Classifications

• • 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
• • 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
• • C—CHEMISTRY; METALLURGY
  • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1003—Preparatory processes
  • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
  • C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1075—Partially aromatic polyimides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1075—Partially aromatic polyimides
  • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • 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
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
  • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
  • G02F1/133723—Polyimide, polyamide-imide
• • 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]
• • 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.

Landscapes

• Chemical & Material Sciences (AREA)
• Physics & Mathematics (AREA)
• Organic Chemistry (AREA)
• Nonlinear Science (AREA)
• Crystallography & Structural Chemistry (AREA)
• Polymers & Plastics (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Mathematical Physics (AREA)
• General Physics & Mathematics (AREA)
• Optics & Photonics (AREA)
• Materials Engineering (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Engineering & Computer Science (AREA)
• Geometry (AREA)
• Liquid Crystal (AREA)
• Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Priority Applications (4)

Applications Claiming Priority (2)

Publications (1)

Family

ID=75437911

Family Applications (1)

Country Status (4)

Citations (4)

Family Cites Families (4)

• 2020
  • 2020-09-30 JP JP2021551405A patent/JP7533470B2/ja active Active
  • 2020-09-30 CN CN202080070176.8A patent/CN114502695A/zh active Pending
  • 2020-09-30 WO PCT/JP2020/037265 patent/WO2021070714A1/ja active Application Filing
  • 2020-09-30 KR KR1020227013831A patent/KR20220075357A/ko unknown
• 2024
  • 2024-06-10 JP JP2024093465A patent/JP2024126027A/ja active Pending

Patent Citations (4)

Also Published As

Similar Documents

Legal Events