WO2021246431A1 - Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides - Google Patents

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

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WO2021246431A1
WO2021246431A1 PCT/JP2021/020937 JP2021020937W WO2021246431A1 WO 2021246431 A1 WO2021246431 A1 WO 2021246431A1 JP 2021020937 W JP2021020937 W JP 2021020937W WO 2021246431 A1 WO2021246431 A1 WO 2021246431A1
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Prior art keywords
liquid crystal
group
crystal alignment
alignment agent
carbon atoms
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PCT/JP2021/020937
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English (en)
Japanese (ja)
Inventor
達也 結城
玲久 小西
雄介 山本
崇 仲井
圭太 慈道
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日産化学株式会社
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Priority to JP2022528857A priority Critical patent/JPWO2021246431A1/ja
Priority to KR1020227038848A priority patent/KR20230021645A/ko
Priority to CN202180039057.0A priority patent/CN115885211A/zh
Publication of WO2021246431A1 publication Critical patent/WO2021246431A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • 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, and a liquid crystal display element.
  • liquid crystal displays have been widely used as display units for personal computers, smartphones, mobile phones, television receivers, and the like.
  • the liquid crystal display device includes, for example, a liquid crystal layer sandwiched between an element substrate and a color filter substrate, a pixel electrode and a common electrode that apply an electric field to the liquid crystal layer, and an alignment film that controls the orientation of liquid crystal molecules in the liquid crystal layer. It is equipped with a thin film transistor (TFT) or the like for switching an electric signal supplied to a pixel electrode.
  • TFT thin film transistor
  • a vertical electric field method such as a TN (Twisted Nematic) method and a VA (Vertical Alignment) method
  • a horizontal electric field method such as an IPS (In-Plane Switching) method and an FFS (Fringe Field Switching) method
  • IPS In-Plane Switching
  • FFS Frringe Field Switching
  • liquid crystal alignment film in industry is a film made of a polymer typified by a polyamic acid and / or an imidized polyimide formed on an electrode substrate, and the surface of the film is made of cotton or nylon. , It is manufactured by performing a so-called rubbing process of rubbing in one direction with a cloth such as polyester.
  • the rubbing process is a simple and highly productive industrially useful method.
  • scratches on the surface of the alignment film generated by the rubbing process, dust generation, the effects of mechanical force and static electricity, and the in-plane alignment process Various problems such as non-uniformity of the above have been clarified.
  • a photo-alignment method for imparting a liquid crystal alignment ability by irradiating with polarized radiation As an orientation treatment method instead of the rubbing treatment, a photo-alignment method for imparting a liquid crystal alignment ability by irradiating with polarized radiation is known.
  • a photoalignment method a method using a photoisomerization reaction, a method using a photocrosslinking reaction, a method using a photodecomposition reaction, and the like have been proposed (see, for example, Non-Patent Document 1 and Patent Document 1).
  • a method for improving the mechanical strength of the liquid crystal alignment film particularly the film strength
  • a method of adding a cross-linking agent to the liquid crystal alignment agent can be mentioned.
  • the stability of the liquid crystal orientation is also important. If the orientation stability is small, the liquid crystal does not return to the initial state when the liquid crystal is driven for a long time, which causes a decrease in contrast and burn-in (hereinafter referred to as AC afterimage).
  • AC afterimage As a means for solving these problems, a liquid crystal alignment agent containing a specific polyimide component and a specific hydroxyalkylamide compound has been proposed (see, for example, Patent Document 2).
  • the liquid crystal alignment agent is usually stored in a very low temperature environment (for example, at ⁇ 20 ° C.) from the time of manufacture to the time of shipment in order to prevent deterioration of the polymer.
  • a very low temperature environment for example, at ⁇ 20 ° C.
  • the film strength of the obtained liquid crystal alignment film is improved and the AC afterimage is suppressed.
  • the solid content contained in the liquid crystal alignment agent was precipitated during storage at a low temperature. Once deposited, the solid content is difficult to redissolve, which may cause problems such as printing defects in the manufacturing process of the liquid crystal display element.
  • the present invention is a liquid crystal alignment agent that can be suitably used for a liquid crystal alignment film having high film strength and a liquid crystal display element in which AC afterimage is suppressed, and a liquid crystal in which solid content does not precipitate during low temperature storage. It is intended to provide an orienting agent. Further, it is an object of the present invention to provide a liquid crystal alignment film obtained from the liquid crystal alignment agent and a liquid crystal display element having the liquid crystal alignment film.
  • a liquid crystal alignment agent containing the following component (A) and component (B).
  • Component Polymer (A) having the ability to orient the liquid crystal display
  • a liquid crystal alignment agent containing the following components (A') and (B').
  • (A') component Polymer (A') having the ability to orient the liquid crystal display.
  • N is an integer of 1 to 30.
  • L 1 ' is a divalent organic group having 1 to 10 carbon atoms, more L 1' may be the same or different.
  • a liquid crystal alignment agent that can be suitably used for a liquid crystal alignment film having high film strength and a liquid crystal display element in which AC afterimage is suppressed, and a liquid crystal alignment agent in which solid content does not precipitate during low temperature storage, and the same. It is possible to provide a liquid crystal alignment film obtained from a liquid crystal alignment agent and a liquid crystal display element having the liquid crystal alignment film.
  • liquid crystal alignment agent containing a specific hydroxyalkylamide compound, a liquid crystal alignment film formed by using the liquid crystal alignment agent, and a liquid crystal display element having the liquid crystal alignment film will be described in detail.
  • the description of the constituent elements is an example as an embodiment of the present invention, and is not specified in these contents.
  • the description of "(meth) acrylic” refers to both acrylic and methacrylic.
  • examples of the "halogen atom” include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
  • the liquid crystal aligning agent of the present invention is a polymer (A) (also referred to as a component (A) in the present invention) or a polymer (A') (also referred to as a component (A') in the present invention) having the ability to orient the liquid crystal. ).
  • the polymer (A') include compounds similar to those of the polymer (A), including preferable specific examples.
  • one aspect of the liquid crystal alignment agent of the present invention is the polymer (A) and the hydroxyalkylamide compound (B) represented by the formula (1) (also referred to as the component (B) in the present invention). contains.
  • another aspect of the liquid crystal alignment agent of the present invention is the hydroxyalkylamide compound (B') represented by the above polymer (A') and the above formula (1') (in the present invention, (B'). Also called an ingredient).
  • the liquid crystal alignment agent of the present invention contains a polymer having the ability to orient the liquid crystal as in the known one, but the polymer is not particularly limited as long as it has the ability to orient the liquid crystal.
  • polymers include polyimide precursors, polyimides of polyimide precursors, polyimides, acrylic polymers, methacrylic polymers, acrylamide polymers, methacrylamide polymers, polystyrenes, polysiloxanes, polyamides, polyesters, polyurethanes, polycarbonates, and polyureas. , Polyphenol (novolak resin), maleimide polymer, polymer introduced with a compound having an isocyanuric acid skeleton or a triazine skeleton, and the like.
  • the 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 compound (preferably tetracarboxylic acid dianhydride) selected from tetracarboxylic acid or a derivative thereof and diamine can be mentioned.
  • the polymer is a (meth) acrylic polymer, (meth) acrylic acid or a derivative thereof, (meth) acrylic acid ester or a derivative thereof can be mentioned.
  • the polymer is a (meth) acrylamide polymer, (meth) acrylamide or a derivative thereof can be mentioned.
  • the polymer is polystyrene, styrene or a derivative thereof may be mentioned.
  • polysiloxane a silane compound having a methoxy group or an ethoxy group can be mentioned.
  • the polymer is a polyamide, examples thereof include at least one dicarboxylic acid component and a diamine component selected from a dicarboxylic acid and a derivative thereof.
  • the polymer is polyester, at least one dicarboxylic acid component and a diol component selected from the dicarboxylic acid and its derivatives can be mentioned.
  • the polymer When the polymer is polyurethane, examples thereof include an isocyanate compound and a compound having a hydroxy group.
  • the polymer When the polymer is polycarbonate, bisphenol derivatives and phosgene or phosgene equivalents (eg, trichlorophosgene) or diphenyl carbonates can be mentioned.
  • the polymer When the polymer is polyurea, bisisocyanate derivatives and diamine components can be mentioned.
  • the polymer is a maleimide polymer, the maleimide derivative alone or copolymerization with styrene may be mentioned.
  • examples of the polymer have a compound having an isocyanuric acid skeleton or a triazine skeleton.
  • the polyimide precursor and the polyimide precursor are selected from the viewpoints of practicality as a liquid crystal alignment agent, mechanical strength of the coating film, and liquid crystal orientation.
  • One or more polymers (hereinafter, also referred to as polyimide-based polymers) selected from the group consisting of polyimides that are imidized products 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 polymerizing (polycondensing) a tetracarboxylic acid component composed of a tetracarboxylic acid dianhydride or a derivative thereof and a diamine component, and this polyimide precursor is used.
  • Polyimide can be obtained by imidization.
  • Derivatives of the tetracarboxylic dianhydride include a tetracarboxylic dianhydride, a tetracarboxylic dianyl ester, or a tetracarboxylic dianhydride.
  • Tetracarboxylic acid component examples include those obtained from a tetracarboxylic acid component containing an aromatic, acyclic aliphatic or alicyclic tetracarboxylic dianhydride.
  • the aromatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups including at least one carboxy group bonded to the aromatic ring.
  • the acyclic aliphatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups bonded to a chain hydrocarbon structure. However, it does not have to be composed only of a chain hydrocarbon structure, and may have an alicyclic structure or an aromatic ring structure as a part thereof.
  • the alicyclic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups including at least one carboxy group bonded to the alicyclic structure. However, none of these four carboxy groups are bonded to the aromatic ring. Further, it does not have to be composed only of an alicyclic structure, and may have a chain hydrocarbon structure or an aromatic ring structure as a part thereof.
  • the polyamic acid according to the present invention is preferably one obtained from a tetracarboxylic acid component containing a tetracarboxylic dianhydride represented by the following formula (2).
  • R 1 to R 4 each independently contain a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, and a fluorine atom. It represents a monovalent organic group or a phenyl group having 1 to 6 carbon atoms.
  • R 5 and R 6 independently represent a hydrogen atom or a methyl group.
  • J and k are integers of 0 or 1.
  • a 1 and a 2 are each independently a single bond, -O -, - CO -, -.
  • X is the above formulas (x-1) to (x-8) and (x-10) to (x).
  • the one selected from -13) can be mentioned.
  • the above formula (x-1) is preferably selected from the group consisting of the following formulas (x1-1) to (x1-6).
  • the amount of the tetracarboxylic dianhydride or its derivative represented by the above formula (2) is preferably 60 to 100 mol% based on 1 mol of the total tetracarboxylic acid component to be reacted with the diamine component, 80. It is 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 at least one diamine selected from the diamines represented by the following formulas (3) and (3i) is preferable.
  • Y 3 represents a divalent organic group represented by the following formula (O).
  • R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • Y 3i is represented by the following formula (O'). Represents a divalent organic group.
  • Ar represents a divalent benzene ring, a biphenyl structure, or a naphthalene ring.
  • the two Ars may be the same or different, and any hydrogen atom in the ring may be substituted with a monovalent substituent.
  • Ar' represents a divalent benzene ring or a biphenyl structure.
  • the two Ar's may be the same or different, and any hydrogen atom in the ring may be substituted with a monovalent substituent.
  • p ' is an integer of 0 or 1 .
  • Examples of the substituent of the ring include a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a fluoroalkyl group having 1 to 10 carbon atoms.
  • Examples thereof include a fluoroalkenyl group having 2 to 10 carbon atoms, a fluoroalkoxy group having 1 to 10 carbon atoms, a carboxy group and a hydroxy group, an alkyloxycarbonyl group having 1 to 10 carbon atoms, a cyano group and a nitro group.
  • the divalent organic group represented by the above formula (O) is preferably a divalent organic group represented by the following formulas (o-1) to (o-16) from the viewpoint of enhancing the liquid crystal orientation.
  • the divalent organic group represented by the above formula (O') is preferably a divalent organic group represented by the above formulas (o-7) to (o-16) from the viewpoint of enhancing the liquid crystal orientation.
  • Preferred specific examples of the diamine represented by the above formula (3i) include compounds represented by the following formulas (3i-1) to (3i-5).
  • the total ratio of the diamine represented by the formula (3) and the diamine represented by the formula (3i) is preferably 1 to 95 mol% with respect to 1 mol of the diamine component, and is preferably 1 to 90 mol%. More preferably, it is more preferably 5 to 90 mol%.
  • 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 a secondary amino group.
  • the 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.
  • Examples of the nitrogen-containing heterocycle that the diamine having a nitrogen-containing structure may have include pyrrole, imidazole, pyrazole, triazole, pyridine, pyrimidine, pyridazine, pyrazine, indole, benzimidazole, purine, quinoline, and isoquinoline.
  • Examples thereof include naphthylidine, quinoxalin, phthalazine, triazine, carbazole, aclysine, piperidine, piperazine, pyrrolidine, hexamethyleneimine and the like.
  • pyridine, pyrimidine, pyrazine, piperidine, piperazine, quinoline, carbazole or acridine are preferable.
  • the secondary amino group and the tertiary amino group that the diamine having the 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.
  • R is preferably a hydrogen atom or a methyl group.
  • diamine having a nitrogen-containing structure examples include 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminocarbazole, and N-methyl-3,6-diaminocarbazole.
  • 1,4-Bis- (4-aminophenyl) -pyrimidine, 3,6-diaminoacridine, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole the following formula (Dp- Examples thereof include compounds represented by 1) to (Dp-9) and compounds represented by the following formulas (z-1) to (z-18).
  • 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 retention rate 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.
  • a 1 is a single bond, -CH 2 -, - C 2 H 4 -, - C (CH 3) 2 -, - CF 2 -, - C (CF 3) 2 -, -O-, -CO-, -NH-, -N (CH 3 )-, -CONH-, -NHCO-, -CH 2 O-, -OCH 2- , -COO-, -OCO-, -CON ( CH 3 )-or -N (CH 3 ) CO-, m1 and m2 independently represent an integer of 0 to 4, and m1 + m2 represent an integer of 1 to 4. Equation (3b-2).
  • m3 and m4 each independently represent an integer of 1 to 5.
  • a 2 represents a linear or branched alkyl group having 1 to 5 carbon atoms
  • m5 represents 1 to 5.
  • a 3 and a 4 are each independently a single bond, -CH 2 -, - C 2 H 4 -, - C (CH 3) 2 -, - CF 2- , -C (CF 3 ) 2- , -O-, -CO-, -NH-, -N (CH 3 )-, -CONH-, -NHCO-, -CH 2 O-, -OCH 2- , -COO -, - OCO -, - CON (CH 3) - or -N (CH 3) CO- represents, m6 is an integer of 1-4).
  • X v1 to X v4 and X p1 to X p2 are independently-(CH 2 ) a- (a is an integer of 1 to 15), -CONH-, -NHCO-, and -CON (CH). 3) -, - NH -, - O -, - CH 2 O -, - CH 2 OCO -, - COO-, or -OCO- represent, X v5 is -O -, - CH 2 O - , - CH 2 Represents OCO-, -COO-, or -OCO-.
  • X a is a single bond, -O-, -NH-, or -O- (CH 2 ) m- O- (m is an integer of 1 to 6).
  • R v1 to R v4 and R 1a to R 1b independently represent 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. Represents a group.
  • a diamine having 6 to 30 carbon atoms having the above group "-N (D)-(D represents a carbamate-based protecting group)" in the molecule is represented by the following formulas (5-1) to (5-10). Examples include the represented compounds.
  • liquid crystal alignment agent of the present invention is characterized by containing the hydroxyalkylamide compound (B) represented by the following formula (1).
  • R is an alkyl group having 1 to 6 carbon atoms
  • R 1 and R 2 are independently hydrogen atoms or monovalent organic groups having 1 to 6 carbon atoms
  • A is a divalent organic group having 1 to 30 carbon atoms. Represents.
  • the alkyl group having 1 to 6 carbon atoms of R in the above formula (1) includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group and a tert-butyl group. , N-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group and the like.
  • the monovalent organic group having 1 to 6 carbon atoms of R 1 and R 2 in the above formula (1) includes an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and 2 to 6 carbon atoms.
  • Alkinyl group, or a hetero atom-containing group containing a group having a hetero atom between carbons of these groups, and a part or all of the hydrogen atoms of the above-mentioned alkyl group, alkenyl group, alkynyl group and hetero atom-containing group are substituted. Examples include groups substituted with groups.
  • Examples of the group having a 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, and examples thereof include -O- and -NR- (R).
  • R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -CO-, -S-, -CO-, and a group combining these. Of these, —O— is preferable.
  • substituents examples 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, hydroxy group and the like can be mentioned.
  • R 1 in the above formula (1) is preferably a hydrogen atom or a methyl group
  • R 2 is preferably a hydrogen atom
  • the divalent organic group having 1 to 30 carbon atoms of A in the above formula (1) includes, for example, a divalent hydrocarbon group and a divalent group having the above heteroatom between carbon and carbon of the hydrocarbon group.
  • heteroatom-containing group the divalent divalent organic group in which some or all of the hydrogen atoms substituted with substituents exemplified above R 1, R 2 hydrocarbon groups and divalent heteroatom-containing groups having And so on.
  • Examples of the divalent hydrocarbon group include alkenes such as methane, ethane, propane, and butane; alkenes such as ethylene, propene, butene, and pentene; and alkynes such as ethine, propine, butine, and pentine having 1 to 1 carbon atoms.
  • alkenes such as methane, ethane, propane, and butane
  • alkenes such as ethylene, propene, butene, and pentene
  • alkynes such as ethine, propine, butine, and pentine having 1 to 1 carbon atoms.
  • 30 chain hydrocarbons cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornan, adamantan and other cycloalkanes, cyclopropene, cyclobutene, cyclopentene, cyclohexene, norbornene and other cycloalkenes
  • hydrocarbons such as aromatic hydrocarbons having 6 to 30 carbon atoms such as hydrocarbons, benzene, toluene, xylene, mesitylene, naphthalene, methylnaphthalene, dimethylnaphthalene, anthracene and the like 2 Hydrocarbon groups of valence and the like can be mentioned.
  • a divalent hydrocarbon group having 1 to 30 carbon atoms is preferable, and a divalent chain hydrocarbon having 1 to 30 carbon atoms or an aromatic having 6 to 30 carbon atoms is more preferable.
  • a divalent hydrocarbon group obtained by removing two hydrogen atoms from a group hydrocarbon is preferable.
  • the divalent chain hydrocarbon having 1 to 30 carbon atoms is preferably a divalent chain hydrocarbon having 2 to 30 carbon atoms, and more preferably a divalent chain hydrocarbon having 2 to 16 carbon atoms.
  • the hydroxyalkylamide compound represented by the above formula (1) is preferably any of the compounds represented by the following formulas (b-1) to (b-3).
  • the preferable content of the hydroxyalkylamide compound represented by the above formula (1) in the liquid crystal alignment agent of the present invention is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the component (A), 0.1. ⁇ 30 parts by mass is more preferable.
  • ⁇ (B') component> Another aspect of the liquid crystal alignment agent of the present invention is characterized by containing a hydroxyalkylamide compound (B') represented by the following formula (1').
  • R ' is a group "* -C (R 2') 2 -C (R 1 ') 2 -OH " (* represents a bond .
  • N is an integer of 1 to 30.
  • L 1 ' is a divalent organic group having 1 to 10 carbon atoms, more L 1' may be the same or different.
  • the monovalent organic group having 1 to 6 carbon atoms and R 2 '' R 1 in the formula (1) ' can be mentioned structure illustrated in R 1 and R 2 in the formula (1), It is the same as R 1 and R 2 , respectively, including preferable specific examples.
  • Divalent organic groups for example, a divalent hydrocarbon group having 1 to 10 carbon atoms having 1 to 10 carbon atoms 'L 1 in the formula (1)', the carbon of the hydrocarbon group - above between carbon
  • a divalent heteroatom-containing group including a group having a heteroatom, a part or all of the hydrogen atoms contained in the divalent hydrocarbon group and the divalent heteroatom-containing group are R 1 , R in the above formula (1).
  • Examples thereof include a divalent organic group substituted with the substituent exemplified in 2.
  • Specific examples of the divalent hydrocarbon group include the hydrocarbon group exemplified by A in the above formula (1).
  • the 'L 1 in the formula (1)' is preferably a divalent hydrocarbon group having 1 to 10 carbon atoms, more preferably a divalent chain hydrocarbon of 1 to 10 carbon atoms, or C 6 -C A divalent hydrocarbon group obtained by removing 2 hydrogen atoms from 10 aromatic hydrocarbons is preferable.
  • the divalent chain hydrocarbon having 1 to 10 carbon atoms is preferably a divalent chain hydrocarbon having 2 to 10 carbon atoms, and more preferably a divalent chain hydrocarbon having 2 to 8 carbon atoms.
  • n in the above formula (1') an integer of 1 to 20 is more preferable, and an integer of 2 to 20 is further preferable.
  • the hydroxyalkylamide compound represented by the above formula (1') is preferably any of the compounds represented by the following formulas (b'-1) to (b'-5).
  • the preferable content of the hydroxyalkylamide compound represented by the above formula (1') in the liquid crystal alignment agent of the present invention is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the component (A'), and is 0. .1 to 30 parts by mass is more preferable.
  • the polyimide precursor polyamic acid used in the present invention can be produced by the following method. Specifically, the tetracarboxylic acid component and the diamine component are reacted 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 (. It can be synthesized by subjecting it to a polycondensation reaction).
  • organic solvent used in the above reaction examples include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, ⁇ -butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, and the like.
  • examples thereof include 1,3-dimethyl-2-imidazolidinone.
  • the polymer has high solvent solubility, it is represented by methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the following formulas [D-1] to [D-3].
  • D 1 represents an alkyl group having 1 to 3 carbon atoms
  • D 2 represents an alkyl group having 1 to 3 carbon atoms
  • D-3 represents an alkyl group having 1 to 4 carbon atoms.
  • the reaction can be carried out at any concentration, but is preferably 1 to 50% by mass, more preferably 5 to 30% by mass.
  • the initial reaction can be carried out at a high concentration and then the solvent can be added.
  • the ratio of the total number of moles of the diamine component to the total number of moles of the tetracarboxylic acid component is preferably 0.8 to 1.2. Similar to a normal polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the polyamic acid produced.
  • 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 antisolvent 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 a terminal-modified polymer obtained by using an appropriate terminal encapsulant together with the tetracarboxylic acid derivative and diamine as described above when producing the polyimide precursor.
  • the terminal modifier include acid anhydrides such as acetic anhydride, maleic anhydride, nagic anhydride, phthalic anhydride, itaconic anhydride, cyclohexanedicarboxylic acid anhydride, 3-hydroxyphthalic anhydride, and trimetic acid anhydride.
  • Di-tert-butyl dicarbonate Di-tert-butyl dicarbonate; aniline, 2-aminophenol, 3-aminophenol, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-amino Examples thereof include monoamine compounds such as benzoic acid; monoisocyanate compounds such as ethyl isocyanate, phenyl isocyanate and naphthyl isocyanate.
  • the ratio of the terminal modifier to be used is preferably 40 mol parts or less, more preferably 30 mol parts or less, based on 100 mol parts in total of the 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.
  • the ring closure rate (also referred to as imidization rate) of the functional group of the polyamic acid or the polyamic acid ester does not necessarily have to be 100%, and can be arbitrarily adjusted according to the intended use and purpose.
  • thermal imidization in which the solution of the polyamic acid or the polyamic acid ester is heated as it is, or a catalyst is added to the solution of the polyamic acid or the polyamic acid ester.
  • Catalytic imidization can be mentioned.
  • the temperature for thermal imidization is 100 to 400 ° C., preferably 120 to 250 ° C., and it is preferable to remove the water produced by the imidization reaction from the outside of the system.
  • Catalyst imidization can be carried out by adding a basic catalyst and an acid anhydride to a solution of the polymer and stirring at ⁇ 20 to 250 ° C., preferably 0 to 180 ° C.
  • the amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times the amount of the amic acid group or the amic acid ester group, and the amount of the acid anhydride is 1 to 1 to 1 to the amic acid group or the amic acid ester group. It is 50 mol times, preferably 3 to 30 mol times.
  • the basic catalyst include pyridine, triethylamine, trimethylamine, and tributylamine trioctylamine.
  • 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, and among them, acetic anhydride is preferable because it facilitates purification after the reaction is completed.
  • the imidization rate by catalytic imidization can be controlled by adjusting the amount of catalyst, the reaction temperature, and the reaction time.
  • the reaction solution When recovering the produced polyimide from the reaction solution of catalyst imidization, the reaction solution may be put into a solvent and precipitated.
  • the solvent used for precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellsolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, water and the like.
  • the polymer put into a solvent and precipitated can be collected by filtration and then dried at room temperature or by heating under normal pressure or reduced pressure.
  • impurities in the polymer can be reduced.
  • the solvent at this time include alcohols, ketones, hydrocarbons, and the like, and it is preferable to use three or more kinds of solvents selected from these because the efficiency of purification is further improved.
  • the polyamic acid, polyamic acid ester and polyimide used in the present invention preferably have a solution viscosity of, for example, 10 to 1000 mPa ⁇ s when the solution is made into a solution having a concentration of 10 to 15% by mass, from the viewpoint of workability. , Not particularly limited.
  • the solution viscosity (mPa ⁇ s) of the polymer is a polymer having a concentration of 10 to 15% by mass prepared by using a good solvent of the polymer (for example, ⁇ -butyrolactone, N-methyl-2-pyrrolidone, etc.). The values of the solution were measured at 25 ° C. using an E-type rotational viscometer.
  • the polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the polyamic acid, polyamic acid ester and polyimide is preferably 1,000 to 500,000, more preferably 2,000. ⁇ 500,000.
  • the molecular weight distribution (Mw / Mn) represented by the ratio of Mw to the polystyrene-equivalent number average molecular weight (Mn) measured by GPC is preferably 15 or less, more preferably 10 or less. Within such a molecular weight range, good liquid crystal orientation of the liquid crystal display element can be ensured.
  • liquid crystal alignment agent for example, the hydroxyalkylamide compound of the above formula (1) or (1') is contained in a solution in which a polymer having the ability to orient the liquid crystal is dissolved in a solvent.
  • a polymer having the ability to orient the liquid crystal examples include the added form.
  • the content (concentration) of the polymer contained in the liquid crystal alignment agent of the present invention can be appropriately changed by setting the thickness of the coating film to be formed, but it is a point that a uniform and defect-free coating film is formed. 1% by mass or more is preferable, and 10% by mass or less is preferable from the viewpoint of storage stability of the solution.
  • the content of the hydroxyalkylamide compound of the above formula (1) or (1') is the content of the polymer contained in the liquid crystal alignment agent and the hydroxyalkylamide compound of the above formula (1) or (1'). It is preferably 1 to 15% by mass, more preferably 2 to 10% by mass, and particularly preferably 2 to 8% by mass with respect to the total of.
  • the solvent contained in the liquid crystal alignment agent is not particularly limited as long as the polymer component is uniformly dissolved.
  • Specific examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethyllactamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethylsulfoxide, and ⁇ -butyrolactone.
  • ⁇ -Valerolactone 1,3-dimethyl-2-imidazolidinone, methylethylketone, cyclohexanone, cyclopentanone, 3-methoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, N- (n-propyl) -2-pyrrolidone, N-isopropyl-2-pyrrolidone, N- (n-butyl) -2-pyrrolidone, N- (tert-butyl) -2-pyrrolidone, N- (n-pentyl) ) -2-Pyrrolidone, N-methoxypropyl-2-pyrrolidone, N-ethoxyethyl-2-pyrrolidone, N-methoxybutyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone (collectively, "good solvent”) Also known as).
  • N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide or ⁇ -butyrolactone are preferable.
  • the content of the good solvent is preferably 20 to 99% by mass, more preferably 20 to 90% by mass, and particularly preferably 30 to 80% by mass based on the total amount of the solvent contained in the liquid crystal alignment agent.
  • the solvent contained in the liquid crystal alignment agent is a mixed solvent in which a solvent (also referred to as a poor solvent) that improves the coatability when the liquid crystal alignment agent is applied and the surface smoothness of the coating film is used in addition to the above solvent. Is preferred. Specific examples of the solvent to be used in combination are described below, but the present invention is not limited thereto.
  • diisopropyl ether diisobutyl ether, diisobutylcarbinol (2,6-dimethyl-4-heptanol)
  • ethylene glycol dimethyl ether ethylene glycol diethyl ether
  • ethylene glycol dibutyl ether 1,2-butoxyetan
  • diethylene glycol dimethyl ether diethylene glycol diethyl ether.
  • the content of the poor solvent is preferably 1 to 80% by mass, more preferably 10 to 80% by mass, and particularly preferably 20 to 70% by mass, based on the total amount of the solvent contained in the liquid crystal alignment agent.
  • the type and content of the poor solvent are appropriately selected according to the liquid crystal alignment agent coating device, coating conditions, coating environment, and the like.
  • diisobutylcarbinol diisobutylcarbinol, propylene glycol monobutyl ether, propylene glycol diacetate, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monobutyl ether, ethylene.
  • Glycol monobutyl ether acetate or diisobutyl ketone is preferred.
  • Preferred solvent combinations of good and poor solvents include N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone and ⁇ -butyrolactone and ethylene glycol monobutyl ether, and N-methyl-2-.
  • the liquid crystal alignment agent of the present invention may additionally contain a component other than the polymer component and the solvent (hereinafter, also referred to as an additive component).
  • additive components include an adhesion aid for enhancing the adhesion between the liquid crystal alignment film and the substrate and the adhesion between the liquid crystal alignment film and the sealing material, and a compound for increasing the strength of the liquid crystal alignment film (hereinafter,).
  • Also referred to as a crosslinkable compound a dielectric for adjusting the dielectric constant and electrical resistance of the liquid crystal alignment film, a conductive substance, and the like can be mentioned.
  • the crosslinkable compound includes, for example, an oxylanyl group, an oxetanyl group, a protected isocyanate group, a protected isothiocyanate group, and an oxazoline ring structure from the viewpoint of exhibiting good resistance to AC afterimages and improving film strength.
  • a compound selected from the compounds represented by the following formula (e) can be mentioned.
  • (A is an integer of .m 1-6 representing the (m + n) valent organic group having an aromatic ring
  • n represents 0 to 4 representing an integer .
  • R e is R f, each independently, hydrogen Represents an atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkynyl group having 2 to 6 carbon atoms.
  • the aromatic ring of A may be substituted with a monovalent group.
  • Specific examples of the valent group include monovalent organic groups represented by Ar substituents of the above formula (O) (excluding alkoxy groups having 1 to 10 carbon atoms).
  • the compound having an oxylanyl group examples include the compound described in paragraph [0037] of JP-A No. 10-338880 and the compound having a triazine ring as a skeleton described in International Publication No. 2017/170483. Examples thereof include compounds having more than one oxylanyl group.
  • the compound having an oxetanyl group include the compounds having two or more oxetanyl groups described in paragraphs [0170] to [0175] of International Publication No. 2011/132751.
  • the compound having a protected isocyanate group include the compounds having two or more protected isocyanate groups described in paragraphs [0046] to [0047] of Japanese Patent Application Laid-Open No. 2014-224978, International Publication No. 2015/141598.
  • the compounds having three or more protected isocyanate groups described in paragraphs [0119] to [0120] of the above are mentioned, and the compounds represented by the following formulas (bi-1) to (bi-3) may be used. ..
  • Specific examples of the compound having a protected isothiocyanate group include the compounds having two or more protected isothiocyanate groups described in Japanese Patent Application Laid-Open No. 2016-2000798.
  • Specific examples of the compound having a group containing an oxazoline ring structure include compounds containing two or more oxazoline structures described in paragraph [0115] of Japanese Patent Application Laid-Open No. 2007-286597.
  • Specific examples of the compound having a group containing a Meldrum's acid structure include the compound having two or more Meldrum's acid structures described in International Publication No. 2012/091088.
  • Specific examples of the compound having a cyclocarbonate group include the compound described in International Publication No. 2011/155577.
  • hydroxyalkylamide compounds other than the compounds represented by the above formulas (1) and (1') include International Publication No. 2015/072554 and paragraph [0058] of Japanese Patent Application Laid-Open No. 2016-118753.
  • the compound may be a compound represented by the following formulas (hd1-1) to (hd1-4).
  • Examples of the (m + n) -valent organic group having an aromatic ring in A of the above formula (e) include an (m + n) -valent aromatic hydrocarbon group having 6 to 30 carbon atoms and an aromatic hydrocarbon group having 6 to 30 carbon atoms. Examples thereof include a (m + n) valent organic group bonded directly or via a linking group, and a (m + n) valent group having an aromatic heterocycle. Examples of the aromatic hydrocarbon include benzene and naphthalene.
  • aromatic heterocycle examples include a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, an isoquinoline ring, a carbazole ring, a pyridazine ring, a pyrazine ring, a benzimidazole ring, an indole ring, a quinoxaline ring, and an acridin ring. And so on.
  • the linking group includes an alkylene group having 1 to 10 carbon atoms, -NR- (R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), an alkylene group having a fluorine atom and 1 to 10 carbon atoms, or the above-mentioned alkylene group. Examples thereof include a group obtained by removing one hydrogen atom from the group, a divalent or trivalent cyclohexane ring, and the like. Any hydrogen atom of the alkylene group may be substituted with an organic group such as a fluorine atom or a trifluoromethyl group. Specific examples include the compounds described in International Publication No. 2010/074269 and the compounds represented by the following formulas (e-1) to (e-10).
  • the above compound is an example of a crosslinkable compound, and is not limited thereto.
  • components other than the above disclosed in International Publication No. 2015/060357 on pages 53 [0105] to 55 [0116] can be mentioned.
  • two or more kinds of crosslinkable compounds may be combined.
  • the content of the crosslinkable compound in the liquid crystal aligning agent of the present invention is preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the polymer component contained in the liquid crystal aligning agent, and the crosslinking reaction proceeds. In addition, from the viewpoint of exhibiting good resistance to AC afterimages, it is more preferably 1 to 15 parts by mass.
  • adhesion aid examples include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, and N.
  • -Styryltrimethoxysilane 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxy Silane cups such as silane, tris- (trimethoxysilylpropyl) isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isoxapropyltriethoxysilane, etc. Ring agent can be mentioned.
  • silane coupling agent when used, it should be 0.1 to 30 parts by mass with respect to 100 parts by mass of the polymer component contained in the liquid crystal alignment agent from the viewpoint of exhibiting good resistance to AC afterimage. It is preferable, more preferably 0.1 to 20 parts by mass.
  • the liquid crystal alignment film of the present invention is formed by using the liquid crystal alignment agent of the present invention.
  • Preferred embodiments of the method for producing a liquid crystal alignment film of the present invention include, for example, a step of applying the above liquid crystal alignment agent to a substrate (step (1)) and a step of firing the applied liquid crystal alignment agent (step (2)).
  • a method for producing a liquid crystal alignment film including a step (step (3)) of aligning the film obtained in the step (2) can be mentioned.
  • the substrate to which the liquid crystal alignment agent used in the present invention is applied is not particularly limited as long as it is a highly transparent substrate, and a glass substrate, a silicon nitride substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like can also be used. At that time, it is preferable to use a substrate on which an ITO electrode or the like for driving the liquid crystal is formed, from the viewpoint of simplifying the process. Further, in the reflective liquid crystal display element, an opaque object such as a silicon wafer can be used if only one side of the 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, inkjet method, spray method and the like. Among them, the coating method by the inkjet method and the film forming method can be preferably used.
  • the step (2) is a step of firing the liquid crystal alignment agent applied on the substrate to form a film.
  • the solvent is evaporated by a heating means such as a hot plate, a heat circulation type oven or an IR (infrared) type oven, or the heat of the amic acid or the amic acid ester in the polymer is generated. It can be imidized.
  • the drying and firing steps after applying the liquid crystal alignment agent of the present invention can be performed at any temperature and time, and may be performed a plurality of times.
  • the temperature at which the solvent of the liquid crystal alignment agent is evaporated can be, for example, 40 to 180 ° C.
  • the firing time is not particularly limited, and examples thereof include 1 to 10 minutes or 1 to 5 minutes.
  • a step of firing in a temperature range of, for example, 150 to 300 ° C. or 150 to 250 ° C. can be performed. ..
  • the firing time is not particularly limited, and examples thereof include a firing time of 5 to 40 minutes or 5 to 30 minutes. 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.
  • the step (3) is, in some cases, a step of orienting the film obtained in the step (2). That is, in a vertically oriented liquid crystal display element such as a VA method or a PSA mode, the formed coating film can be used as it is as a liquid crystal alignment film, but the coating film may be subjected to an alignment ability imparting treatment.
  • a method for aligning the liquid crystal alignment film 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, heat treatment is performed at a temperature of 150 to 250 ° C.
  • 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 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 substrate having the film-like substance may be irradiated while being heated at 50 to 250 ° C.
  • 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 contact-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 substance 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.
  • the solvent at the time of the contact treatment may be heated at room temperature, but is preferably 10 to 80 ° C. Above all, 20 to 50 ° C. is preferable.
  • ultrasonic treatment or the like may be performed as necessary.
  • rinsing also referred to as rinsing
  • firing with a low boiling point solvent such as water, methanol, ethanol, 2-propanol, acetone, or methyl ethyl ketone.
  • the firing temperature is preferably 150 to 300 ° C. Above all, 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 for the coating film irradiated with the above radiation is more preferably at 50 to 300 ° C. for 1 to 30 minutes, and even more preferably at 120 to 250 ° C. for 1 to 30 minutes.
  • the liquid crystal display element of the present invention has the liquid crystal alignment film of the present invention.
  • 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 method or an FFS method 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 manufactured by obtaining a substrate with a liquid crystal alignment film obtained from the liquid crystal alignment agent of the present invention, producing a liquid crystal cell by a known method, and arranging the liquid crystal in the liquid crystal cell. Can be done. Specifically, the following two methods can be mentioned.
  • the first method first, two substrates are arranged facing each other through a gap (cell gap) so that the liquid crystal alignment films face each other.
  • the peripheral portions of the two substrates are bonded together using a sealant, and the liquid crystal composition is injected and filled into the surface of the substrate and the cell gap partitioned by the sealant to contact the film surface, and then the injection holes are sealed. Stop.
  • the second method is a method called the ODF (One Drop Fill) method.
  • ODF One Drop Fill
  • an ultraviolet light-curable sealant is applied to a predetermined place on one of the two substrates on which the liquid crystal alignment film is formed, and the liquid crystal composition is further applied to a predetermined number of places on the liquid crystal alignment film surface. Is dropped. Then, the other substrate is bonded so that the liquid crystal alignment film faces each other, and the liquid crystal composition is spread over the entire surface of the substrate and brought into contact with the film surface. Next, the entire surface of the substrate is irradiated with ultraviolet light to cure the sealant.
  • the two substrates are arranged so as to face each other so that the rubbing directions of the coating films are opposite to each other at a predetermined angle, for example, orthogonal or antiparallel.
  • the orientation directions are arranged so as to face each other at a predetermined angle, for example, orthogonal or antiparallel.
  • the sealing agent for example, an epoxy resin containing a curing agent and aluminum oxide spheres as a spacer can be used.
  • the liquid crystal include a nematic liquid crystal and a smectic liquid crystal, and among them, the nematic liquid crystal is preferable.
  • 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. Examples of the polarizing plate include a polarizing plate in which a polarizing film called "H film" in which polyvinyl alcohol is stretch-oriented and iodine is absorbed sandwiched between a cellulose acetate protective film or a polarizing plate made of the H film itself. ..
  • NMP N-methyl-2-pyrrolidone
  • GBL ⁇ -butyl lactone
  • BCS butyl cellosolve
  • DMF N, N-dimethylformamide
  • DAH-1 to DAH-2 Compounds represented by the following formulas (DAH-1) to (DAH-2), respectively.
  • AD-1 Compound represented by the following formula (AD-1)
  • AD-2 Compound represented by the following formula (AD-2). The compound was synthesized by the synthetic method described in Japanese Patent Publication No. 2018-537481 (paragraphs [0079] to [0080], FIG. 5).
  • AD-3 A compound represented by the following formula (AD-3).
  • the viscosity of the polyamic acid solution is measured using an E-type viscometer (TVE-22H, manufactured by Toki Sangyo Co., Ltd.) at a sample volume of 1.1 mL, a cone rotor TE-1 (1 ° 34', R24), and a temperature of 25 ° C. did.
  • E-type viscometer TVE-22H, manufactured by Toki Sangyo Co., Ltd.
  • Liquid crystal alignment agents (AL-2) to (AL-3) can be obtained by performing the same operation as in Comparative Example 1 except that AD-2 to AD-3 are used instead of AD-1. rice field.
  • a liquid crystal cell having a configuration of an FFS mode liquid crystal display element was manufactured.
  • a substrate with electrodes was prepared.
  • a glass substrate having a rectangular shape of 30 mm ⁇ 35 mm and a thickness of 0.7 mm was used.
  • An ITO electrode having a solid pattern forming a counter electrode as a first layer is formed on the substrate, and a film is formed on the counter electrode of the first layer as a second layer by a CVD method.
  • a SiN (silicon nitride) film was formed.
  • As the SiN film of the second layer a film having a film thickness of 500 nm that functions as an interlayer insulating film was used.
  • a comb-shaped pixel electrode formed by patterning an ITO film as the third layer is arranged, and two pixels of the first pixel and the second pixel are formed.
  • the size of each pixel was 10 mm in length and about 5 mm in width.
  • the counter electrode of the first layer and the pixel electrode of the third layer were electrically insulated by the action of the SiN film of the second layer.
  • the pixel electrode of the third layer has a comb-teeth shape in which a plurality of electrode elements having a width of 3 ⁇ m in which the central portion is bent at an internal angle of 160 ° are arranged in parallel with an interval of 6 ⁇ m.
  • the pixel had a first region and a second region with a line connecting the bent portions of the plurality of electrode elements as a boundary.
  • liquid crystal alignment agents (AL-1) to (AL-3) obtained in Comparative Example 1 and Examples 1 and 2 were filtered through a filter having a pore size of 1.0 ⁇ m, and then the substrate with the electrode was prepared. It was applied by spin coating to a glass substrate having a columnar spacer having a height of 4 ⁇ m and having an ITO film formed on the back surface. After drying on a hot plate at 80 ° C. for 2 minutes, baking was performed at 230 ° C. for 30 minutes using an IR oven to form a coating film having a thickness of 100 nm. The surface of the coating film was irradiated with polarized ultraviolet rays at 300 mJ / cm 2 to perform an orientation treatment.
  • Firing was performed again at 230 ° C. for 30 minutes using an IR oven to obtain a substrate with a liquid crystal alignment film.
  • a set of the above two substrates is printed with a sealant (XN-1500T manufactured by Mitsui Chemicals, Inc.) around it, leaving the liquid crystal injection port, and the other substrate is oriented with the liquid crystal alignment film surface facing 0.
  • the sealant was cured to prepare an empty cell.
  • a liquid crystal MLC-3019 manufactured by Merck & Co., Inc.
  • the FFS-driven liquid crystal cell obtained as described above was heated at 110 ° C. for 1 hour, left overnight, and then the following afterimage evaluation was performed.
  • the rotation angle when the liquid crystal cell was rotated from the angle at which the second region of the first pixel became the darkest to the angle at which the first region became the darkest was calculated as the angle ⁇ .
  • the second region and the first region were compared, and the same angle ⁇ was calculated.
  • the average value of the angles ⁇ of the first pixel and the second pixel was calculated as the angle ⁇ of the liquid crystal cell.
  • a rubbing resistance test was conducted to confirm the strength of the liquid crystal alignment film formed by using the liquid crystal alignment agents obtained in Examples 1 and 2 and Comparative Example 1.
  • the liquid crystal alignment agents (AL-1) to (AL-3) obtained in Comparative Example 1 and Examples 1 and 2 were applied to the ITO surface of a glass substrate having an ITO electrode on the entire surface by spin coating. After drying on a hot plate at 80 ° C. for 2 minutes, baking was performed at 230 ° C. for 30 minutes using an IR oven to form a coating film having a thickness of 100 nm. The surface of the coating film was irradiated with polarized ultraviolet rays at 300 mJ / cm 2 to perform an orientation treatment.
  • Firing was performed again at 230 ° C. for 30 minutes using an IR oven to obtain a substrate with a liquid crystal alignment film.
  • the substrate with the liquid crystal alignment film obtained as described above is rubbed with a rayon cloth (roller diameter: 120 mm, roller rotation speed: 1000 rpm, moving speed: 20 mm / sec, pushing length: 0.6 mm), and then a microscope. Observation was performed and the rubbing resistance of the liquid crystal alignment film was evaluated. Those with no rubbing streaks on the film surface were evaluated as " ⁇ ", and those with streaks were evaluated as "x".
  • Table 1 shows the evaluation results of the afterimage evaluation for the FFS-driven liquid crystal cell and the evaluation results of the rubbing resistance test of the liquid crystal alignment film in Comparative Example 1 and Examples 1 and 2.
  • the cross-linking agent solutions (Sol-1) to (Sol-3) of Comparative Example 2 and Examples 3 to 4 are used. , The following low temperature storage stability test was performed.
  • AD-2 having an alkylamide moiety and having an alkyl group on N of the amide group
  • AD-3 having an alkylamide moiety and having an ethylene glycol chain is oriented. It was found that when applied to the agent, a good liquid crystal orientation and high rubbing resistance can be imparted, and an orientation agent having excellent low temperature storage stability can be formed.
  • the liquid crystal alignment film obtained from the liquid crystal alignment agent of the present invention can be suitably used for various liquid crystal display elements represented by IPS drive type and FFS drive type liquid crystal display elements. These display elements are not limited to liquid crystal displays intended for display, and are also useful in dimming windows and optical shutters that control the transmission and blocking of light.

Abstract

L'invention concerne un agent d'alignement de cristaux liquides qui peut être utilisé de façon appropriée pour un film d'alignement de cristaux liquides ayant une résistance de film élevée et pour un élément d'affichage à cristaux liquides dans lequel des images rémanentes CA sont supprimées, et qui ne précipite pas de contenu solide lorsqu'il est stocké à basse température. L'invention concerne en outre un film d'alignement de cristaux liquides obtenu à partir dudit agent d'alignement de cristaux liquides, et un élément d'affichage à cristaux liquides comportant ledit film d'alignement de cristaux liquides.　L'agent d'alignement de cristaux liquides contient un composant (A) et un composant (B). Composant (A) : L'invention concerne un polymère (A) ayant la capacité d'aligner des cristaux liquides. Composant (B) : Un composé hydroxyalkylamide (B) est représenté par la formule (1). (R représente un groupe alkyle en C1-6, R1 et R2 représentent chacun indépendamment un atome d'hydrogène ou un groupe organique monovalent en C1-6, et A représente un groupe organique divalent en C1-30.)
PCT/JP2021/020937 2020-06-05 2021-06-02 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides WO2021246431A1 (fr)

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CN202180039057.0A CN115885211A (zh) 2020-06-05 2021-06-02 液晶取向剂、液晶取向膜以及液晶显示元件

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5117970A (fr) * 1974-03-25 1976-02-13 Roehm & Haas Gmbh
WO2015072554A1 (fr) * 2013-11-15 2015-05-21 日産化学工業株式会社 Agent d'alignement de cristaux liquides et élément d'affichage à cristaux liquides l'utilisant

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3893659B2 (ja) 1996-03-05 2007-03-14 日産化学工業株式会社 液晶配向処理方法
JP7259328B2 (ja) 2016-11-18 2023-04-18 日産化学株式会社 液晶配向剤、液晶配向膜、及び液晶表示素子

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5117970A (fr) * 1974-03-25 1976-02-13 Roehm & Haas Gmbh
WO2015072554A1 (fr) * 2013-11-15 2015-05-21 日産化学工業株式会社 Agent d'alignement de cristaux liquides et élément d'affichage à cristaux liquides l'utilisant

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KR20230021645A (ko) 2023-02-14

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