is high. It is considered that a liquid crystal alignment film having orientation can be obtained. Therefore, in the IPS drive method and the FFS drive method, even when the liquid crystal display element is driven for a long time, the liquid crystal returns to the same state as before the drive, so that it is considered that a liquid crystal display element with less seizure can be obtained.
- the aromatic compound of the above formula (1) is preferably a compound represented by the following formula (b1).
- R has the same meaning as in the above formula (1).
- n is an integer of 2 to 6, and when n is 2, A represents a single bond or a divalent linking group, and when n is 3 to 6, A represents an n-valent organic group.
- n-valent organic group examples include an n-valent hydrocarbon group, an n-valent heteroatom-containing group containing a group having a heteroatom between carbons of the hydrocarbon group or at the end of the hydrocarbon group, and the above-mentioned carbonization.
- examples thereof include an n-valent organic group in which a part or all of the hydrogen atoms of the hydrogen group and the heteroatom-containing group are substituted with a substituent.
- the divalent linking group in A includes a divalent hydrocarbon group, a divalent heteroatom-containing group containing a group having a heteroatom between carbons of the hydrocarbon group or at the end of the hydrocarbon group, and the above-mentioned carbonization.
- a divalent linking group in which some or all of the hydrogen atoms of the hydrogen group and the heteroatom-containing group are substituted with a substituent, -S ( O) 2- , -CO-, -O-, -S-,- NR-CO- (R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -NR-CO-NR- (R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), etc. Can be mentioned.
- n-valent hydrocarbon group examples include alkanes such as methane, ethane, propane and butane; alkens such as ethylene, propylene, butylene and penten; and 1 to 30 carbon atoms such as alkins such as ethine, propine, butine and pentin.
- Aromatic hydrocarbons having 6 to 30 carbon atoms such as hydrogen, benzene, toluene, xylene, mesityrene, naphthalene, methylnaphthalene, dimethylnaphthalene, and anthracene, and some of the carbon-carbon bonds of the chain hydrocarbons are the above fats.
- Examples thereof include n-valent groups obtained by removing n hydrogen atoms from a hydrocarbon selected from the group consisting of cyclic hydrocarbons and hydrocarbons replaced with the above aromatic hydrocarbons.
- Examples of the divalent hydrocarbon group include a divalent group obtained by removing two hydrogen atoms from the hydrocarbon exemplified in the above n-valent hydrocarbon group.
- Examples of the group having the hetero atom include a group having at least one selected from the group consisting of an oxygen atom, a nitrogen atom, a silicon atom, a phosphorus atom and a sulfur atom.
- Specific examples include -O-, -NR- (R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -CO-, -S-, -CO-, and a group combining these. And so on. Of these, —O— is preferable.
- substituents include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy group such as methoxy group, ethoxy group and propoxy group; alkoxycarbonyl group such as methoxycarbonyl group and ethoxycarbonyl group; methoxy. Alkoxycarbonyloxy groups such as carbonyloxy group and ethoxycarbonyloxy group; cyano group, nitro group and the like can be mentioned.
- n is preferably 2 and A is preferably a single bond or a divalent linking group.
- the divalent linking group preferably has a structure represented by the following formula (a-1) or (a-2).
- the formula (a-1), in (a-2), R 1 , R 1 ', R 2, R 2' are independently a hydrogen atom or a C 1-4, preferably or 1 carbon atoms 2
- m1 and m2 are independently integers of 1 to 18, preferably 1 to 6.
- n is an integer of 1 to 6, preferably 1 to 4.
- "*" represents a bond.
- the aromatic compound of the above formula (1) has a molecular weight of preferably 2000 or less, more preferably 1500 or less, from the viewpoint of enhancing the reactivity with the decomposition products generated by the photoalignment method. ..
- the molecular weight of the aromatic compound is preferably 150 or more, more preferably 200 or more, from the viewpoint of suppressing sublimation of the aromatic compound by firing.
- Preferred examples of the aromatic compound of the above formula (1) include compounds selected from the group consisting of the following formulas (b-1) to (b-7).
- the compounds of the following formulas (b-1) to (b-4) are novel compounds not disclosed in the prior art.
- the liquid crystal aligning agent of the present invention containing the aromatic compound of the above formula (1) contains a polymer having an ability to orient the liquid crystal as in the known one, but such a polymer orients the liquid crystal. It is not particularly limited as long as it has the ability to make it.
- polymers include polyimide precursors, polyimides which are imidized polyimide precursors, acrylic polymers, methacrylic polymers, acrylamide polymers, methacrylicamide polymers, polystyrenes, polysiloxanes, polyamides, polyesters, polyurethanes, polycarbonates, and polyureas. , Polyphenol (Novolak resin), Maleimide polymer, Isocyanuric acid skeleton, Triazine skeleton-introduced polymer. Such a polymer can be used alone or in combination of two or more.
- raw materials for producing these polymers include the following.
- the polymer is a polyimide precursor such as polyamic acid or polyamic acid ester or polyimide, at least one tetracarboxylic acid component selected from tetracarboxylic acid or a derivative thereof and diamine; If the polymer is a (meth) acrylic polymer, (meth) acrylic acid or a derivative thereof, (meth) acrylic acid ester or a derivative thereof; if the polymer is a (meth) acrylamide polymer, (meth) acrylamide or a derivative thereof. ;
- the polymer is polystyrene, styrene or a derivative thereof; when the polymer is polysiloxane, a silane compound having a methoxy group or an ethoxy group; when the polymer is polyamide, at least selected from a dicarboxylic acid and a derivative thereof.
- the polymer is polyester, at least one dicarboxylic acid component and diol component selected from dicarboxylic acid and its derivatives;
- the polymer When the polymer is polyurethane, it is a compound having isocyanate, compound and hydroxyl group; when the polymer is polycarnate, it is a bisphenol derivative and phosgene or phosgene equivalent (for example, trichlorophosgene) or diphenyl carbonate; When the polymer is polyurea, the bisisocyanate derivative and the diamine component; when the polymer is a maleimide polymer, the maleimide derivative alone or copolymerization with styrene; In the case of a polymer into which a compound having an isocyanuric acid skeleton or a triazine skeleton is introduced, a compound having an isocyanuric acid skeleton or a triazine skeleton.
- the polymers contained in the liquid crystal aligning agent of the present invention include, among others, a polyimide precursor and an imide of the polyimide precursor from the viewpoint of practicality as a liquid crystal aligning agent, mechanical and electrical characteristics of a coating film.
- a polyimide precursor and an imide of the polyimide precursor from the viewpoint of practicality as a liquid crystal aligning agent, mechanical and electrical characteristics of a coating film.
- One or more polymers (hereinafter, also referred to as polyimide-based polymers) selected from the group consisting of polyimides as compounds are preferable.
- the polyimide-based polymer can be produced by a known method.
- polyamic acid which is a polyimide precursor
- polyimide precursor is obtained by subjecting a tetracarboxylic acid component composed of a tetracarboxylic dianhydride or a derivative thereof and a diamine component to a polycondensation reaction, and this polyimide precursor is used.
- Polyimide can be obtained by imidization.
- the polyamic acid as a polyimide precursor examples include those obtained from a tetracarboxylic acid component containing an aromatic, aliphatic or alicyclic tetracarboxylic dianhydride.
- the aromatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxyl groups including at least one carboxyl group bonded to the aromatic ring.
- the aliphatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxyl groups bonded to a chain hydrocarbon structure. However, it does not have to be composed of only a chain hydrocarbon structure, and a part thereof may have an alicyclic structure or an aromatic ring structure.
- the alicyclic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxyl groups including at least one carboxyl group bonded to the alicyclic structure. However, none of these four carboxyl groups are bonded to the aromatic ring. Further, it is not necessary to have only an alicyclic structure, and a chain hydrocarbon structure or an aromatic ring structure may be partially provided.
- the polyamic acid of the present invention is preferably one obtained from a tetracarboxylic acid component containing a tetracarboxylic dianhydride represented by the following formula (2).
- X is preferably a structure selected from the following (x-1) to (x-13).
- R 1 to R 4 are independently hydrogen atoms, halogen atoms, alkyl groups having 1 to 6 carbon atoms, and alkenyl groups having 2 to 6 carbon atoms, respectively.
- R 5 and R 6 each independently represent a hydrogen atom or a methyl group.
- j and k are independently integers of 0 or 1.
- a 1 and A 2 independently represent single bonds, -O-, -CO-, -COO-, phenylene, -SO 2- , or -CONH-, respectively.
- Two A 2 may be the same or different.
- * 1 is a bond that binds to one acid anhydride group
- * 2 is a bond that binds to the other acid anhydride group.
- the above formula (x-1) is preferably selected from the group consisting of the following formulas (x1-1) to (x1-6).
- * 1 represents a bond that binds to one acid anhydride group
- * 2 represents a bond that binds to the other acid anhydride group. ..
- Preferred specific examples of the above formulas (x-12) and (x-13) include the following formulas (x-14) to (x-29).
- "*" in the formula represents a coupling position.
- the amount of the tetracarboxylic dianhydride or its derivative represented by the above formula (2) is preferably 60 to 100 mol% with respect to 1 mol of the total tetracarboxylic acid component to be reacted with the diamine component, and is 80. More preferably ⁇ 100 mol%, still more preferably 90-100 mol%.
- the diamine component used for producing the polyimide precursor is not particularly limited, but a diamine component containing a diamine represented by the following formula (3) is preferable.
- a 1 is an alkylene group having 2 to 14 carbon atoms, or -O-, -CO-, -OCO- or-under the condition that at least one of -CH 2- possessed by the alkylene is not continuous.
- a 1 is more preferably -O-, -CO-, -OCO- or -COO- under the condition that at least one of the alkylene group having 2 to 12 carbon atoms or -CH 2- possessed by the alkylene is not continuous.
- a 2 represents a halogen atom, a hydroxy group, an amino group, a thiol group, a nitro group, a phosphoric acid group, or a monovalent organic group having 1 to 20 carbon atoms.
- a 2 may be the same or different.
- a is an integer of 0 to 4, and when a plurality of a exist, a may be the same or different.
- b and c are independently integers of 1 or 2
- d is an integer of 0 or 1.
- the diamine represented by the above formula (3) the diamine represented by the following formulas (3d-1) to (3d-9) is preferable. (In equations (3d-8) and (3d-9), the two m's may be the same or different.)
- the diamine represented by the above formula (3) the diamine represented by the following formulas (3-1) to (3-12) is more preferable.
- the amount of the diamine represented by the above formula (3) is preferably 60 to 100 mol%, more preferably 80 to 100 mol%, based on 1 mol of the total diamine component to be reacted with the tetracarboxylic acid component. 90-100 mol% is more preferred.
- the polyimide-based polymer used in the present invention has a nitrogen-containing heterocycle (excluding the imide ring of the polyimide), a secondary amino group, and a third, from the viewpoint of increasing the voltage retention of the obtained liquid crystal alignment film. It may have at least one nitrogen-containing structure (hereinafter, also referred to as a nitrogen-containing structure) selected from the group consisting of primary amino groups.
- a polyimide-based polymer having a nitrogen-containing structure can be obtained by using a monomer having a nitrogen-containing structure, for example, a diamine having a nitrogen-containing structure as at least a part of a raw material.
- nitrogen-containing heterocycle examples include pyrrole, imidazole, pyrazole, triazole, pyridine, pyrimidine, pyridazine, pyrazine, indol, benzoimidazole, purine, quinoline, isoquinoline, naphthylidine, quinoxaline, phthalazine, triazine, carbazole, aclysine and piperidine.
- the secondary amino group and the tertiary amino group that the diamine having a nitrogen-containing structure may have are represented by, for example, the following formula (n).
- R represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
- "*" Represents a bond that binds to a hydrocarbon group.
- Examples of the monovalent hydrocarbon group of R in the above formula (n) include an alkyl group such as a methyl group, an ethyl group and a propyl group; a cycloalkyl group such as a cyclohexyl group; and an aryl such as a phenyl group and a methylphenyl group. Examples include containing groups.
- R is preferably a hydrogen atom or a methyl group.
- amine having a nitrogen-containing structure examples include 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminocarbazole, and N-methyl-3,6-.
- the ratio of diamine having a nitrogen-containing structure is preferably 1 mol% or more, more preferably 2 mol% or more, based on the total amount of diamine used for synthesis, from the viewpoint of increasing the voltage holding ratio of the liquid crystal display element.
- the usage ratio is preferably 90 mol% or less, more preferably 80 mol% or less.
- the polyimide-based polymer used in the present invention may contain other diamines other than the diamines described above. Examples of other diamines are given below, but the present invention is not limited thereto.
- Diamine having a urea bond a diamine having an amide bond such as a diamine represented by the following formulas (u-4) to (u-7), 2- (2,4-diaminophenoxy) ethyl methacrylate, 2,4 Diamines having photopolymerizable groups such as -diamino-N, N-diallylaniline at the ends, cholestanyloxy-3,5-diaminobenzene, cholestenyloxy-3,5-diaminobenzene, cholestanyloxy-2,4 It has a steroid skeleton such as -diaminobenzene, cholestanyl 3,5-diaminobenzoate, cholestenyl 3,5-diaminobenzoate, lanostanyl 3,5-diaminobenzoate, and 3,6-bis (4-aminobenzoyloxy) cholesterol.
- X v1 to X v4 and X p1 to X p2 are independently ⁇ (CH 2 ) a ⁇ (a is an integer of 1 to 15).
- X v5 represents -O-, -CH 2 O-, -CH 2 OCO-, -COO-, or -OCO-.
- Xa is single bond, -O-, -NH-, -O- (CH 2).
- R v1 to R v4 and R 1a to R 1b independently indicate an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkoxyalkyl group having 2 to 20 carbon atoms.
- a diamine having a siloxane bond such as 1,3-bis (3-aminopropyl) -tetramethyldisiloxane, and a group "-N (D)-" (D) such as the following formulas (5-1) to (5-11).
- a radical polymerization initiator function such as 5-diaminobenzoate, 4,4-diaminobenzophenone, and 3,4'-diaminobenzophenone.
- the polyamic acid which is a polyimide precursor used in the present invention, can be produced by the following method. Specifically, the tetracarboxylic acid component and the diamine component are mixed in the presence of an organic solvent at ⁇ 20 to 150 ° C., preferably 0 to 50 ° C. for 30 minutes to 24 hours, preferably 1 to 12 hours (heavy). It can be synthesized by reacting (condensation).
- the organic solvent used in the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, or ⁇ -butyrolactone because of the solubility of the monomer and the polymer, and these may be used in combination of two or more. Good.
- the concentration of the polymer is preferably 1 to 30% by mass, more preferably 5 to 20% by mass, from the viewpoint that precipitation of the polymer is unlikely to occur and a high molecular weight polymer is easily obtained.
- the polyamic acid obtained in the above reaction can be recovered by precipitating the polyamic acid by injecting the reaction solution into a poor solvent while stirring well. Further, the purified polyamic acid powder can be obtained by performing precipitation several times, washing with a poor solvent, and then drying at room temperature or by heating.
- the poor solvent is not particularly limited, and examples thereof include water, methanol, ethanol, hexane, butyl cellosolve, acetone, and toluene.
- the polyimide precursor is a polyamic acid ester
- the polyimide precursor may be an end-sealing polymer obtained by using an appropriate end-capping agent together with the tetracarboxylic acid derivative and diamine as described above when producing the polyimide precursor.
- the terminal encapsulant include acid monoanhydrides such as maleic anhydride, nadic acid anhydride, phthalic anhydride, itaconic anhydride, cyclohexanedicarboxylic acid anhydride, 3-hydroxyphthalic anhydride, and trimetic acid anhydride.
- Di-tert-butyl carbonate Di-tert-butyl carbonate; aniline, 2-aminophenol, 3-aminophenol, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid
- Monoamine compounds such as acids; monoisocyanate compounds such as ethyl isocyanate, phenylisocyanate and naphthylisocyanate can be mentioned.
- the proportion of the end-capping agent used is preferably 40 mol parts or less, and more preferably 30 mol parts or less, based on 100 mol parts of the total diamine component used.
- the polyimide used in the present invention can be produced by imidizing a polyamic acid or a polyamic acid ester, which is a polyimide precursor, by a known method.
- a catalyst to the solution of the polyamic acid obtained by the reaction of the diamine component and the tetracarboxylic acid component (chemical).
- Imidization can be carried out by stirring the polymer to be imidized in an organic solvent in the presence of a basic catalyst and an acid anhydride.
- the solvent used in the above-mentioned polymerization reaction can be used.
- the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Among them, pyridine is preferable because it has an appropriate basicity for advancing the reaction.
- the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride and the like. Among them, acetic anhydride is preferable because it facilitates purification after the reaction is completed.
- the temperature at which the imidization reaction is carried out is ⁇ 20 to 140 ° C., preferably 0 to 100 ° C., and the reaction time can be 1 to 100 hours.
- the amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times, that of the amic acid group, and the amount of acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol times that of the amic acid group. It is double.
- the imidization rate of the obtained polymer can be controlled by adjusting the amount of catalyst, the temperature, and the reaction time.
- the imidization rate as used herein is the ratio of the imide group to the total amount of the imide group derived from the tetracarboxylic dianhydride or its derivative and the carboxyl group (or its derivative).
- the imidization ratio does not necessarily have to be 100%, and can be arbitrarily adjusted according to the application and purpose.
- the imidization ratio of the polyimide used in the present invention is preferably 20 to 100%, more preferably 50 to 99%.
- the polyimide solution obtained as described above can be injected into a poor solvent with stirring to precipitate a polymer. Precipitation is carried out several times, and after washing with a poor solvent, a purified polyimide powder can be obtained at room temperature or by heating and drying.
- the poor solvent is not particularly limited, and examples thereof include methanol, acetone, hexane, butyl cellsolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, and benzene.
- the molecular weight of the polyimide precursor and the polyimide produced as described above is preferably 2,000 to 500,000, more preferably 5,000 to 300,000, and further preferably 10,000 in terms of weight average molecular weight. ⁇ 100,000.
- the number average molecular weight is preferably 1,000 to 250,000, more preferably 2,500 to 150,000, and even more preferably 5,000 to 50,000.
- the liquid crystal alignment agent of the present invention has a form in which the aromatic compound of the above formula (1) is added to a solution in which a polymer having the ability to orient the liquid crystal is dissolved in a solvent.
- the content (concentration) of the polymer contained in the liquid crystal aligning agent of the present invention can be appropriately changed by setting the thickness of the coating film to be formed, but the point is that a uniform and defect-free coating film is formed. From the viewpoint of storage stability of the solution, it is preferably 10% by mass or less.
- the content (concentration) of the aromatic compound of the above formula (1) added to the liquid crystal alignment agent of the present invention is preferably 0.1 to 5% by mass, preferably 0.15 to 5% by mass.
- the content of the aromatic compound of the above formula (1) is such that the total content of the polymer contained in the liquid crystal alignment agent and the aromatic compound of the above formula (1) is 1 to 15% by mass. It is preferably present, more preferably 2 to 10% by mass, and particularly preferably 2 to 8% by mass.
- the solvent used for the liquid crystal alignment agent of the present invention is not particularly limited as long as it is a solvent that dissolves the aromatic compound of the above formula (1) and the above polymer. Specific examples are given below. For example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, ⁇ -butyrolactone, 1,3-dimethyl-2-imidazolidinone.
- 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 is an alkyl group having 1 to 4 carbon atoms).
- the solvent in the present invention is, among others, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, ⁇ -butyrolactone, 3-methoxy-N, N-dimethylpropanamide, or 1,3-dimethyl-2-. Imidazolidinone (hereinafter, these are also referred to as good solvents) is preferable.
- the liquid crystal alignment agent of the present invention can contain a solvent (also referred to as a poor solvent) that improves the coating film property and surface smoothness of the liquid crystal alignment film when the liquid crystal alignment agent is applied.
- a solvent also referred to as a poor solvent
- These poor solvents are preferably 1 to 80% by mass of the total solvent contained in the liquid crystal alignment agent. Of these, 10 to 80% by mass is preferable. More preferably, it is 20 to 70% by mass.
- butyl cellosolve 1-butoxy-2-propanol
- butyl cellosolve acetate dipropylene glycol monomethyl ether, diacetone alcohol, diethylene glycol diethyl ether, diisopentyl ether, propylene glycol diacetate, diisobutyl ketone, ethyl carbitol or di
- propylene glycol dimethyl ether it is preferable to use propylene glycol dimethyl ether.
- the liquid crystal alignment agent of the present invention contains at least one substituent selected from the group consisting of a crosslinkable compound having an epoxy group, an isocyanate group, an oxetanyl group or a cyclocarbonate group, a hydroxy group, a hydroxyalkyl group and a lower alkoxyalkyl group.
- a crosslinkable compound having a polymerizable unsaturated bond or a crosslinkable compound having a polymerizable unsaturated bond (excluding the aromatic compound of the formula (1)) may be contained. It is preferable that the crosslinkable compound has two or more of these substituents and polymerizable unsaturated bonds. Two or more kinds of crosslinkable compounds may be combined.
- the preferable crosslinkable compound include compounds represented by the following formulas (CL-1) to (CL-11).
- the content of the crosslinkable compound in the liquid crystal aligning agent of the present invention is preferably 0.1 to 150 parts by mass, more preferably 0.1 to 100 parts by mass, based on 100 parts by mass of all the polymers.
- the liquid crystal alignment agent of the present invention can contain a compound that improves the thickness uniformity and surface smoothness of the film-like material obtained by applying the liquid crystal alignment agent.
- a compound that improves the thickness uniformity and surface smoothness of the film-like material obtained by applying the liquid crystal alignment agent examples include a fluorine-based surfactant, a silicone-based surfactant, and a nonion-based surfactant.
- Ftop EF301, EF303, EF352 (above, manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd.), Megafuck F171, F173, R-30 (above, manufactured by DIC Corporation), Florard FC430, FC431 (above, 3M Ltd.), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (all manufactured by AGC Corporation) and the like.
- liquid crystal alignment agent as a compound that promotes charge transfer in the liquid crystal alignment film and promotes charge removal of the element, [0194] to [0194] of International Publication No. WO2011 / 132751 (published 2011.10.27). 0200], nitrogen-containing heterocyclic amines represented by the formulas [M1] to [M156] can also be added.
- This amine may be added directly to the liquid crystal alignment agent, but it is preferably added after making a solution having a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass.
- This solvent is not particularly limited as long as it dissolves the specific polymer.
- the liquid crystal alignment film of the present invention is a film obtained by applying the above liquid crystal alignment agent to a substrate, drying and firing.
- the substrate is not particularly limited as long as it is a highly transparent substrate, and examples thereof include a glass substrate, a silicon nitride substrate, a plastic substrate such as an acrylic substrate and a polycarbonate substrate, and the like.
- a substrate on which an ITO electrode or the like for driving a liquid crystal is formed is preferable from the viewpoint of simplifying the process.
- an opaque object such as a silicon wafer can be used if only one substrate is used, and a material that reflects light such as aluminum can also be used for the electrode in this case.
- Examples of the method of applying the liquid crystal alignment agent to the substrate to form a film include screen printing, offset printing, flexographic printing, an inkjet method, a spray method, and the like. Of these, the coating and film forming methods by the inkjet method can be preferably used.
- the solvent can be evaporated to form a film (film) by a heating means such as a hot plate, a heat circulation type oven, or an IR (infrared) type oven. Any temperature and time can be selected for the drying and firing steps after applying the liquid crystal alignment agent. Usually, it may be calcined at 50 to 180 ° C.
- the film-like material after firing is too thin, the reliability of the liquid crystal display element may decrease, so 5 to 300 nm is preferable, and 10 to 200 nm is more preferable.
- a rubbing treatment method may be used, but a photoalignment treatment method is preferable.
- a photo-alignment treatment method the surface of the film-like material is irradiated with radiation deflected in a certain direction, and in some cases, it is fired at a temperature of 150 to 250 ° C. to achieve liquid crystal orientation (liquid crystal alignment ability).
- the radiation ultraviolet rays having a wavelength of 100 to 800 nm or visible light can be used. Among them, ultraviolet rays having a wavelength of preferably 100 to 400 nm, more preferably 200 to 400 nm.
- the substrate having the film-like substance may be irradiated while being heated at 50 to 250 ° C.
- the irradiation amount of the above radiation is preferably 1 to 10,000 mJ / cm 2. Of these, 100 to 5,000 mJ / cm 2 is preferable.
- the liquid crystal alignment film thus produced can stably orient liquid crystal molecules in a certain direction.
- the liquid crystal alignment film irradiated with polarized radiation can be treated with water or a solvent, or the liquid crystal alignment film irradiated with radiation can be heat-treated.
- the solvent used for the contact treatment is not particularly limited as long as it is a solvent that dissolves the decomposition product generated from the film-like material by irradiation with radiation.
- Specific examples include water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, methyl lactate, diacetone alcohol, 3-.
- Examples thereof include methyl methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate, cyclohexyl acetate and the like.
- water, 2-propanol, 1-methoxy-2-propanol or ethyl lactate are preferable from the viewpoint of versatility and solvent safety. More preferred are water, 1-methoxy-2-propanol or ethyl lactate.
- the solvent may be used alone or in combination of two or more.
- Examples of the above contact treatment include immersion treatment and spray treatment (also referred to as spray treatment).
- the treatment time in these treatments is preferably 10 seconds to 1 hour from the viewpoint of efficiently dissolving the decomposition products generated from the film-like material by irradiation with radiation. Above all, it is preferable to carry out the immersion treatment for 1 to 30 minutes. Further, the solvent at the time of the contact treatment may be heated at room temperature, but is preferably 10 to 80 ° C. Of these, 20 to 50 ° C. is preferable. In addition, from the viewpoint of solubility of the decomposed product, ultrasonic treatment or the like may be performed as necessary.
- rinsing also referred to as rinsing
- firing temperature is preferably 150 to 300 ° C. Of these, 180 to 250 ° C. is preferable. More preferably, it is 200 to 230 ° C.
- the firing time is preferably 10 seconds to 30 minutes. Of these, 1 to 10 minutes is preferable.
- the heat treatment of the above-mentioned radiation-irradiated coating film is more preferably 50 to 300 ° C. for 1 to 30 minutes, and further preferably 120 to 250 ° C. for 1 to 30 minutes.
- the liquid crystal alignment film of the present invention is suitable as a liquid crystal alignment film for a transverse electric field type liquid crystal display element such as an IPS system or an FFS system from the viewpoint of obtaining high liquid crystal alignment, and is particularly suitable for an FFS type liquid crystal display element. It is useful as a liquid crystal alignment film.
- the liquid crystal display element is obtained by obtaining a substrate with a liquid crystal alignment film obtained from the liquid crystal alignment agent of the present invention, then producing a liquid crystal cell by a known method, and using the liquid crystal cell.
- a liquid crystal display element having a passive matrix structure will be described as an example.
- a liquid crystal display element having an active matrix structure in which a switching element such as a TFT (Thin Film Transistor) is provided in each pixel portion constituting the image display may be used.
- a transparent glass substrate is prepared, and a common electrode is provided on one substrate and a segment electrode is provided on the other substrate.
- These electrodes can be, for example, ITO electrodes and are patterned so as to display a desired image.
- an insulating film is provided on each substrate so as to cover the common electrode and the segment electrode.
- the insulating film can be, for example, a film of SiO 2- TiO 2 formed by the sol-gel method.
- a liquid crystal alignment film is formed on each substrate, the other substrate is overlapped on one substrate so that the liquid crystal alignment film surfaces face each other, and the periphery is bonded with a sealant.
- a spacer is usually mixed in the sealant in order to control the substrate gap, and that the spacer for controlling the substrate gap is also sprayed on the in-plane portion where the sealant is not provided.
- a part of the sealing agent is provided with an opening in which the liquid crystal can be filled from the outside.
- the liquid crystal material is injected into the space surrounded by the two substrates and the sealant through the opening provided in the sealant, and then the opening is sealed with an adhesive.
- a vacuum injection method may be used, or a method utilizing a capillary phenomenon in the atmosphere may be used.
- the liquid crystal material either a positive type liquid crystal material or a negative type liquid crystal material may be used, but a negative type liquid crystal material is preferable.
- the polarizing plate is installed. Specifically, a pair of polarizing plates are attached to the surfaces of the two substrates opposite to the liquid crystal layer.
- T-1 to T-4 are novel compounds that have not been published in the literature, and the synthesis method will be described in detail in Synthesis Examples 1 to 4 below.
- reaction solution was poured into ethyl acetate (1000 g), neutralized with 1N-hydrochloric acid aqueous solution (1000 g), and washed with pure water (1000 g).
- the obtained organic layer was concentrated, and the obtained crude product was isolated by silica gel column chromatography (eluent: hexane only) to obtain 4.7 g of a white solid. From the results of 1 H-NMR shown below, it was confirmed that this solid was [T-1].
- GPC apparatus Shodex (GPC-101), column: Shodex (series of KD803 and KD805), column temperature: 50 ° C., eluent: N, N-dimethylformamide (lithium bromide-water as an additive) Japanese product (LiBr ⁇ H 2 O) 30 mmol / L, phosphoric acid / anhydrous crystal (o-phosphoric acid) 30 mmol / L, tetrahydrofuran (THF) 10 ml / L), flow velocity: 1.0 ml / min Standard samples for use: TSK standard polyethylene oxide manufactured by Toso (weight average molecular weight (Mw) about 900,000, 150,000, 100,000, 30,000) and polyethylene glycol manufactured by Polymer Laboratory (peak top molecular weight (Mp)).
- Mw weight average molecular weight
- Mp peak top molecular weight
- FT-NMR Fourier transform infrared magnetic resonance apparatus
- Example 1 The polyimide solution (A) (3.80 g) obtained in Synthesis Example 8 and the polyamic acid solution (B) (4.56 g) obtained in Synthesis Example 6 were weighed into a 100 mL Erlenmeyer flask, and T-1 (0. 114 g), NMP (1.64 g), GBL (6.00 g), and BCS (4.00 g) were added and stirred at room temperature for 3 hours to obtain a liquid crystal aligning agent (1). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment agent, and it was confirmed that the solution was uniform.
- Example 2 to 5 Liquid crystal alignment agents (2) of Examples 2 to 5 in the same manner as in Example 1 except that T-2, T-3, T-4, or T-5 was used instead of T-1, respectively. ⁇ (5) was obtained. It was confirmed that all of these liquid crystal alignment agents (2) to (5) were uniform solutions without any abnormalities such as turbidity and precipitation.
- Comparative Example 2 A liquid crystal alignment agent (7) was obtained by the same method as in Example 1 except that T-6 was used instead of T-1.
- the liquid crystal alignment agents (6) and (7) obtained in Comparative Examples 1 and 2 did not show any abnormalities such as turbidity and precipitation, and it was confirmed that they were uniform solutions.
- Example 6 The liquid crystal alignment agent (1) obtained in Example 1 was filtered through a filter having a pore size of 1.0 ⁇ m, and then coated on a glass substrate with a transparent electrode by a spin coating method. Dried for 2 minutes at 80 ° C. on a hot plate, the extinction ratio 26 via a polarizing plate coated surface: After the first ultraviolet rays linearly polarized wavelength 254nm was irradiated 0.25 J / cm 2, the hot air circulation 230 ° C. It was baked in a formula oven for 20 minutes to obtain a substrate with a liquid crystal alignment film having a film thickness of 100 nm.
- the two obtained substrates were combined into a set, and a spacer having a diameter of 6 ⁇ m was sprayed on the liquid crystal alignment film surface of one of the substrates.
- a sealant was printed on this substrate, and another substrate was bonded so that the liquid crystal alignment film surfaces faced each other and the orientation direction was 0 °, and then the sealant was cured to prepare an empty cell.
- a liquid crystal MLC-7026-100 manufactured by Merck & Co., Inc.
- no flow orientation was confirmed, and the orientation was good.
- This cell was heat-treated at 120 ° C. for 60 minutes to prepare a liquid crystal cell.
- Examples 7 to 10, Comparative Examples 3 to 4 Liquid crystal cells were prepared in the same manner as in Example 6 except that the liquid crystal alignment agents shown in Table 1 were used instead of the liquid crystal alignment agent (1), and the liquid crystal orientation and voltage retention were evaluated. Carried out. Table 1 shows the liquid crystal orientation and voltage retention of the obtained liquid crystal cells.
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Abstract
Description
本発明は、下記式(1)で表される構造を2つ以上有する芳香族化合物を含有することを特徴とする液晶配向剤、該液晶配向剤から得られる液晶配向膜、該液晶配向膜を有する液晶表示素子、更には、該液晶配向剤に用いる新規化合物にある。
The present invention comprises a liquid crystal alignment agent containing two or more aromatic compounds having two or more structures represented by the following formula (1), a liquid crystal alignment film obtained from the liquid crystal alignment agent, and the liquid crystal alignment film. It is a liquid crystal display element having a liquid crystal display element, and further, a novel compound used for the liquid crystal alignment agent.
本発明の液晶配向剤は、下記式(1)で表される構造を2つ以上有する芳香族化合物(以下、式(1)の芳香族化合物という場合がある。)を含有することを特徴とする。
The liquid crystal alignment agent of the present invention is characterized by containing an aromatic compound having two or more structures represented by the following formula (1) (hereinafter, may be referred to as an aromatic compound of the formula (1)). To do.
光配向法による配向処理では、例えば、基板表面に形成された液晶配向剤から形成される膜状物の表面には、ほぼ直線に偏光した高エネルギーUV光が照射されるが、この場合、UV光の照射により、膜状物を構成する有機物の分解物が生成し、これが液晶配向膜中の電圧保持率の低下をもたらす不純物となり、このため、液晶配向膜の電圧保持率を低下させるものと思われる。
しかし、本発明の液晶配向剤では、UV光の照射によって上記不純物が生成した場合、該不純物と反応しうる官能基を上記式(1)の芳香族化合物が有するため、これが電圧保持率の低下をもたらす不純物と反応することにより、得られる液晶配向膜に含まれる該不純物を低減せしめることができる。このため、本発明の液晶配向剤から得られる液晶配向膜は、高い電圧保持率を保持するものと思われる。
また、本発明の液晶配向剤に含有される上記式(1)の芳香族化合物は、平面性の高い構造を有するため、得られる液晶配向膜の液晶配向性が阻害されることなく、高い液晶配向性を有する液晶配向膜が得られるものと思われる。従って、IPS駆動方式やFFS駆動方式において、液晶表示素子を長時間駆動させた際でも液晶が駆動前と同じ状態に戻るため、焼き付きの少ない液晶表示素子が得られるものと思われる。 In the liquid crystal alignment agent of the present invention, by containing the aromatic compound of the above formula (1) as an additive, a photoalignment that causes a chemical change by irradiation with radiation or the like is caused as specifically illustrated in the examples described later. Even in the case of alignment treatment by the method, it is possible to obtain a liquid crystal alignment film in a liquid crystal display element having a high voltage retention rate and good liquid crystal alignment under a harsh environment. The mechanism is not always clear, but it can be considered as follows.
In the alignment treatment by the photo-alignment method, for example, the surface of a film-like material formed from a liquid crystal alignment agent formed on the surface of a substrate is irradiated with high-energy UV light polarized in a substantially linear manner. In this case, UV By irradiating with light, decomposition products of organic substances constituting the film-like substance are generated, which become impurities that cause a decrease in the voltage retention rate in the liquid crystal alignment film, and therefore, the voltage retention rate of the liquid crystal alignment film is reduced. Seem.
However, in the liquid crystal alignment agent of the present invention, when the impurities are generated by irradiation with UV light, the aromatic compound of the above formula (1) has a functional group capable of reacting with the impurities, which lowers the voltage retention rate. By reacting with the impurities that bring about the above, the impurities contained in the obtained liquid crystal alignment film can be reduced. Therefore, the liquid crystal alignment film obtained from the liquid crystal alignment agent of the present invention is considered to maintain a high voltage retention rate.
Further, since the aromatic compound of the above formula (1) contained in the liquid crystal alignment agent of the present invention has a highly flat structure, the liquid crystal orientation of the obtained liquid crystal alignment film is not hindered and the liquid crystal is high. It is considered that a liquid crystal alignment film having orientation can be obtained. Therefore, in the IPS drive method and the FFS drive method, even when the liquid crystal display element is driven for a long time, the liquid crystal returns to the same state as before the drive, so that it is considered that a liquid crystal display element with less seizure can be obtained.
Aにおける2価の連結基としては、2価の炭化水素基、この炭化水素基の炭素-炭素間又は炭化水素基の末端にヘテロ原子を有する基を含む2価のヘテロ原子含有基、上記炭化水素基及びヘテロ原子含有基が有する一部又は全部の水素原子を置換基で置換した2価の連結基、-S(=O)2-、-CO-、-O-、-S-、-NR-CO-(Rは、水素原子又は炭素数1~6のアルキル基を表す。)、-NR-CO-NR-(Rは水素原子又は炭素数1~6のアルキル基を表す)等が挙げられる。 Examples of the n-valent organic group include an n-valent hydrocarbon group, an n-valent heteroatom-containing group containing a group having a heteroatom between carbons of the hydrocarbon group or at the end of the hydrocarbon group, and the above-mentioned carbonization. Examples thereof include an n-valent organic group in which a part or all of the hydrogen atoms of the hydrogen group and the heteroatom-containing group are substituted with a substituent.
The divalent linking group in A includes a divalent hydrocarbon group, a divalent heteroatom-containing group containing a group having a heteroatom between carbons of the hydrocarbon group or at the end of the hydrocarbon group, and the above-mentioned carbonization. A divalent linking group in which some or all of the hydrogen atoms of the hydrogen group and the heteroatom-containing group are substituted with a substituent, -S (= O) 2- , -CO-, -O-, -S-,- NR-CO- (R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -NR-CO-NR- (R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), etc. Can be mentioned.
上記式(b1)において、nは2であるのが好ましく、Aは、単結合又は2価の連結基であるのが好ましい。 Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy group such as methoxy group, ethoxy group and propoxy group; alkoxycarbonyl group such as methoxycarbonyl group and ethoxycarbonyl group; methoxy. Alkoxycarbonyloxy groups such as carbonyloxy group and ethoxycarbonyloxy group; cyano group, nitro group and the like can be mentioned.
In the above formula (b1), n is preferably 2 and A is preferably a single bond or a divalent linking group.
上記式(1)の芳香族化合物を含有される本発明の液晶配向剤は、既知のものと同様に、液晶を配向させる能力を有する重合体を含有するが、かかる重合体は、液晶を配向させる能力を有するものであれば特に限定されない。
かかる重合体としては、例えば、ポリイミド前駆体、ポリイミド前駆体のイミド化物であるポリイミド、アクリルポリマー、メタクリルポリマー、アクリルアミドポリマー、メタクリルアミドポリマー、ポリスチレン、ポリシロキサン、ポリアミド、ポリエステル、ポリウレタン、ポリカーネート、ポリウレア、ポリフェノール(ノボラック樹脂)、マレイミドポリマー、イソシアヌル酸骨格、トリアジン骨格を有した化合物を導入した重合体が挙げられる。かかる重合体は、1種または2種以上を組み合わせて用いることができる。 <Polymer>
The liquid crystal aligning agent of the present invention containing the aromatic compound of the above formula (1) contains a polymer having an ability to orient the liquid crystal as in the known one, but such a polymer orients the liquid crystal. It is not particularly limited as long as it has the ability to make it.
Examples of such polymers include polyimide precursors, polyimides which are imidized polyimide precursors, acrylic polymers, methacrylic polymers, acrylamide polymers, methacrylicamide polymers, polystyrenes, polysiloxanes, polyamides, polyesters, polyurethanes, polycarbonates, and polyureas. , Polyphenol (Novolak resin), Maleimide polymer, Isocyanuric acid skeleton, Triazine skeleton-introduced polymer. Such a polymer can be used alone or in combination of two or more.
重合体が、ポリアミック酸、ポリアミック酸エステル等のポリイミド前駆体やポリイミドの場合は、テトラカルボン酸若しくはその誘導体から選択される少なくとも一種のテトラカルボン酸成分とジアミン;
重合体が(メタ)アクリルポリマーの場合は、(メタ)アクリル酸若しくはその誘導体、(メタ)アクリル酸エステル若しくはその誘導体;重合体が(メタ)アクリルアミドポリマーの場合は、(メタ)アクリルアミド若しくはその誘導体; Examples of raw materials for producing these polymers include the following.
When the polymer is a polyimide precursor such as polyamic acid or polyamic acid ester or polyimide, at least one tetracarboxylic acid component selected from tetracarboxylic acid or a derivative thereof and diamine;
If the polymer is a (meth) acrylic polymer, (meth) acrylic acid or a derivative thereof, (meth) acrylic acid ester or a derivative thereof; if the polymer is a (meth) acrylamide polymer, (meth) acrylamide or a derivative thereof. ;
重合体がポリエステルの場合はジカルボン酸及びその誘導体から選択される少なくとも一種のジカルボン酸成分とジオール成分; When the polymer is polystyrene, styrene or a derivative thereof; when the polymer is polysiloxane, a silane compound having a methoxy group or an ethoxy group; when the polymer is polyamide, at least selected from a dicarboxylic acid and a derivative thereof. A kind of dicarboxylic acid component and diamine component;
When the polymer is polyester, at least one dicarboxylic acid component and diol component selected from dicarboxylic acid and its derivatives;
重合体がポリウレアの場合は、ビスイソシアネート誘導体とジアミン成分;重合体がマレイミドポリマーの場合は、マレイミド誘導体単独若しくはスチレンとの共重合;
重合体がイソシアヌル酸骨格やトリアジン骨格を有した化合物を導入したポリマーの場合は、イソシアヌル酸骨格やトリアジン骨格を有した化合物。 When the polymer is polyurethane, it is a compound having isocyanate, compound and hydroxyl group; when the polymer is polycarnate, it is a bisphenol derivative and phosgene or phosgene equivalent (for example, trichlorophosgene) or diphenyl carbonate;
When the polymer is polyurea, the bisisocyanate derivative and the diamine component; when the polymer is a maleimide polymer, the maleimide derivative alone or copolymerization with styrene;
In the case of a polymer into which a compound having an isocyanuric acid skeleton or a triazine skeleton is introduced, a compound having an isocyanuric acid skeleton or a triazine skeleton.
本発明の液晶配向剤に含有される重合体としては、なかでも、液晶配向剤としての実用性、塗布膜の機械的、及び電気的特性の観点から、ポリイミド前駆体、及びポリイミド前駆体のイミド化物であるポリイミドからなる群から選ばれる1つ以上の重合体(以下、ポリイミド系重合体ともいう。)が好ましい。
上記ポリイミド系重合体は、既知の方法で製造できる。例えば、ポリイミド前駆体であるポリアミック酸は、テトラカルボン酸二無水物若しくはその誘導体からなるテトラカルボン酸成分と、ジアミン成分と、を重(縮)合反応させることにより得られ、このポリイミド前駆体をイミド化することによりポリイミドが得られる。 <Polyimide-based polymer>
The polymers contained in the liquid crystal aligning agent of the present invention include, among others, a polyimide precursor and an imide of the polyimide precursor from the viewpoint of practicality as a liquid crystal aligning agent, mechanical and electrical characteristics of a coating film. One or more polymers (hereinafter, also referred to as polyimide-based polymers) selected from the group consisting of polyimides as compounds are preferable.
The polyimide-based polymer can be produced by a known method. For example, polyamic acid, which is a polyimide precursor, is obtained by subjecting a tetracarboxylic acid component composed of a tetracarboxylic dianhydride or a derivative thereof and a diamine component to a polycondensation reaction, and this polyimide precursor is used. Polyimide can be obtained by imidization.
ポリイミド前駆体であるポリアミック酸は、例えば、芳香族、脂肪族若しくは脂環式テトラカルボン酸二無水物を含むテトラカルボン酸成分から得られるものが挙げられる。ここで、芳香族テトラカルボン酸二無水物は、芳香環に結合する少なくとも1つのカルボキシル基を含めて4つのカルボキシル基が分子内脱水することにより得られる酸二無水物である。脂肪族テトラカルボン酸二無水物は、鎖状炭化水素構造に結合する4つのカルボキシル基が分子内脱水することにより得られる酸二無水物である。但し、鎖状炭化水素構造のみで構成されている必要はなく、その一部に脂環式構造や芳香環構造を有していてもよい。 <Tetracarboxylic acid component>
Examples of the polyamic acid as a polyimide precursor include those obtained from a tetracarboxylic acid component containing an aromatic, aliphatic or alicyclic tetracarboxylic dianhydride. Here, the aromatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxyl groups including at least one carboxyl group bonded to the aromatic ring. The aliphatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxyl groups bonded to a chain hydrocarbon structure. However, it does not have to be composed of only a chain hydrocarbon structure, and a part thereof may have an alicyclic structure or an aromatic ring structure.
また、脂環式構造のみで構成されている必要はなく、その一部に鎖状炭化水素構造や芳香環構造を有していてもよい。 The alicyclic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxyl groups including at least one carboxyl group bonded to the alicyclic structure. However, none of these four carboxyl groups are bonded to the aromatic ring.
Further, it is not necessary to have only an alicyclic structure, and a chain hydrocarbon structure or an aromatic ring structure may be partially provided.
R5及びR6は、それぞれ独立して、水素原子又はメチル基を表す。j及びkは、それぞれ独立して、0又は1の整数である。A1及びA2は、それぞれ独立して、単結合、-O-、-CO-、-COO-、フェニレン、-SO2-、又は-CONH-を表す。2つのA2は同一でも異なってもよい。*1は一方の酸無水物基に結合する結合手であり、*2は他方の酸無水物基に結合する結合手である。) In the above formulas (x-1) to (x-13), R 1 to R 4 are independently hydrogen atoms, halogen atoms, alkyl groups having 1 to 6 carbon atoms, and alkenyl groups having 2 to 6 carbon atoms, respectively. , A alkynyl group having 2 to 6 carbon atoms, a monovalent organic group having 1 to 6 carbon atoms having a fluorine atom, or a phenyl group.
R 5 and R 6 each independently represent a hydrogen atom or a methyl group. j and k are independently integers of 0 or 1. A 1 and A 2 independently represent single bonds, -O-, -CO-, -COO-, phenylene, -SO 2- , or -CONH-, respectively. Two A 2 may be the same or different. * 1 is a bond that binds to one acid anhydride group, and * 2 is a bond that binds to the other acid anhydride group. )
ポリイミド前駆体の製造に用いられるジアミン成分は特に限定されないが、下記式(3)で表されるジアミンを含むジアミン成分が好ましい。
The diamine component used for producing the polyimide precursor is not particularly limited, but a diamine component containing a diamine represented by the following formula (3) is preferable.
A2は、ハロゲン原子、ヒドロキシ基、アミノ基、チオール基、ニトロ基、リン酸基、又は炭素数1~20の1価の有機基を表す。A2が複数存在する場合、A2は同一でも異なってもよい。aは0~4の整数であり、aが複数存在する場合、aは同一でも異なってもよい。b及びcは、それぞれ独立して、1又は2の整数であり、dは0又は1の整数である。 In the above formula (3), A 1 is an alkylene group having 2 to 14 carbon atoms, or -O-, -CO-, -OCO- or-under the condition that at least one of -CH 2- possessed by the alkylene is not continuous. Represents a group substituted with -COO-. A 1 is more preferably -O-, -CO-, -OCO- or -COO- under the condition that at least one of the alkylene group having 2 to 12 carbon atoms or -CH 2- possessed by the alkylene is not continuous. It is a group substituted with, more preferably -O-, -CO-, -OCO- under the condition that at least one of the alkylene group having 2 to 10 carbon atoms or -CH 2- possessed by the alkylene is not continuous. Alternatively, it is a group substituted with -COO-.
A 2 represents a halogen atom, a hydroxy group, an amino group, a thiol group, a nitro group, a phosphoric acid group, or a monovalent organic group having 1 to 20 carbon atoms. When there are a plurality of A 2 , A 2 may be the same or different. a is an integer of 0 to 4, and when a plurality of a exist, a may be the same or different. b and c are independently integers of 1 or 2, and d is an integer of 0 or 1.
上記式(n)中のRの1価の炭化水素基としては、例えば、メチル基、エチル基、プロピル基等のアルキル基;シクロヘキシル基等のシクロアルキル基;フェニル基、メチルフェニル基等のアリール含有基等が挙げられる。Rは、好ましくは水素原子又はメチル基である。 The secondary amino group and the tertiary amino group that the diamine having a nitrogen-containing structure may have are represented by, for example, the following formula (n).
Examples of the monovalent hydrocarbon group of R in the above formula (n) include an alkyl group such as a methyl group, an ethyl group and a propyl group; a cycloalkyl group such as a cyclohexyl group; and an aryl such as a phenyl group and a methylphenyl group. Examples include containing groups. R is preferably a hydrogen atom or a methyl group.
4-(2-(メチルアミノ)エチル)アニリン、4-(2-アミノエチル)アニリン、4,4’-ジアミノジフェニルメタン、4,4’-ジアミノベンゾフェノン、4,4’-ジアミノジフェニルエーテル、下記式(g-1)~(g-9)で表されるジアミンなどの光配向性基を有するジアミン、1-(4-アミノフェニル)-1,3,3-トリメチル-1H-インダン-5-アミン、1-(4-アミノフェニル)-2,3-ジヒドロ-1,3,3-トリメチル-1H-インデン-6-アミン、3,5-ジアミノ安息香酸等のカルボキシル基含有ジアミン、1,3-ビス(4-アミノフェノキシ)ベンゼン、1,4-ビス(4-アミノフェノキシ)ベンゼン、ビス[4-(4-アミノフェノキシ)フェニル]エーテル、4,4’-ビス(4-アミノフェノキシ)ビフェニル、1,4-ジアミノナフタレン、1,5-ジアミノナフタレン、2,6-ジアミノナフタレン、2,7-ジアミノナフタレン、2,2’-ビス[4-(4-アミノフェノキシ)フェニル]プロパン、2,2’-ビス[4-(4-アミノフェノキシ)フェニル]ヘキサフルオロプロパン、2,2’-ビス(4-アミノフェニル)プロパン、下記式(u-1)~(u-3)で表されるジアミンなどのウレア結合を有するジアミン、下記式(u-4)~(u-7)で表されるジアミンなどのアミド結合を有するジアミン、メタクリル酸2-(2,4-ジアミノフェノキシ)エチル、2,4-ジアミノ-N,N-ジアリルアニリン等の光重合性基を末端に有するジアミン、コレスタニルオキシ-3,5-ジアミノベンゼン、コレステニルオキシ-3,5-ジアミノベンゼン、コレスタニルオキシ-2,4-ジアミノベンゼン、3,5-ジアミノ安息香酸コレスタニル、3,5-ジアミノ安息香酸コレステニル、3,5-ジアミノ安息香酸ラノスタニル、3,6-ビス(4-アミノベンゾイルオキシ)コレスタン等のステロイド骨格を有するジアミン、下記式(V-1)~(V-6)で表されるジアミン、 The polyimide-based polymer used in the present invention may contain other diamines other than the diamines described above. Examples of other diamines are given below, but the present invention is not limited thereto.
4- (2- (Methylamino) ethyl) aniline, 4- (2-aminoethyl) aniline, 4,4'-diaminodiphenylmethane, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenyl ether, the following formula ( Diamines having photoorienting groups such as diamines represented by g-1) to (g-9), 1- (4-aminophenyl) -1,3,3-trimethyl-1H-indan-5-amine, Carboxyl group-containing diamines such as 1- (4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-inden-6-amine, 3,5-diaminobenzoic acid, 1,3-bis (4-Aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] ether, 4,4'-bis (4-aminophenoxy) biphenyl, 1 , 4-Diaminonaphthalene, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,2'-bis [4- (4-aminophenoxy) phenyl] propane, 2,2' -Bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2'-bis (4-aminophenyl) propane, amines represented by the following formulas (u-1) to (u-3), etc. Diamine having a urea bond, a diamine having an amide bond such as a diamine represented by the following formulas (u-4) to (u-7), 2- (2,4-diaminophenoxy) ethyl methacrylate, 2,4 Diamines having photopolymerizable groups such as -diamino-N, N-diallylaniline at the ends, cholestanyloxy-3,5-diaminobenzene, cholestenyloxy-3,5-diaminobenzene, cholestanyloxy-2,4 It has a steroid skeleton such as -diaminobenzene, cholestanyl 3,5-diaminobenzoate, cholestenyl 3,5-diaminobenzoate, lanostanyl 3,5-diaminobenzoate, and 3,6-bis (4-aminobenzoyloxy) cholesterol. Diamines, diamines represented by the following formulas (V-1) to (V-6),
本発明に用いられるポリイミド前駆体であるポリアミック酸は、以下の方法により製造できる。具体的には、上記テトラカルボン酸成分と上記ジアミン成分とを有機溶媒の存在下で-20~150℃、好ましくは0~50℃において、30分~24時間、好ましくは1~12時間(重縮合)反応させることによって合成できる。
上記の反応に用いる有機溶媒は、モノマー及びポリマーの溶解性からN,N-ジメチルホルムアミド、N-メチル-2-ピロリドン、又はγ-ブチロラクトンが好ましく、これらは2種以上を混合して用いてもよい。ポリマーの濃度は、ポリマーの析出が起こりにくく、かつ高分子量体が得やすいという観点から、1~30質量%が好ましく、5~20質量%がより好ましい。 <Manufacturing method of polyamic acid>
The polyamic acid, which is a polyimide precursor used in the present invention, can be produced by the following method. Specifically, the tetracarboxylic acid component and the diamine component are mixed in the presence of an organic solvent at −20 to 150 ° C., preferably 0 to 50 ° C. for 30 minutes to 24 hours, preferably 1 to 12 hours (heavy). It can be synthesized by reacting (condensation).
The organic solvent used in the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, or γ-butyrolactone because of the solubility of the monomer and the polymer, and these may be used in combination of two or more. Good. The concentration of the polymer is preferably 1 to 30% by mass, more preferably 5 to 20% by mass, from the viewpoint that precipitation of the polymer is unlikely to occur and a high molecular weight polymer is easily obtained.
末端封止剤としては、例えば無水マレイン酸、無水ナジック酸、無水フタル酸、無水イタコン酸、シクロヘキサンジカルボン酸無水物、3-ヒドロキシフタル酸無水物、トリメット酸無水物等の酸一無水物や二炭酸ジ-tert-ブチル;アニリン、2-アミノフェノール、3-アミノフェノール、4-アミノサリチル酸、5-アミノサリチル酸、6-アミノサリチル酸、2-アミノ安息香酸、3-アミノ安息香酸、4-アミノ安息香酸等のモノアミン化合物;エチルイソシアネート、フェニルイソシアネート、ナフチルイソシアネート等のモノイソシアネート化合物等を挙げられる。
末端封止剤の使用割合は、使用するジアミン成分の合計100モル部に対して、40モル部以下とすることが好ましく、30モル部以下とすることがより好ましい。 The polyimide precursor may be an end-sealing polymer obtained by using an appropriate end-capping agent together with the tetracarboxylic acid derivative and diamine as described above when producing the polyimide precursor.
Examples of the terminal encapsulant include acid monoanhydrides such as maleic anhydride, nadic acid anhydride, phthalic anhydride, itaconic anhydride, cyclohexanedicarboxylic acid anhydride, 3-hydroxyphthalic anhydride, and trimetic acid anhydride. Di-tert-butyl carbonate; aniline, 2-aminophenol, 3-aminophenol, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid Monoamine compounds such as acids; monoisocyanate compounds such as ethyl isocyanate, phenylisocyanate and naphthylisocyanate can be mentioned.
The proportion of the end-capping agent used is preferably 40 mol parts or less, and more preferably 30 mol parts or less, based on 100 mol parts of the total diamine component used.
本発明に用いられるポリイミドは、ポリイミド前駆体であるポリアミック酸又はポリアミック酸エステルを既知の方法によりイミド化することにより製造できる。
例えば、ポリアミック酸からポリイミドを製造する場合、ジアミン成分とテトラカルボン酸成分との反応で得られたポリアミック酸の溶液に触媒を添加する(化学的)イミド化が簡便である。イミド化は、イミド化させたい重合体を、有機溶媒中において塩基性触媒と酸無水物の存在下で攪拌することにより行うことができる。 <Polyimide manufacturing method>
The polyimide used in the present invention can be produced by imidizing a polyamic acid or a polyamic acid ester, which is a polyimide precursor, by a known method.
For example, when polyimide is produced from a polyamic acid, it is convenient to add a catalyst to the solution of the polyamic acid obtained by the reaction of the diamine component and the tetracarboxylic acid component (chemical). Imidization can be carried out by stirring the polymer to be imidized in an organic solvent in the presence of a basic catalyst and an acid anhydride.
なお、本明細書でいうイミド化率とは、テトラカルボン酸二無水物またはその誘導体由来のイミド基とカルボキシル基(またはその誘導体)との合計量に占めるイミド基の割合のことである。ポリイミドにおいては、イミド化率は必ずしも100%である必要はなく、用途や目的に応じて任意に調整できる。本発明で用いられるポリイミドのイミド化率は、20~100%が好ましく、50~99%がより好ましい。 The temperature at which the imidization reaction is carried out is −20 to 140 ° C., preferably 0 to 100 ° C., and the reaction time can be 1 to 100 hours. The amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times, that of the amic acid group, and the amount of acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol times that of the amic acid group. It is double. The imidization rate of the obtained polymer can be controlled by adjusting the amount of catalyst, the temperature, and the reaction time.
The imidization rate as used herein is the ratio of the imide group to the total amount of the imide group derived from the tetracarboxylic dianhydride or its derivative and the carboxyl group (or its derivative). In polyimide, the imidization ratio does not necessarily have to be 100%, and can be arbitrarily adjusted according to the application and purpose. The imidization ratio of the polyimide used in the present invention is preferably 20 to 100%, more preferably 50 to 99%.
上記貧溶媒は、特に限定されないが、メタノール、アセトン、ヘキサン、ブチルセルソルブ、ヘプタン、メチルエチルケトン、メチルイソブチルケトン、エタノール、トルエン、ベンゼン等が挙げられる。 The polyimide solution obtained as described above can be injected into a poor solvent with stirring to precipitate a polymer. Precipitation is carried out several times, and after washing with a poor solvent, a purified polyimide powder can be obtained at room temperature or by heating and drying.
The poor solvent is not particularly limited, and examples thereof include methanol, acetone, hexane, butyl cellsolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, and benzene.
本発明の液晶配向剤は、液晶を配向させる能力を有する重合体が溶媒中に溶解された溶液中に、上記式(1)の芳香族化合物が添加された形態を有する。
本発明の液晶配向剤に含有される重合体の含有量(濃度)は、形成させようとする塗膜の厚みの設定によっても適宜変更できるが、均一で欠陥のない塗膜を形成させるという点から1質量%以上が好ましく、溶液の保存安定性の点からは10質量%以下が好ましい。
また、本発明の液晶配向剤に添加される上記式(1)の芳香族化合物の含有量(濃度)は、0.1~5質量%であるのが好ましく、0.15~5質量%であるのがより好ましく、0.2~5質量%であるのが特に好ましい。
また、上記式(1)の芳香族化合物の含有量は、液晶配向剤に含有される上記重合体と上記式(1)の芳香族化合物との含有量の合計が、1~15質量%であるのが好ましく、2~10質量%であるのがより好ましく、2~8質量%であるのが特に好ましい。 <Liquid crystal alignment agent>
The liquid crystal alignment agent of the present invention has a form in which the aromatic compound of the above formula (1) is added to a solution in which a polymer having the ability to orient the liquid crystal is dissolved in a solvent.
The content (concentration) of the polymer contained in the liquid crystal aligning agent of the present invention can be appropriately changed by setting the thickness of the coating film to be formed, but the point is that a uniform and defect-free coating film is formed. From the viewpoint of storage stability of the solution, it is preferably 10% by mass or less.
The content (concentration) of the aromatic compound of the above formula (1) added to the liquid crystal alignment agent of the present invention is preferably 0.1 to 5% by mass, preferably 0.15 to 5% by mass. It is more preferable to have it, and it is particularly preferable that it is 0.2 to 5% by mass.
The content of the aromatic compound of the above formula (1) is such that the total content of the polymer contained in the liquid crystal alignment agent and the aromatic compound of the above formula (1) is 1 to 15% by mass. It is preferably present, more preferably 2 to 10% by mass, and particularly preferably 2 to 8% by mass.
例えば、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、N-メチル-2-ピロリドン、N-エチル-2-ピロリドン、ジメチルスルホキシド、γ-ブチロラクトン、1,3-ジメチル-2-イミダゾリジノン、メチルエチルケトン、シクロヘキサノン、シクロペンタノン、3-メトキシ-N,N-ジメチルプロパンアミド又は4-ヒドロキシ-4-メチル-2-ペンタノン、下記の式[D-1]~式[D-3]で示される溶媒等を挙げることができる。 The solvent used for the liquid crystal alignment agent of the present invention is not particularly limited as long as it is a solvent that dissolves the aromatic compound of the above formula (1) and the above polymer. Specific examples are given below.
For example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone. , Methylethylketone, cyclohexanone, cyclopentanone, 3-methoxy-N, N-dimethylpropanamide or 4-hydroxy-4-methyl-2-pentanone, represented by the following formulas [D-1] to [D-3]. The solvent and the like can be mentioned.
本発明における溶媒は、なかでも、N-メチル-2-ピロリドン、N-エチル-2-ピロリドン、γ-ブチロラクトン、3-メトキシ-N,N-ジメチルプロパンアミド、又は1,3-ジメチル-2-イミダゾリジノン(以下、これらを良溶媒ともいう。)が好ましい。
The solvent in the present invention is, among others, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, 3-methoxy-N, N-dimethylpropanamide, or 1,3-dimethyl-2-. Imidazolidinone (hereinafter, these are also referred to as good solvents) is preferable.
なかでも、ブチルセロソルブ、1-ブトキシ‐2-プロパノール、ブチルセロソルブアセタート、ジプロピレングリコールモノメチルエーテル、ジアセトンアルコール、ジエチレングリコールジエチルエーテル、ジイソペンチルエーテル、プロピレングリコールジアセタート、ジイソブチルケトン、エチルカルビトール又はジプロピレングリコールジメチルエーテルを用いることが好ましい。 Specific examples of the poor solvent are given below. Ethylene, 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-ethanediol , 1,2-Propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-Methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, dipropyl ether, dibutyl ether, dihexyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1, 2-Butoxyethane, Diethylene glycol dimethyl ether, Diethylene glycol diethyl ether, Diethylene glycol methyl ethyl ether, Diethylene glycol dibutyl ether, 2-Pentanone, 3-Pentanone, 2-Hexanone, 2-Heptanone, 4-Heptanone, 3-ethoxybutyl acetate, 1- Methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetylate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, 2- (methoxymethoxy) ethanol, butyl cellosolve, ethylene glycol monoisoamyl Ether, ethylene glycol monohexyl ether, 2- (hexyloxy) ethanol, furfuryl alcohol, diethylene glycol, propylene glycol, 1-butoxy-2-propanol, 1- (butoxyethoxy) propanol, propylene glycol monomethyl ether acetate, dipropylene Glycol, Dipropylene Glycol Monomethyl A Tel, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, butyl cellosolve acetate, ethylene glycol monoacetate, ethylene glycol diacetate. , Diethylene glycol monoethyl ether acetate, diacetone alcohol, propylene glycol diacetate, diisopentyl ether, diethylene glycol monobutyl ether acetate, 2- (2-ethoxyethoxy) ethyl acetate, diethylene glycol acetate, triethylene glycol, tri Ethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate , Methyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, n-propyl lactate, n-butyl lactate , Isoamyl lactic acid, diisobutyl ketone, ethyl carbitol, solvents represented by the above formulas [D-1] to [D-3], and the like.
Among them, butyl cellosolve, 1-butoxy-2-propanol, butyl cellosolve acetate, dipropylene glycol monomethyl ether, diacetone alcohol, diethylene glycol diethyl ether, diisopentyl ether, propylene glycol diacetate, diisobutyl ketone, ethyl carbitol or di It is preferable to use propylene glycol dimethyl ether.
かかる化合物としては、フッ素系界面活性剤、シリコーン系界面活性剤、ノ二オン系界面活性剤等が挙げられる。より具体的には、例えば、エフトップEF301、EF303、EF352(以上、三菱マテリアル電子化成社製)、メガファックF171、F173、R-30(以上、DIC社製)、フロラードFC430、FC431(以上、スリーエム社製)、アサヒガードAG710、サーフロンS-382、SC101、SC102、SC103、SC104、SC105、SC106(以上、AGC社製)等が挙げられる。 In addition, the liquid crystal alignment agent of the present invention can contain a compound that improves the thickness uniformity and surface smoothness of the film-like material obtained by applying the liquid crystal alignment agent.
Examples of such a compound include a fluorine-based surfactant, a silicone-based surfactant, and a nonion-based surfactant. More specifically, for example, Ftop EF301, EF303, EF352 (above, manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd.), Megafuck F171, F173, R-30 (above, manufactured by DIC Corporation), Florard FC430, FC431 (above, 3M Ltd.), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (all manufactured by AGC Corporation) and the like.
本発明の液晶配向膜は、上記の液晶配向剤を基板に塗布し、乾燥、焼成して得られる膜である。基板としては透明性の高い基板であれば特に限定されず、ガラス基板、窒化珪素基板、アクリル基板やポリカーボネート基板等のプラスチック基板等が挙げられる。液晶を駆動させるためのITO電極等が形成された基板は、プロセスの簡素化の点から好ましい。反射型の液晶表示素子では、片側の基板のみにならばシリコンウエハー等の不透明な物でも使用でき、この場合の電極にはアルミニウム等の光を反射する材料も使用できる。 <Liquid crystal alignment film / liquid crystal display element>
The liquid crystal alignment film of the present invention is a film obtained by applying the above liquid crystal alignment agent to a substrate, drying and firing. The substrate is not particularly limited as long as it is a highly transparent substrate, and examples thereof include a glass substrate, a silicon nitride substrate, a plastic substrate such as an acrylic substrate and a polycarbonate substrate, and the like. A substrate on which an ITO electrode or the like for driving a liquid crystal is formed is preferable from the viewpoint of simplifying the process. In the reflective liquid crystal display element, an opaque object such as a silicon wafer can be used if only one substrate is used, and a material that reflects light such as aluminum can also be used for the electrode in this case.
液晶配向剤を基板上に塗布した後は、ホットプレート、熱循環型オーブン又はIR(赤外線)型オーブン等の加熱手段により、溶媒を蒸発させて膜状物(被膜)とすることができる。液晶配向剤を塗布した後の乾燥、焼成工程は、任意の温度と時間を選択できる。通常、含有される溶媒を十分に除去するために50~180℃で1~10分焼成するか、更に熱イミド化を行うためにその後、150~300℃で5~120分焼成してもよい。焼成後の膜状物は、薄すぎると液晶表示素子の信頼性が低下する場合があるので、5~300nmが好ましく、10~200nmがより好ましい。 Examples of the method of applying the liquid crystal alignment agent to the substrate to form a film include screen printing, offset printing, flexographic printing, an inkjet method, a spray method, and the like. Of these, the coating and film forming methods by the inkjet method can be preferably used.
After the liquid crystal aligning agent is applied onto the substrate, the solvent can be evaporated to form a film (film) by a heating means such as a hot plate, a heat circulation type oven, or an IR (infrared) type oven. Any temperature and time can be selected for the drying and firing steps after applying the liquid crystal alignment agent. Usually, it may be calcined at 50 to 180 ° C. for 1 to 10 minutes to sufficiently remove the contained solvent, or may then be calcined at 150 to 300 ° C. for 5 to 120 minutes for further thermal imidization. .. If the film-like material after firing is too thin, the reliability of the liquid crystal display element may decrease, so 5 to 300 nm is preferable, and 10 to 200 nm is more preferable.
更に、上記の方法で、偏光された放射線を照射した液晶配向膜に、水や溶媒を用いて、これらと処理するか、放射線を照射した液晶配向膜を加熱処理することもできる。 Further, when irradiating with radiation, in order to improve the liquid crystal orientation, the substrate having the film-like substance may be irradiated while being heated at 50 to 250 ° C. The irradiation amount of the above radiation is preferably 1 to 10,000 mJ / cm 2. Of these, 100 to 5,000 mJ / cm 2 is preferable. The liquid crystal alignment film thus produced can stably orient liquid crystal molecules in a certain direction.
Further, by the above method, the liquid crystal alignment film irradiated with polarized radiation can be treated with water or a solvent, or the liquid crystal alignment film irradiated with radiation can be heat-treated.
上記の放射線を照射した塗膜に対する加熱処理は、50~300℃で1~30分とすることがより好ましく、120~250℃で1~30分とすることがさらに好ましい。 After the above contact treatment, it is preferable to perform rinsing (also referred to as rinsing) or firing with a low boiling point solvent such as water, methanol, ethanol, 2-propanol, acetone, or methyl ethyl ketone. At that time, either one of rinsing and firing may be performed, or both may be performed. The firing temperature is preferably 150 to 300 ° C. Of these, 180 to 250 ° C. is preferable. More preferably, it is 200 to 230 ° C. The firing time is preferably 10 seconds to 30 minutes. Of these, 1 to 10 minutes is preferable.
The heat treatment of the above-mentioned radiation-irradiated coating film is more preferably 50 to 300 ° C. for 1 to 30 minutes, and further preferably 120 to 250 ° C. for 1 to 30 minutes.
液晶セルの作製方法の一例として、パッシブマトリクス構造の液晶表示素子を例にとり説明する。なお、画像表示を構成する各画素部分にTFT(Thin Film Transistor)等のスイッチング素子を設けたアクティブマトリクス構造の液晶表示素子であってもよい。 The liquid crystal alignment film of the present invention is suitable as a liquid crystal alignment film for a transverse electric field type liquid crystal display element such as an IPS system or an FFS system from the viewpoint of obtaining high liquid crystal alignment, and is particularly suitable for an FFS type liquid crystal display element. It is useful as a liquid crystal alignment film. The liquid crystal display element is obtained by obtaining a substrate with a liquid crystal alignment film obtained from the liquid crystal alignment agent of the present invention, then producing a liquid crystal cell by a known method, and using the liquid crystal cell.
As an example of a method for manufacturing a liquid crystal cell, a liquid crystal display element having a passive matrix structure will be described as an example. A liquid crystal display element having an active matrix structure in which a switching element such as a TFT (Thin Film Transistor) is provided in each pixel portion constituting the image display may be used.
<溶媒>
DMF:N,N-ジメチルホルムアミド、 NMP:N-メチル-2-ピロリドン
GBL:γ-ブチロラクトン、 BCS:ブチルセロソルブ
<ジアミン>
DA-1:1,2-ビス(4-アミノフェノキシ)エタン
DA-2:N-tert-ブトキシカルボニル-N-(2-(4-アミノフェニル)エチル)-N-(4-アミノベンジル)アミン
DA-3:p-フェニレンジアミン、 DA-4:下記式(DA-4)参照
DA-5:4,4’-ジアミノジフェニルアミン
DA-6:4,4’-ジアミノジフェニルメタン Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. The abbreviations of compounds and the methods for measuring their properties in the following are as follows.
<Solvent>
DMF: N, N-dimethylformamide, NMP: N-methyl-2-pyrrolidone GBL: γ-butyrolactone, BCS: Butyl cellosolve <diamine>
DA-1: 1,2-bis (4-aminophenoxy) ethane DA-2: N-tert-butoxycarbonyl-N- (2- (4-aminophenyl) ethyl) -N- (4-aminobenzyl) amine DA-3: p-phenylenediamine, DA-4: Refer to the following formula (DA-4) DA-5: 4,4'-diaminodiphenylamine DA-6: 4,4'-diaminodiphenylmethane
装置:フーリエ変換型超伝導核磁気共鳴装置(FT-NMR)「AVANCE III」(BRUKER製)500MHz。
溶媒:重水素化クロロホルム(CDCl3)又は重水素化N,N-ジメチルスルホキシド([D6]-DMSO)。標準物質:テトラメチルシラン(TMS)。 < 1 1 H-NMR measurement>
Device: Fourier transform type superconducting nuclear magnetic resonance device (FT-NMR) "AVANCE III" (manufactured by BRUKER) 500 MHz.
Solvent: Deuterated chloroform (CDCl 3 ) or deuterated N, N-dimethyl sulfoxide ([D 6 ] -DMSO). Standard substance: Tetramethylsilane (TMS).
1H-NMR(500MHz,[D6]-DMSO):δ7.57-7.60(d,4H),7.25-7.27(d,4H),4.80-4.81(m,2H),4.76-4.77(m,2H),3.34(s,4H),1.65(s,6H) In a 1 L four-necked flask, 4,4'-biphenyldiboronic acid (22.5 g, 93 mmol), 3-chloro-2-methyl-1-propene (95.1 g, 1050 mmol), Najera catalyst I (0. 244 g, 0.3 mmol), tetrabutylammonium bromide (13.5 g, 42 mmol), potassium carbonate (116.1 g, 840 mmol), DMF (250 g), and pure water (13 g) were charged and stirred at 130 ° C. After completion of the reaction, the reaction solution was poured into ethyl acetate (1000 g), neutralized with 1N-hydrochloric acid aqueous solution (1000 g), and washed with pure water (1000 g). The obtained organic layer was concentrated, and the obtained crude product was isolated by silica gel column chromatography (eluent: hexane only) to obtain 4.7 g of a white solid. From the results of 1 H-NMR shown below, it was confirmed that this solid was [T-1].
1 1 H-NMR (500 MHz, [D 6 ] -DMSO): δ7.57-7.60 (d, 4H), 7.25-7.27 (d, 4H), 4.80-4.81 (m) , 2H), 4.76-4.77 (m, 2H), 3.34 (s, 4H), 1.65 (s, 6H)
1H-NMR(500MHz,CDCl3):δ6.83(s,4H),4.78-4.79(m,2H),4.72-4.73(m,2H),4.09(s,4H),3.20(s,4H),2.30(s,12H),1.67(s,6H) [T-2-2] (17.3 g, 98 mmol), 1,2-bis (tosyloxy) ethane (18.5 g, 50 mmol), potassium carbonate (20.7 g, 150 mmol), and DMF in a 500 mL four-necked flask. (170 g) was charged and stirred at 80 ° C. After completion of the reaction, the reaction system was poured into ethyl acetate (500 g), and the organic layer was washed with pure water (1000 g). The obtained organic layer was concentrated, and the crude product was isolated by silica gel column chromatography (eluent: ethyl acetate / hexane = 1/30 (volume ratio)) to obtain 10.0 g of a transparent liquid. .. From the results of 1 H-NMR shown below, it was confirmed that this liquid was [T-2].
1 1 H-NMR (500 MHz, CDCl 3 ): δ6.83 (s, 4H), 4.78-4.79 (m, 2H), 4.72-4.73 (m, 2H), 4.09 ( s, 4H), 3.20 (s, 4H), 2.30 (s, 12H), 1.67 (s, 6H)
1H-NMR(500MHz,CDCl3):δ7.09-7.11(d,4H),6.87-6.89(d,4H),4.78-4.79(m,2H),4.70-4.71(m,2H),4.30(s,4H),3.26(s,4H),1.67(s,6H) After completion of the reaction, the reaction solution was poured into ethyl acetate (600 g) and washed with pure water (1200 g). The obtained organic layer was concentrated, and the crude product was isolated by silica gel column chromatography (eluent: ethyl acetate / hexane = 1/30 (volume ratio)) to obtain 1.6 g of a white solid. .. From the results of 1 H-NMR shown below, it was confirmed that this solid was the target [T-3].
1 1 H-NMR (500 MHz, CDCl 3 ): δ7.09-7.11 (d, 4H), 6.87-6.89 (d, 4H), 4.78-4.79 (m, 2H), 4.70-4.71 (m, 2H), 4.30 (s, 4H), 3.26 (s, 4H), 1.67 (s, 6H)
1H-NMR(500MHz,[D6]-DMSO):δ7.02(s,4H),5.87-5.96(m,2H),5.05-5.09(m,2H),5.00-5.03(m,2H),4.04(s,4H),3.24-3.25(d,4H),2.22(s,12H) [T-4-2] (30.3 g, 187 mmol), 1,2-bis (tosyloxy) ethane (34.4 g, 93 mmol), potassium carbonate (38.6 g, 279 mmol), and DMF (360 g) was charged and stirred at 80 ° C. After completion of the reaction, the reaction system was poured into ethyl acetate (1000 g), and the organic layer was washed with pure water (2000 g). The obtained organic layer was concentrated, and the crude product was isolated by silica gel column chromatography (eluent: ethyl acetate / hexane = 1/80 (volume ratio)) to obtain 18.7 g of a transparent liquid. .. From the results of 1 H-NMR shown below, it was confirmed that this liquid was the target [T-4].
1 1 H-NMR (500 MHz, [D 6 ] -DMSO): δ7.02 (s, 4H), 5.87-5.96 (m, 2H), 5.05-5.09 (m, 2H), 5.00-5.03 (m, 2H), 4.04 (s, 4H), 3.24-3.25 (d, 4H), 2.22 (s, 12H)
E型粘度計TVE-22H(東機産業社製)を用い、サンプル量1.1mL、コーンロータTE-1(1°34’、R24)、温度25℃で測定した。 <Measurement method of viscosity>
Using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.), the measurement was performed at a sample volume of 1.1 mL, a cone rotor TE-1 (1 ° 34', R24), and a temperature of 25 ° C.
GPC(常温ゲル浸透クロマトグラフィー)装置によって測定し、ポリエチレングリコール、ポリエチレンオキシド換算値として数平均分子量(Mn)と重量平均分子量(Mw)を算出した。
GPC装置:Shodex社製(GPC-101)、カラム:Shodex社製(KD803、KD805の直列)、カラム温度:50℃、溶離液:N,N-ジメチルホルムアミド(添加剤として、臭化リチウム-水和物(LiBr・H2O)が30mmol/L、リン酸・無水結晶(o-リン酸)が30mmol/L、テトラヒドロフラン(THF)が10ml/L)、流速:1.0ml/分
検量線作成用標準サンプル:東ソー社製 TSK 標準ポリエチレンオキサイド(重量平均分子量(Mw) 約900,000、150,000、100,000、30,000)、及び、ポリマーラボラトリー社製 ポリエチレングリコール(ピークトップ分子量(Mp)約12,000、4,000、1,000)。測定は、ピークが重なるのを避けるため、900,000、100,000、12,000、1,000の4種類を混合したサンプル、及び150,000、30,000、4,000の3種類を混合したサンプルの2サンプルを別々に測定した。 <Measurement method of molecular weight>
It was measured by a GPC (normal temperature gel permeation chromatography) apparatus, and the number average molecular weight (Mn) and the weight average molecular weight (Mw) were calculated as polyethylene glycol and polyethylene oxide equivalent values.
GPC apparatus: Shodex (GPC-101), column: Shodex (series of KD803 and KD805), column temperature: 50 ° C., eluent: N, N-dimethylformamide (lithium bromide-water as an additive) Japanese product (LiBr · H 2 O) 30 mmol / L, phosphoric acid / anhydrous crystal (o-phosphoric acid) 30 mmol / L, tetrahydrofuran (THF) 10 ml / L), flow velocity: 1.0 ml / min Standard samples for use: TSK standard polyethylene oxide manufactured by Toso (weight average molecular weight (Mw) about 900,000, 150,000, 100,000, 30,000) and polyethylene glycol manufactured by Polymer Laboratory (peak top molecular weight (Mp)). ) Approximately 12,000, 4,000, 1,000). For the measurement, in order to avoid overlapping peaks, a sample in which four types of 900,000, 100,000, 12,000, and 1,000 were mixed, and three types of 150,000, 30,000, and 4,000 were used. Two samples of the mixed sample were measured separately.
ポリイミド粉末20mgをNMRサンプル管(NMRサンプリングチューブスタンダード,φ5(草野科学社製))に入れ、重水素化ジメチルスルホキシド(DMSO-d6,0.05%TMS(テトラメチルシラン)混合品)(0.53mL)を添加し、超音波をかけて完全に溶解させた。この溶液をフーリエ変換型超伝導核磁気共鳴装置(FT-NMR)「AVANCE III」(BRUKER社製)を用いて500MHzのプロトンNMRを測定した。イミド化率は、イミド化前後で変化しない構造に由来するプロトンを基準プロトンとして決め、このプロトンのピーク積算値と、9.5ppm~10.0ppm付近に現れるアミド酸のNH基に由来するプロトンピーク積算値とを用い以下の式によって求めた。
イミド化率(%)=(1-α・x/y)×100
上記式において、xはアミック酸のNH基由来のプロトンピーク積算値、yは基準プロトンのピーク積算値、αはポリアミック酸(イミド化率が0%)の場合におけるアミック酸のNH基プロトン1個に対する基準プロトンの個数割合である。 <Measurement method of imidization rate>
20 mg of polyimide powder was placed in an NMR sample tube (NMR sampling tube standard, φ5 (manufactured by Kusano Kagaku Co., Ltd.)), and deuterated dimethyl sulfoxide (DMSO-d 6 , 0.05% TMS (tetramethylsilane) mixture) (0). .53 mL) was added and ultrasonically applied to completely dissolve. This solution was measured for proton NMR at 500 MHz using a Fourier transform infrared magnetic resonance apparatus (FT-NMR) “AVANCE III” (manufactured by BRUKER). The imidization rate is determined by using a proton derived from a structure that does not change before and after imidization as a reference proton, and the peak integrated value of this proton and the proton peak derived from the NH group of amic acid appearing in the vicinity of 9.5 ppm to 10.0 ppm. It was calculated by the following formula using the integrated value.
Imidization rate (%) = (1-α · x / y) × 100
In the above formula, x is the integrated proton peak value derived from the NH group of the amic acid, y is the integrated peak value of the reference proton, and α is one NH group proton of the amic acid in the case of polyamic acid (imidization rate is 0%). It is the number ratio of the reference protons to.
撹拌装置付き及び窒素導入管付きの100mLの四つ口フラスコに、DA-1(3.91g、16.0mmol)、DA-2(2.19g、6.41mmol)、DA-3(0.519g、4.80mmol)、及びDA-4(1.54g、4.81mmol)を量り取り、NMP(46.2g)を加えて、窒素を送りながら撹拌し溶解させた。このジアミン溶液を撹拌しながらCA-1(5.70g、25.4mmol)及びCA-2(1.20g、4.80mmol)を添加し、更に固形分濃度が15質量%になるようにNMP(39.1g)を加え、40℃で24時間撹拌してポリアミック酸溶液(A)(粘度:450mPa・s)を得た。ポリアミック酸の分子量は、Mn=11,200、Mw=26,900であった。 (Synthesis Example 5)
DA-1 (3.91 g, 16.0 mmol), DA-2 (2.19 g, 6.41 mmol), DA-3 (0.519 g) in a 100 mL four-necked flask with a stirrer and a nitrogen inlet tube. 4.80 mmol) and DA-4 (1.54 g, 4.81 mmol) were weighed, NMP (46.2 g) was added, and the mixture was stirred and dissolved while feeding nitrogen. While stirring this diamine solution, CA-1 (5.70 g, 25.4 mmol) and CA-2 (1.20 g, 4.80 mmol) were added, and NMP (NMP) was added so that the solid content concentration became 15% by mass. 39.1 g) was added, and the mixture was stirred at 40 ° C. for 24 hours to obtain a polyamic acid solution (A) (viscosity: 450 mPa · s). The molecular weight of the polyamic acid was Mn = 11,200 and Mw = 26,900.
撹拌装置付き及び窒素導入管付きの100mのL四つ口フラスコに、DA-5(5.10g、25.6mmol)及びDA-6(1.27g、6.41mmol)を取り、NMP(36.1g)を加えて、窒素を送りながら撹拌し溶解させた。このジアミン溶液を撹拌しながらCA-2(4.00g、16.0mmol)及びCA-3(4.42g、15.0mmol)を添加し、更に固形分濃度が15質量%になるようにNMP(47.7g)を加え、50℃で24時間撹拌してポリアミック酸溶液(B)(粘度:904mPa・s)を得た。ポリアミック酸の分子量は、Mn=14,600、Mw=37,500であった。 (Synthesis Example 6)
DA-5 (5.10 g, 25.6 mmol) and DA-6 (1.27 g, 6.41 mmol) were taken in a 100 m L four-necked flask with a stirrer and a nitrogen introduction tube, and NMP (36. 1 g) was added, and the mixture was stirred and dissolved while feeding nitrogen. While stirring this diamine solution, CA-2 (4.00 g, 16.0 mmol) and CA-3 (4.42 g, 15.0 mmol) were added, and NMP (NMP) was added so that the solid content concentration became 15% by mass. 47.7 g) was added, and the mixture was stirred at 50 ° C. for 24 hours to obtain a polyamic acid solution (B) (viscosity: 904 mPa · s). The molecular weight of the polyamic acid was Mn = 14,600 and Mw = 37,500.
撹拌装置付き及び窒素導入管付きの100mlの四つ口フラスコに得られたポリアミック酸溶液(A)(30g)を量り取り、NMP(15.0g)を加え、30分撹拌した。得られたポリアミック酸溶液に、無水酢酸(4.89g)及びピリジン(1.51g)を加えて、50℃で2時間30分加熱し、化学イミド化を行った。得られた反応液をメタノール(154mL)に撹拌しながら投入し、析出した沈殿物をろ取し、続いて、メタノール(154mL)で3回洗浄した。得られた樹脂粉末を60℃で12時間乾燥することで、ポリイミド樹脂粉末(A)を得た。このポリイミド樹脂粉末のイミド化率は64%であり、Mn=9,900、Mw=20,000であった。 (Synthesis Example 7)
The obtained polyamic acid solution (A) (30 g) was weighed in a 100 ml four-necked flask equipped with a stirrer and a nitrogen introduction tube, NMP (15.0 g) was added, and the mixture was stirred for 30 minutes. Acetic anhydride (4.89 g) and pyridine (1.51 g) were added to the obtained polyamic acid solution, and the mixture was heated at 50 ° C. for 2 hours and 30 minutes for chemical imidization. The obtained reaction solution was added to methanol (154 mL) with stirring, and the precipitated precipitate was collected by filtration, followed by washing with methanol (154 mL) three times. The obtained resin powder was dried at 60 ° C. for 12 hours to obtain a polyimide resin powder (A). The imidization ratio of this polyimide resin powder was 64%, Mn = 9,900, and Mw = 20,000.
合成例7で得られたポリイミド樹脂粉末(A)(3.00g)を100mL三角フラスコに量り取り、固形分濃度が12%になるようにNMP(22.0g)を加え、70℃で24時間撹拌し溶解させてポリイミド溶液(A)を得た。 (Synthesis Example 8)
The polyimide resin powder (A) (3.00 g) obtained in Synthesis Example 7 is weighed in a 100 mL Erlenmeyer flask, NMP (22.0 g) is added so that the solid content concentration becomes 12%, and the temperature is 70 ° C. for 24 hours. The mixture was stirred and dissolved to obtain a polyimide solution (A).
合成例8で得られたポリイミド溶液(A)(3.80g)と合成例6で得られたポリアミック酸溶液(B)(4.56g)を100mL三角フラスコに量り取り、T-1(0.114g)、NMP(1.64g)、GBL(6.00g)、及びBCS(4.00g)を添加して室温で3時間撹拌し、液晶配向剤(1)を得た。この液晶配向剤に、濁りや析出等の異常は見られず、均一な溶液であることが確認された。 (Example 1)
The polyimide solution (A) (3.80 g) obtained in Synthesis Example 8 and the polyamic acid solution (B) (4.56 g) obtained in Synthesis Example 6 were weighed into a 100 mL Erlenmeyer flask, and T-1 (0. 114 g), NMP (1.64 g), GBL (6.00 g), and BCS (4.00 g) were added and stirred at room temperature for 3 hours to obtain a liquid crystal aligning agent (1). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment agent, and it was confirmed that the solution was uniform.
T-1の代わりに、それぞれ、T-2、T-3、T-4、又はT-5を用いた以外は実施例1と同様の方法により実施例2~5の液晶配向剤(2)~(5)を得た。これらの液晶配向剤(2)~(5)には、いずれも、濁りや析出等の異常は見られず、均一な溶液であることが確認された。 (Examples 2 to 5)
Liquid crystal alignment agents (2) of Examples 2 to 5 in the same manner as in Example 1 except that T-2, T-3, T-4, or T-5 was used instead of T-1, respectively. ~ (5) was obtained. It was confirmed that all of these liquid crystal alignment agents (2) to (5) were uniform solutions without any abnormalities such as turbidity and precipitation.
合成例8で得られたポリイミド溶液(A)(3.80g)と合成例6で得られたポリアミック酸溶液(B)(4.56g)を100mLの三角フラスコに量り取り、NMP(1.64g)、GBL(6.00g)、及びBCS(4.00g)を添加して室温で3時間撹拌し、液晶配向剤(6)を得た。 (Comparative Example 1)
The polyimide solution (A) (3.80 g) obtained in Synthesis Example 8 and the polyamic acid solution (B) (4.56 g) obtained in Synthesis Example 6 were weighed into a 100 mL Erlenmeyer flask and NMP (1.64 g). ), GBL (6.00 g), and BCS (4.00 g) were added and stirred at room temperature for 3 hours to obtain a liquid crystal aligning agent (6).
T-1の代わりにT-6を用いた以外は実施例1と同様の方法により液晶配向剤(7)を得た。
なお、上記比較例1、2で得られた液晶配向剤(6)、(7)には、いずれも、濁りや析出等の異常は見られず、均一な溶液であることが確認された。 (Comparative Example 2)
A liquid crystal alignment agent (7) was obtained by the same method as in Example 1 except that T-6 was used instead of T-1.
The liquid crystal alignment agents (6) and (7) obtained in Comparative Examples 1 and 2 did not show any abnormalities such as turbidity and precipitation, and it was confirmed that they were uniform solutions.
実施例1で得られた液晶配向剤(1)を孔径1.0μmのフィルターで濾過した後、透明電極付きガラス基板上にスピンコート法により塗布した。80℃のホットプレート上で2分間乾燥させ、塗膜面に偏光板を介して消光比26:1の直線偏光した波長254nmの紫外線を0.25J/cm2照射した後、230℃の熱風循環式オーブンで20分間焼成を行い、膜厚100nmの液晶配向膜付き基板を得た。
得られた上記基板2枚を一組とし、一方の基板の液晶配向膜面に、直径6μmのスペーサーを散布した。この基板上にシール剤を印刷し、もう1枚の基板を、液晶配向膜面が向き合い、配向方向が0°になるようにして張り合わせた後、シール剤を硬化させて空セルを作製した。この空セルに減圧注入法によって、液晶MLC-7026-100(メルク社製)を注入し、注入口を封止して、液晶セルを得た。液晶セルの初期配向性を確認したところ、流動配向は確認されず、配向性は良好であった。このセルを120℃で60分間熱処理して、液晶セルを作製した。 (Example 6)
The liquid crystal alignment agent (1) obtained in Example 1 was filtered through a filter having a pore size of 1.0 μm, and then coated on a glass substrate with a transparent electrode by a spin coating method. Dried for 2 minutes at 80 ° C. on a hot plate, the extinction ratio 26 via a polarizing plate coated surface: After the first ultraviolet rays linearly polarized wavelength 254nm was irradiated 0.25 J / cm 2, the hot air circulation 230 ° C. It was baked in a formula oven for 20 minutes to obtain a substrate with a liquid crystal alignment film having a film thickness of 100 nm.
The two obtained substrates were combined into a set, and a spacer having a diameter of 6 μm was sprayed on the liquid crystal alignment film surface of one of the substrates. A sealant was printed on this substrate, and another substrate was bonded so that the liquid crystal alignment film surfaces faced each other and the orientation direction was 0 °, and then the sealant was cured to prepare an empty cell. A liquid crystal MLC-7026-100 (manufactured by Merck & Co., Inc.) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain a liquid crystal cell. When the initial orientation of the liquid crystal cell was confirmed, no flow orientation was confirmed, and the orientation was good. This cell was heat-treated at 120 ° C. for 60 minutes to prepare a liquid crystal cell.
上記手順で作製した液晶セルにおける液晶配向状態を偏光顕微鏡(ニコン社製、ECLIPSE E600 POL)を用いて観察した。液晶の配向が確認でき、且つ流動配向がないものを「良好」とし、配向が確認できないもの及び、流動配向があるものを「不良」と判定した。 [Evaluation method of liquid crystal orientation]
The liquid crystal orientation state in the liquid crystal cell produced by the above procedure was observed using a polarizing microscope (ECLIPSE E600 POL manufactured by Nikon Corporation). Those in which the orientation of the liquid crystal could be confirmed and there was no flow orientation were judged as "good", and those in which the orientation could not be confirmed and those with flow orientation were judged as "poor".
上記液晶セルをバックライト上に5日間置きエージングした後、60℃の温度下で1Vの電圧を60μs間印加し、500ms後の電圧を測定して、電圧がどのくらい保持できているかを電圧保持率として計算した。電圧保持率の測定には、東陽テクニカ社製のVHR-1を使用した。
この結果、液晶配向剤(1)からなる配向膜の60℃における電圧保持率は61.7%であった。 [Measurement of voltage retention]
After aging the liquid crystal cell on the backlight for 5 days, a voltage of 1 V is applied for 60 μs at a temperature of 60 ° C., and the voltage after 500 ms is measured to determine how much the voltage can be maintained. Calculated as. VHR-1 manufactured by Toyo Corporation was used for measuring the voltage holding ratio.
As a result, the voltage retention rate of the alignment film made of the liquid crystal alignment agent (1) at 60 ° C. was 61.7%.
液晶配向剤(1)の代わりに、それぞれ、表1に示した液晶配向剤を用いた以外は、実施例6と同様の方法で液晶セルを作製し、液晶配向性及び電圧保持率の評価を実施した。それぞれ得られた液晶セルの液晶配向性及び電圧保持率を表1に示す。 (Examples 7 to 10, Comparative Examples 3 to 4)
Liquid crystal cells were prepared in the same manner as in Example 6 except that the liquid crystal alignment agents shown in Table 1 were used instead of the liquid crystal alignment agent (1), and the liquid crystal orientation and voltage retention were evaluated. Carried out. Table 1 shows the liquid crystal orientation and voltage retention of the obtained liquid crystal cells.
Claims (20)
- 下記式(1)で表される構造を2つ以上有する芳香族化合物を含有することを特徴とする液晶配向剤。
- 前記芳香族化合物が、下記式(b1)で表される化合物である請求項1に記載の液晶配向剤。
- 前記式(b1)におけるnが2であり、Aが単結合又は2価の連結基を表す請求項2に記載の液晶配向剤。 The liquid crystal alignment agent according to claim 2, wherein n in the formula (b1) is 2, and A represents a single bond or a divalent linking group.
- 前記式(b1)において、nが2である場合の2価の連結基が、下記式(a-1)又は(a-2)で表される基である請求項2又は3に記載の液晶配向剤。
- 前記芳香族化合物が、分子量2000以下の化合物である請求項1~4のいずれか1項に記載の液晶配向剤。 The liquid crystal alignment agent according to any one of claims 1 to 4, wherein the aromatic compound is a compound having a molecular weight of 2000 or less.
- 前記芳香族化合物の含有量が、液晶配向剤の全量に対して、0.1~5質量%である請求項1~6のいずれか1項に記載の液晶配向剤。 The liquid crystal alignment agent according to any one of claims 1 to 6, wherein the content of the aromatic compound is 0.1 to 5% by mass with respect to the total amount of the liquid crystal alignment agent.
- 液晶を配向させる能力を有する重合体をさらに含有する請求項1~7のいずれか1項に記載の液晶配向剤。 The liquid crystal aligning agent according to any one of claims 1 to 7, further containing a polymer having an ability to orient the liquid crystal.
- ポリイミド前駆体及び該ポリイミド前駆体のイミド化物であるポリイミドからなる群から選ばれる少なくとも1種の重合体を含有する請求項1~8のいずれか1項に記載の液晶配向剤。 The liquid crystal alignment agent according to any one of claims 1 to 8, which contains at least one polymer selected from the group consisting of a polyimide precursor and a polyimide which is an imide of the polyimide precursor.
- 前記ポリイミド前駆体が、下記式(2)で表されるテトラカルボン酸二無水物を含有するテトラカルボン酸成分を用いて得られる請求項9に記載の液晶配向剤。
- 前記(x-1)が、下記式(x1-1)~(x1-6)からなる群から選ばれる請求項10に記載の液晶配向剤。
- 前記ポリイミド前駆体が、下記式(3)で表されるジアミンを含有するジアミン成分を用いて得られる請求項9~11のいずれか1項に記載の液晶配向剤。
- 前記ポリイミド前駆体が、窒素含有複素環(但し、ポリイミドが有するイミド環を除く。)、第二級アミノ基及び第三級アミノ基からなる群から選ばれる少なくとも一種の窒素含有構造を有するジアミンを含有するジアミン成分を用いて得られる請求項9~13のいずれか1項に記載の液晶配向剤。 The polyimide precursor is a diamine having at least one nitrogen-containing structure selected from the group consisting of a nitrogen-containing heterocycle (excluding the imide ring of the polyimide), a secondary amino group and a tertiary amino group. The liquid crystal aligning agent according to any one of claims 9 to 13, which is obtained by using the contained diamine component.
- 請求項1~14のいずれかに記載の液晶配向剤を基板に塗布し、焼成し、得られる膜に偏光された放射線を照射する液晶配向膜の製造方法。 A method for producing a liquid crystal alignment film, wherein the liquid crystal alignment agent according to any one of claims 1 to 14 is applied to a substrate, fired, and the obtained film is irradiated with polarized radiation.
- 温度150~250℃で焼成する請求項15に記載の液晶配向膜の製造方法。 The method for producing a liquid crystal alignment film according to claim 15, which is fired at a temperature of 150 to 250 ° C.
- 請求項1~14のいずれか1項に記載の液晶配向剤から形成されてなる液晶配向膜。 A liquid crystal alignment film formed from the liquid crystal alignment agent according to any one of claims 1 to 14.
- 請求項17に記載の液晶配向膜を具備する液晶表示素子。 A liquid crystal display element including the liquid crystal alignment film according to claim 17.
- IPS駆動方式又はFFS駆動方式である請求項18に記載の液晶表示素子。 The liquid crystal display element according to claim 18, which is an IPS drive system or an FFS drive system.
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6323913A (en) * | 1986-07-15 | 1988-02-01 | アモコ コ−ポレ−シヨン | Bismaleimide recipe containing olefin ether modifier |
JPH0224309A (en) * | 1988-07-13 | 1990-01-26 | Hitachi Ltd | Composition |
JPH04306244A (en) * | 1990-07-30 | 1992-10-29 | Shell Internatl Res Maatschappij Bv | Polyimide composition |
JP2009109987A (en) * | 2007-10-09 | 2009-05-21 | Chisso Corp | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
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JP3893659B2 (en) | 1996-03-05 | 2007-03-14 | 日産化学工業株式会社 | Liquid crystal alignment treatment method |
JP5177150B2 (en) * | 2008-01-25 | 2013-04-03 | 日産化学工業株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
KR102438830B1 (en) * | 2016-08-03 | 2022-08-31 | 닛산 가가쿠 가부시키가이샤 | Liquid crystal display element having a liquid crystal panel having a curved shape, and liquid crystal aligning agent therefor |
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- 2020-09-30 CN CN202080070176.8A patent/CN114502695A/en active Pending
- 2020-09-30 JP JP2021551405A patent/JPWO2021070714A1/ja active Pending
- 2020-09-30 KR KR1020227013831A patent/KR20220075357A/en unknown
- 2020-10-06 TW TW109134554A patent/TW202128963A/en unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6323913A (en) * | 1986-07-15 | 1988-02-01 | アモコ コ−ポレ−シヨン | Bismaleimide recipe containing olefin ether modifier |
JPH0224309A (en) * | 1988-07-13 | 1990-01-26 | Hitachi Ltd | Composition |
JPH04306244A (en) * | 1990-07-30 | 1992-10-29 | Shell Internatl Res Maatschappij Bv | Polyimide composition |
JP2009109987A (en) * | 2007-10-09 | 2009-05-21 | Chisso Corp | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
Also Published As
Publication number | Publication date |
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JPWO2021070714A1 (en) | 2021-04-15 |
TW202128963A (en) | 2021-08-01 |
KR20220075357A (en) | 2022-06-08 |
CN114502695A (en) | 2022-05-13 |
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