WO2018117133A1 - Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et dispositif d'affichage à cristaux liquides - Google Patents

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

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WO2018117133A1
WO2018117133A1 PCT/JP2017/045625 JP2017045625W WO2018117133A1 WO 2018117133 A1 WO2018117133 A1 WO 2018117133A1 JP 2017045625 W JP2017045625 W JP 2017045625W WO 2018117133 A1 WO2018117133 A1 WO 2018117133A1
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liquid crystal
formula
substrate
group
polymer
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PCT/JP2017/045625
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English (en)
Japanese (ja)
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永井　健太郎
尚士 鉄谷
秀則 石井
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日産化学工業株式会社
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Priority to CN201780086602.5A priority Critical patent/CN110300922B/zh
Priority to JP2018558020A priority patent/JP7151485B2/ja
Priority to CN202210349222.9A priority patent/CN114702393A/zh
Priority to KR1020197020490A priority patent/KR102521135B1/ko
Publication of WO2018117133A1 publication Critical patent/WO2018117133A1/fr
Priority to JP2022000347A priority patent/JP7279823B2/ja

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
    • C07C211/49—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring having at least two amino groups bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/76—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings and etherified hydroxy groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
    • C07C217/82—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring
    • C07C217/84—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring the oxygen atom of at least one of the etherified hydroxy groups being further bound to an acyclic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C219/34—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having amino groups and esterified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/52—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/52—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C229/54—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of the same non-condensed six-membered aromatic ring
    • C07C229/60—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of the same non-condensed six-membered aromatic ring with amino and carboxyl groups bound in meta- or para- positions
    • 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
    • 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
    • C09K19/56—Aligning agents
    • 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
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
    • G02F1/133788—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation by light irradiation, e.g. linearly polarised light photo-polymerisation

Definitions

  • the present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film, and a liquid crystal display element for producing a liquid crystal display element having excellent image sticking characteristics.
  • the liquid crystal display element is known as a light, thin, and low power consumption display device and has been remarkably developed in recent years.
  • the liquid crystal display element is configured, for example, by sandwiching a liquid crystal layer between a pair of transparent substrates provided with electrodes.
  • an organic film made of an organic material is used as the liquid crystal alignment film so that the liquid crystal is in a desired alignment state between the substrates.
  • the liquid crystal alignment film is a component of the liquid crystal display element, and is formed on the surface of the substrate that holds the liquid crystal in contact with the liquid crystal, and plays a role of aligning the liquid crystal in a certain direction between the substrates.
  • the liquid crystal alignment film may be required to play a role of controlling the pretilt angle of the liquid crystal in addition to the role of aligning the liquid crystal in a certain direction such as a direction parallel to the substrate.
  • alignment control ability is given by performing an alignment treatment on the organic film constituting the liquid crystal alignment film.
  • the rubbing method is a method of rubbing (rubbing) the surface of an organic film such as polyvinyl alcohol, polyamide or polyimide on a substrate with a cloth such as cotton, nylon or polyester in the rubbing direction (rubbing direction).
  • This is a method of aligning liquid crystals. Since this rubbing method can easily realize a relatively stable alignment state of liquid crystals, it has been used in the manufacturing process of conventional liquid crystal display elements.
  • an organic film used for the liquid crystal alignment film a polyimide-based organic film excellent in reliability such as heat resistance and electrical characteristics has been mainly selected.
  • Anisotropy is formed in the organic film constituting the liquid crystal alignment film by linearly polarized light or collimated light, and the liquid crystal is aligned according to the anisotropy.
  • a decomposition type photo-alignment method is known as a main photo-alignment method.
  • the polyimide film is irradiated with polarized ultraviolet rays, and anisotropic decomposition is caused by utilizing the polarization direction dependence of the ultraviolet absorption of the molecular structure. Then, the liquid crystal is aligned by the polyimide remaining without being decomposed (see, for example, Patent Document 1).
  • photocrosslinking type and photoisomerization type photo-alignment methods are also known.
  • polyvinyl cinnamate is used and irradiated with polarized ultraviolet rays to cause a dimerization reaction (crosslinking reaction) at the double bond portion of two side chains parallel to the polarized light. Then, the liquid crystal is aligned in a direction perpendicular to the polarization direction (see, for example, Non-Patent Document 1).
  • the liquid crystal alignment film alignment treatment method by the photo alignment method does not require rubbing, and there is no fear of generation of dust or static electricity.
  • An alignment process can also be performed on a substrate of a liquid crystal display element having an uneven surface, which is a method for aligning a liquid crystal alignment film suitable for an industrial soot production process.
  • the photo-alignment method eliminates the rubbing process itself as compared with the rubbing method that has been used industrially as an alignment treatment method for liquid crystal display elements, and thus has a great advantage. And compared with the rubbing method in which the alignment control ability becomes almost constant by rubbing, the photo alignment method can control the alignment control ability by changing the irradiation amount of polarized light.
  • the photo-alignment method in order to achieve the same degree of alignment control ability as in the rubbing method, a large amount of polarized light irradiation may be required or stable liquid crystal alignment may not be realized. .
  • the present invention provides a substrate having a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element, which has high efficiency and orientation control ability, and has excellent image sticking characteristics, a horizontal electric field drive type liquid crystal display element having the substrate, and
  • An object of the present invention is to provide a compound to be given, more specifically, a novel diamine capable of improving the reliability with little addition without affecting the orientation.
  • X is a single bond or a divalent organic group
  • Y and Z are each independently a divalent organic group containing alkylene
  • R 1 and R 2 are each independently a monovalent group.
  • An organic group, R 3 is an alkyl group having 1 to 4 carbon atoms, and m and n are each independently an integer of 0 to 4).
  • It contains at least one polymer selected from the group consisting of a polyimide precursor that is a polymer of a diamine component containing the diamine and tetracarboxylic dianhydride and a polyimide that is an imidized product thereof, and an organic solvent.
  • a polyimide precursor that is a polymer of a diamine component containing the diamine and tetracarboxylic dianhydride and a polyimide that is an imidized product thereof, and an organic solvent.
  • X 1 is a tetravalent organic group derived from a tetracarboxylic acid derivative
  • Y 1 is a divalent organic group derived from a diamine containing the structure of Formula (1)
  • R 11 Is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
  • R 3 is an alkyl group having 1 to 4 carbon atoms.
  • liquid crystal aligning agent according to 4 or 5 above, wherein the polymer having the structural unit represented by the formula (3) is contained in an amount of 10 mol% or more based on the total polymer contained in the liquid crystal aligning agent.
  • liquid crystal aligning agent according to any one of the above 4 to 6, wherein the organic solvent contains at least one selected from the group consisting of 4-hydroxy-4-methyl-2-pentanone and diethylene glycol diethyl ether.
  • [I] A step of coating the composition according to any one of 1 to 7 above on a substrate having a conductive film for driving a lateral electric field to form a coating film; [II] a step of irradiating the coating film obtained in [I] with polarized ultraviolet rays; and [III] a step of heating the coating film obtained in [II];
  • substrate which has the said liquid crystal aligning film which obtains the liquid crystal aligning film for horizontal electric field drive type liquid crystal display elements by which orientation control ability was provided by having.
  • a substrate having a liquid crystal alignment film for a lateral electric field drive type liquid crystal display device produced by the method described in 8 above.
  • a lateral electric field drive type liquid crystal display device comprising the substrate according to 9 above.
  • a lateral electric field drive type liquid crystal display device manufactured by the method according to 11 above.
  • X is a single bond or a divalent organic group
  • Y and Z are each independently a divalent organic group containing alkylene
  • R 1 and R 2 are each independently a monovalent group.
  • An organic group, R 3 is an alkyl group having 1 to 4 carbon atoms, and m and n are each independently an integer of 0 to 4).
  • X 1 is a tetravalent organic group derived from a tetracarboxylic acid derivative
  • Y 1 is a divalent organic group derived from a diamine containing the structure of Formula (1)
  • R 11 Is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
  • R 3 is an alkyl group having 1 to 4 carbon atoms.
  • a substrate having a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element which is provided with high efficiency and orientation control ability and has excellent image sticking characteristics, and a horizontal electric field drive type liquid crystal display element having the substrate. Can do.
  • the lateral electric field drive type liquid crystal display device manufactured by the method of the present invention is provided with the alignment control ability with high efficiency, the display characteristics are not impaired even if it is continuously driven for a long time.
  • the polymer composition used in the production method of the present invention has a photosensitive main chain polymer (hereinafter, also simply referred to as main chain polymer) capable of expressing self-organization ability, and the polymer
  • the coating film obtained by using the composition is a film having a photosensitive main chain type polymer that can exhibit self-organization ability.
  • This coating film is subjected to orientation treatment by irradiation with polarized light without being rubbed. And after polarized light irradiation, it passes through the process of heating the main chain type polymer film, and becomes a coating film (hereinafter also referred to as a liquid crystal alignment film) to which alignment control ability is imparted.
  • the slight anisotropy developed by the irradiation of polarized light becomes a driving force, and the main chain polymer itself is efficiently reoriented by self-organization.
  • a highly efficient alignment process can be realized as the liquid crystal alignment film, and a liquid crystal alignment film with high alignment control ability can be obtained.
  • the liquid crystal aligning agent of this invention contains the polymer (henceforth a specific polymer or a main chain polymer) obtained from the diamine component containing the diamine which has a structure represented by following formula (1). It is an alignment agent.
  • a specific polymer or a main chain polymer obtained from the diamine component containing the diamine which has a structure represented by following formula (1). It is an alignment agent.
  • the liquid crystal aligning agent of the present invention is a liquid crystal aligning agent containing a polymer obtained from a diamine having the structure of the following formula (1) (also referred to as a specific diamine in the present invention) and an organic solvent.
  • X is a single bond or a divalent organic group
  • Y and Z are each independently a divalent organic group containing alkylene
  • R 1 and R 2 are each independently a monovalent group.
  • An organic group, R 3 is an alkyl group having 1 to 4 carbon atoms, and m and n are each independently an integer of 0 to 4).
  • Examples of the monovalent organic group herein include an alkyl group, an alkenyl group, an alkoxy group, a fluoroalkyl group, a fluoroalkenyl group, or a fluoroalkoxy group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms.
  • a monovalent organic group a methyl group is preferable.
  • divalent organic group examples include benzene, naphthalene, cyclohexyl group, and groups obtained by substituting these hydrogen atoms with monovalent organic groups. Of these, benzene is preferred as the divalent organic group.
  • Examples of the divalent organic group containing alkylene include an alkylene group, a group composed of an alkylene and an ether bond, a group composed of an alkylene and an ester bond, and an alkylene and an ether in which some or all of the hydrogen atoms are replaced by halogen.
  • Examples include a group composed of a bond, and a group composed of an alkylene and an ester bond in which part or all of the hydrogen atoms are replaced by halogen.
  • the group comprised by alkylene and alkylene and an ether bond is preferable.
  • the number of carbon atoms is preferably 1 or more and 20 or less, and more preferably 1 or more and 10 or less.
  • R 3 is preferably a methyl group or an ethyl group, more preferably a methyl group, from the viewpoint of ease of reaction during polymerization.
  • M and n are preferably 0 in that phenyl groups are easy to overlap with each other due to less steric hindrance and re-orientate in a higher order.
  • the diamine is preferably a diamine represented by the following formula (2).
  • diamine having the structure of the above formula (2) include the following, but are not limited thereto.
  • the method for synthesizing the specific diamine is not particularly limited.
  • the method of using the nitro compound represented by following formula (5) and converting the nitro group which it has into an amino group by a reductive reaction is mentioned.
  • the catalyst used for the above reduction reaction is preferably an activated carbon-supported metal available as a commercial product, and examples thereof include palladium-activated carbon, platinum-activated carbon, and rhodium-activated carbon. Further, palladium catalyst, platinum oxide, Raney nickel, iron, zinc, tin, and the like are not necessarily activated carbon-supporting metal catalysts. In general, iron, zinc, and tin that are widely used are preferable because good results can be obtained.
  • the reaction may be carried out in the presence of activated carbon.
  • the amount of the activated carbon to be used is not particularly limited, but is preferably in the range of 1 to 30% by mass, more preferably 10 to 20% by mass with respect to the dinitro compound X1.
  • the reaction may be carried out under pressure. In this case, in order to avoid reduction of benzene nuclei, it is carried out in a pressure range up to 20 atm. The reaction is preferably carried out in the range up to 10 atm. If necessary, an acid catalyst may be added to shorten the time.
  • a solvent does not react with each raw material, it can be used without a restriction
  • aprotic polar organic solvents DMF, DMSO, DMAc, NMP, etc.
  • ethers Et 2 O, i-Pr 2 O, TBME, CPME, THF, dioxane, etc.
  • aliphatic hydrocarbons penentane, Hexane, heptane, petroleum ether, etc.
  • aromatic hydrocarbons benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin, etc.
  • halogenated hydrocarbons chloroform, dichloromethane, carbon tetrachloride, dichloroethane
  • Lower fatty acid esters methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.
  • nitriles acet
  • solvents can be appropriately selected in consideration of the ease of reaction and the like, and can be used singly or in combination of two or more. If necessary, the solvent can be dried using a suitable dehydrating agent or desiccant and used as a non-aqueous solvent.
  • the amount of the solvent used is not particularly limited, but is 0.1 to 100 times the mass of the nitro compound.
  • the amount is preferably 0.5 to 30 times by mass, more preferably 1 to 10 times by mass.
  • the reaction temperature is not particularly limited, but it is in the range from ⁇ 100 ° C. to the boiling point of the solvent used, preferably ⁇ 50 to 150 ° C.
  • the reaction time is usually 0.05 to 350 hours, preferably 0.5 to 100 hours.
  • the solvent to be used is not particularly limited as long as it does not inhibit the progress of the reaction.
  • aromatic hydrocarbons such as benzene, toluene and xylene
  • aliphatic hydrocarbons such as hexane and heptane.
  • Cycloaliphatic alicyclic hydrocarbons such as diethyl ether, t-butyl methyl ether, ethers such as 1,2-dimethoxyethane, tetrahydrofuran and 1,4-dioxane, esters such as ethyl acetate and ethyl propionate, N , N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2- Examples include amides such as pyrrolidone, amines such as triethylamine, tributylamine and N, N-dimethylaniline, pyridines such
  • a base for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, an alkali metal carbonate such as sodium carbonate or potassium carbonate, sodium hydrogen carbonate, or potassium hydrogen carbonate.
  • Alkali metal bicarbonates such as triethylamine, tributylamine, N, N-dimethylaniline, pyridine, 4- (dimethylamino) pyridine, imidazole, 1,8-diazabicyclo [5,4,0] -7-undecene, etc.
  • An organic base or the like can be used in an amount of 1 to 4 equivalents with respect to the compound represented by the general formula (7).
  • the reaction temperature can be set to an arbitrary temperature from ⁇ 60 ° C. to the reflux temperature of the reaction mixture, and the reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, but is usually arbitrarily within a range of 5 minutes to 100 hours. Can be set.
  • the leaving group X is preferably mesylate (—OMs).
  • OMs mesylate
  • Other preferable leaving groups X include fluorine atom, chlorine atom, bromine atom, iodine atom, tosylate (—OTs) and the like. Can be mentioned.
  • the solvent to be used is not particularly limited as long as it does not inhibit the progress of the reaction.
  • aromatic hydrocarbons such as benzene, toluene and xylene
  • aliphatic hydrocarbons such as hexane and heptane.
  • Cycloaliphatic alicyclic hydrocarbons such as diethyl ether, t-butyl methyl ether, ethers such as 1,2-dimethoxyethane, tetrahydrofuran and 1,4-dioxane, esters such as ethyl acetate and ethyl propionate, N , N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2- Examples include amides such as pyrrolidone, amines such as triethylamine, tributylamine and N, N-dimethylaniline, pyridines such
  • a base for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, an alkali metal carbonate such as sodium carbonate or potassium carbonate, sodium hydrogen carbonate, or potassium hydrogen carbonate.
  • Alkali metal bicarbonates such as triethylamine, tributylamine, N, N-dimethylaniline, pyridine, 4- (dimethylamino) pyridine, imidazole, 1,8-diazabicyclo [5,4,0] -7-undecene, etc.
  • An organic base or the like can be used at 1 to 4 equivalents relative to the compound represented by the general formula (8).
  • the reaction temperature can be set to any temperature from ⁇ 60 ° C. to 25 ° C., and the reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, but can usually be arbitrarily set in the range of 5 minutes to 100 hours.
  • the amount of the reaction substrate may be 1 to 4 equivalents of the compound represented by the formula (10) with respect to 1 equivalent of the compound represented by the formula (9).
  • the solvent to be used is not particularly limited as long as it does not inhibit the progress of the reaction.
  • aromatic hydrocarbons such as benzene, toluene and xylene
  • aliphatic hydrocarbons such as hexane and heptane.
  • Cycloaliphatic alicyclic hydrocarbons such as diethyl ether, t-butyl methyl ether, ethers such as 1,2-dimethoxyethane, tetrahydrofuran and 1,4-dioxane, esters such as ethyl acetate and ethyl propionate, N , N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2- Examples include amides such as pyrrolidone, amines such as triethylamine, tributylamine and N, N-dimethylaniline, pyridines such
  • a base for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, an alkali metal carbonate such as sodium carbonate or potassium carbonate, sodium hydrogen carbonate, or potassium hydrogen carbonate.
  • Alkali metal bicarbonates such as triethylamine, tributylamine, N, N-dimethylaniline, pyridine, 4- (dimethylamino) pyridine, imidazole, 1,8-diazabicyclo [5,4,0] -7-undecene, etc.
  • An organic base or the like can be used in an amount of 1 to 4 equivalents with respect to the compound represented by the general formula (10).
  • the reaction temperature can be set to an arbitrary temperature from ⁇ 60 ° C. to the reflux temperature of the reaction mixture, and the reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, but is usually arbitrarily within a range of 5 minutes to 100 hours. Can be set.
  • the polymer of the present invention is a polymer obtained using the diamine.
  • Specific examples include polyamic acid, polyamic acid ester, polyimide, polyurea, polyamide and the like.
  • a polyimide precursor containing a structural unit represented by the following formula (3) From the viewpoint of use as a liquid crystal aligning agent, a polyimide precursor containing a structural unit represented by the following formula (3), And at least one selected from polyimides as imidized products thereof.
  • X 1 is a tetravalent organic group derived from a tetracarboxylic acid derivative
  • Y 1 is a divalent organic group derived from a diamine containing the structure of formula (1)
  • R 11 Is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
  • R 3 is an alkyl group having 1 to 4 carbon atoms.
  • R 11 is preferably a hydrogen atom, a methyl group or an ethyl group from the viewpoint of ease of imidization by heating.
  • R 3 is preferably a methyl group from the viewpoint of easy reaction during polymerization.
  • X 1 is a tetravalent organic group derived from a tetracarboxylic acid derivative, and its structure is not particularly limited.
  • X 1 in the polyimide precursor is required for the solubility of the polymer in the solvent, the coating property of the liquid crystal aligning agent, the orientation of the liquid crystal when it is used as the liquid crystal alignment film, the voltage holding ratio, the accumulated charge, etc.
  • one type may be used in the same polymer, or two or more types may be mixed. If dare Specific examples of X 1, are listed in paragraph 13 and 14, wherein the WO 2015/119168, such as the structure of formula (X-1) ⁇ (X -46) are mentioned.
  • (A-1), (A-2), and (A-4) are preferable from the viewpoint of photoalignment, and (A-1) is particularly preferable.
  • Y 1 includes a structure in which an amino group and an alkylamino group are removed from the diamine having the structure of Formula (1).
  • Y 1 is particularly preferably a structure obtained by removing an amino group and an alkylamino group from the structure of the above formula (2).
  • the polyimide precursor containing the structural unit represented by the formula (3) is at least selected from the structural unit represented by the following formula (4) and a polyimide that is an imidized product thereof, as long as the effects of the present invention are not impaired.
  • One kind may be included.
  • X 2 is a tetravalent organic group derived from a tetracarboxylic acid derivative
  • Y 2 is a divalent organic group derived from a diamine that does not include the structure of Formula (1) in the main chain direction.
  • R 12 has the same definition as R 11 in formula (3).
  • X 2 include the same structures as those exemplified for X 1 in formula (6), including preferred examples.
  • Y 2 in the polyimide precursor is a divalent organic group derived from a diamine that does not include the structure of formula (1) in the main chain direction, and the structure is not particularly limited. Y 2 depends on the degree of required properties such as the solubility of the polymer in the solvent, the coating property of the liquid crystal aligning agent, the orientation of the liquid crystal when it is used as the liquid crystal alignment film, the voltage holding ratio, and the accumulated charge. 1 type may be selected in the same polymer, and 2 or more types may be mixed.
  • a preferable structure of Y 2 includes a structure of the following formula (11).
  • R 32 is a single bond or a divalent organic group, and a single bond is preferable.
  • R 33 is a structure represented by — (CH 2 ) r —. r is an integer of 2 to 10, preferably 3 to 7. Arbitrary —CH 2 — may be replaced with an ether, ester, amide, urea, or carbamate bond under the condition that they are not adjacent to each other.
  • R 34 is a single bond or a divalent organic group. Any hydrogen atom on the benzene ring may be replaced by a monovalent organic group, and a fluorine atom or a methyl group is preferred.
  • the benzene ring of the specific diamine (2) is not inhibited from at least one kind of reorientation selected from the polyimide precursor containing the structural unit represented by the formula (3) and the imidized polyimide. It preferably contains a partial structure in common with the Y-benzene ring moiety.
  • the liquid crystal orientation is less when the structural unit represented by the formula (3) is smaller. May improve more.
  • R 21 in the formula (3) is an alkyl group, so that imidation is not caused by heating, and the alignment ability of liquid crystal molecules is lowered. Therefore, the structural unit represented by the formula (3) is preferably 1 to 70 mol%, more preferably 5 to 50 mol%, based on the sum of the formula (3) and the formula (4). Particularly preferred is 10 to 30 mol%.
  • the molecular weight of the polyimide precursor used in the present invention is preferably 2,000 to 500,000 in terms of weight average molecular weight, more preferably 5,000 to 300,000, still more preferably 10,000 to 100,000. is there.
  • the polyimide having a divalent group represented by the formula (1) in the main chain include a polyimide obtained by ring-closing the polyimide precursor.
  • the ring closure rate (also referred to as imidation rate) of the amic acid group is not necessarily 100%, and can be arbitrarily adjusted according to the use and purpose.
  • Examples of the method for imidizing the polyimide precursor include thermal imidization in which the polyimide precursor solution is heated as it is, or catalytic imidization in which a catalyst is added to the polyimide precursor solution.
  • liquid crystal aligning agent of this invention contains the polymer (specific polymer) obtained from the diamine component containing the diamine which has a structure represented by Formula (1), there exists an effect as described in this invention.
  • polymer specific polymer
  • two or more kinds of specific polymers having different structures may be contained.
  • polystyrene-phenylmaleimide poly (meta ) Acrylate and the like.
  • the ratio of the specific polymer to the total polymer components is preferably 5% by mass or more, and an example thereof is 5 to 95% by mass.
  • the liquid crystal aligning agent is used for producing a liquid crystal aligning film, and generally takes the form of a coating liquid from the viewpoint of forming a uniform thin film. Also in the liquid crystal aligning agent of this invention, it is preferable that it is a coating liquid containing an above-described polymer component and the organic solvent in which this polymer component is dissolved. At that time, the concentration of the polymer in the liquid crystal aligning agent can be appropriately changed by setting the thickness of the coating film to be formed. From the viewpoint of forming a uniform and defect-free coating film, the content is preferably 1% by mass or more, and from the viewpoint of storage stability of the solution, it is preferably 10% by mass or less. A particularly preferred polymer concentration is 2 to 8% by mass.
  • the organic solvent contained in the liquid crystal aligning agent is not particularly limited as long as the polymer component is uniformly dissolved.
  • Specific examples are N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, ⁇ -butyrolactone, 1,3-dimethyl.
  • -Imidazolidinone methyl ethyl ketone, cyclohexanone, cyclopentanone and the like.
  • N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, or ⁇ -butyrolactone is preferably used.
  • the organic solvent contained in the liquid crystal aligning agent uses a mixed solvent that is used in combination with a solvent that improves the coating properties and the surface smoothness of the coating film when the liquid crystal aligning agent is applied in addition to the above-described solvents.
  • a mixed solvent is also preferably used in the liquid crystal aligning agent of the present invention. Specific examples of the organic solvent to be used in combination are given below, but the organic solvent is not limited to these examples.
  • ethanol isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isopentyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 1,2- Ethane All, 1,2-propanediol, 1,3-propan
  • 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 kind and content of such a solvent are appropriately selected according to the application device, application conditions, application environment, and the like of the liquid crystal aligning agent.
  • the liquid crystal aligning agent of the present invention may additionally contain components other than the polymer component and the organic solvent as long as the effects of the present invention are not impaired.
  • additional components include an adhesion aid for increasing the adhesion between the liquid crystal alignment film and the substrate and the adhesion between the liquid crystal alignment film and the sealing material, a crosslinking agent for increasing the strength of the liquid crystal alignment film, and the liquid crystal alignment.
  • examples thereof include dielectrics and conductive materials for adjusting the dielectric constant and electric resistance of the film. Specific examples of these additional components are as disclosed in various known literatures relating to liquid crystal aligning agents. If an example is given, pages 53 [0105] to 55 of the pamphlet of Japanese Unexamined Patent Publication No. 2015/060357. And the like as disclosed in [0116].
  • the method for producing a substrate having the liquid crystal alignment film of the present invention is as follows. [I] (A) A polymer obtained from a diamine component containing a diamine having a structure represented by the formula (1), and (B) a polymer composition containing an organic solvent is converted into a conductive film for driving a lateral electric field.
  • a lateral electric field drive type liquid crystal display element can be obtained.
  • the second substrate instead of using a substrate having no lateral electric field driving conductive film instead of a substrate having a lateral electric field driving conductive film, the above steps [I] to [III] (for lateral electric field driving) Since a substrate having no conductive film is used, for the sake of convenience, in this application, the steps [I ′] to [III ′] may be abbreviated as steps), thereby providing a first liquid crystal alignment film having alignment controllability. Two substrates can be obtained.
  • the manufacturing method of the horizontal electric field drive type liquid crystal display element is: [IV] A step of obtaining a liquid crystal display element by arranging the first and second substrates obtained above so that the liquid crystal alignment films of the first and second substrates face each other with liquid crystal interposed therebetween; Have Thereby, a horizontal electric field drive type liquid crystal display element can be obtained.
  • step [I] a polymer composition containing a photosensitive main polymer and an organic solvent is applied to a substrate having a conductive film for driving a lateral electric field to form a coating film.
  • ⁇ Board> Although it does not specifically limit about a board
  • the substrate has a conductive film for driving a lateral electric field.
  • the conductive film include, but are not limited to, ITO (Indium Tin Oxide) and IZO (Indium Zinc Oxide) when the liquid crystal display element is a transmission type.
  • examples of the conductive film include a material that reflects light such as aluminum, but are not limited thereto.
  • a method for forming a conductive film on a substrate a conventionally known method can be used.
  • the method for applying the polymer composition described above onto a substrate having a conductive film for driving a lateral electric field is not particularly limited.
  • the application method is generally performed by screen printing, offset printing, flexographic printing, an inkjet method, or the like.
  • Other coating methods include a dipping method, a roll coater method, a slit coater method, a spinner method (rotary coating method), or a spray method, and these may be used depending on the purpose.
  • the polymer composition After the polymer composition is applied on a substrate having a conductive film for driving a transverse electric field, it is heated to 50 to 300 ° C., preferably 50 to 300 ° C. by a heating means such as a hot plate, a thermal circulation oven or an IR (infrared) oven.
  • the film can be obtained by evaporating the solvent at 180 ° C.
  • the drying temperature at this time is preferably lower than that in the step [III] from the viewpoint of liquid crystal alignment stability. If the thickness of the coating film is too thick, it will be disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered.
  • it is preferably 5 nm to 300 nm, more preferably 10 nm to 150 nm. It is. In addition, it is also possible to provide the process of cooling the board
  • step [II] the coating film obtained in step [I] is irradiated with polarized ultraviolet rays.
  • the substrate is irradiated with polarized ultraviolet rays through a polarizing plate from a certain direction.
  • ultraviolet rays to be used ultraviolet rays having a wavelength in the range of 100 nm to 400 nm can be used.
  • the optimum wavelength is selected through a filter or the like depending on the type of coating film to be used.
  • ultraviolet light having a wavelength in the range of 240 nm to 400 nm can be selected and used so that a photodegradation reaction can be selectively induced.
  • the ultraviolet light for example, light emitted from a high-pressure mercury lamp or a metal halide lamp can be used.
  • the irradiation amount of polarized ultraviolet rays depends on the coating film used.
  • the amount of irradiation is polarized ultraviolet light that realizes the maximum value of ⁇ A (hereinafter also referred to as ⁇ Amax), which is the difference between the ultraviolet light absorbance in a direction parallel to the polarization direction of polarized ultraviolet light and the ultraviolet light absorbance in a direction perpendicular to the polarization direction of the polarized ultraviolet light.
  • the amount is preferably in the range of 1% to 70%, more preferably in the range of 1% to 50%.
  • step [III] the ultraviolet-irradiated coating film polarized in step [II] is heated.
  • An orientation control ability can be imparted to the coating film by heating.
  • a heating means such as a hot plate, a heat circulation type oven, or an IR (infrared) type oven can be used.
  • the heating temperature can be determined in consideration of the temperature at which good liquid crystal alignment stability and electrical characteristics are exhibited in the coating film used.
  • the heating temperature is preferably within a temperature range in which the main chain polymer exhibits good liquid crystal alignment stability. If the heating temperature is too low, the anisotropy effect due to heat and thermal imidization tend to be insufficient, and if the heating temperature is too high, the anisotropy imparted by polarized light exposure In this case, it may be difficult to reorient in one direction due to self-organization.
  • the thickness of the coating film formed after heating is preferably 5 nm to 300 nm, more preferably 50 nm to 150 nm, for the same reason described in the step [I].
  • the production method of the present invention can realize highly efficient introduction of anisotropy into the coating film. And a board
  • the step [IV] is performed in the same manner as in the above [I ′] to [III ′], similarly to the substrate (first substrate) obtained in [III] and having the liquid crystal alignment film on the conductive film for lateral electric field driving.
  • the obtained liquid crystal alignment film-attached substrate (second substrate) having no conductive film is placed oppositely so that both liquid crystal alignment films face each other through liquid crystal, and a liquid crystal cell is formed by a known method.
  • This is a step of manufacturing a lateral electric field drive type liquid crystal display element.
  • a substrate having no lateral electric field driving conductive film was used in place of the substrate having the lateral electric field driving conductive film in the step [I].
  • steps [I] to [III] It can be carried out in the same manner as in steps [I] to [III]. Since the difference between the steps [I] to [III] and the steps [I ′] to [III ′] is only the presence or absence of the conductive film, the description of the steps [I ′] to [III ′] is omitted. To do.
  • the first and second substrates described above are prepared, spacers are dispersed on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is on the inside.
  • the other substrate is bonded and the liquid crystal is injected under reduced pressure, or the liquid crystal is dropped on the liquid crystal alignment film surface on which the spacers are dispersed, and then the substrate is bonded and sealed.
  • Etc. can be illustrated.
  • the diameter of the spacer at this time is preferably 1 ⁇ m to 30 ⁇ m, more preferably 2 ⁇ m to 10 ⁇ m. This spacer diameter determines the distance between the pair of substrates that sandwich the liquid crystal layer, that is, the thickness of the liquid crystal layer.
  • substrate with a coating film of this invention irradiates the polarized ultraviolet-ray, after apply
  • high-efficiency anisotropy is introduced into the main chain polymer film, and a substrate with a liquid crystal alignment film having a liquid crystal alignment control ability is manufactured.
  • the coating film used in the present invention the introduction of highly efficient anisotropy into the coating film is realized by utilizing the principle of molecular reorientation induced by self-assembly based on the photoreaction of the main chain.
  • the main chain type polymer has a photodegradable group as a photoreactive group
  • a liquid crystal display element is formed.
  • the coating film used in the method of the present invention is a liquid crystal alignment film having anisotropy introduced with high efficiency and excellent alignment control ability by sequentially performing irradiation of polarized ultraviolet rays on the coating film and heat treatment. can do.
  • the irradiation amount of polarized ultraviolet rays to the coating film and the heating temperature in the heat treatment are optimized. Thereby, introduction of anisotropy into the coating film with high efficiency can be realized.
  • the optimal irradiation amount of polarized ultraviolet light for introducing highly efficient anisotropy into the coating film used in the present invention is the irradiation amount of polarized ultraviolet light that optimizes the amount of photodegradation reaction of the photosensitive group in the coating film.
  • the amount of photoreaction is not sufficient. In that case, sufficient self-organization does not proceed even after heating.
  • the optimum amount of the photolytic reaction of the photosensitive group by irradiation with polarized ultraviolet light is preferably 0.1 to 90 mol% of the polymer film. More preferably, it is 1 mol% to 80 mol%.
  • the amount of photodecomposition reaction of the photosensitive group in the main chain of the polymer film is optimized by optimizing the irradiation amount of polarized ultraviolet rays. Then, in combination with the subsequent heat treatment, highly efficient introduction of anisotropy into the coating film used in the present invention is realized. In that case, a suitable amount of polarized ultraviolet rays can be determined based on the evaluation of ultraviolet absorption of the coating film used in the present invention.
  • the ultraviolet absorption in the direction parallel to the polarization direction of the polarized ultraviolet ray and the ultraviolet absorption in the vertical direction after the irradiation with the polarized ultraviolet ray are measured.
  • ⁇ A which is the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of polarized ultraviolet rays and the ultraviolet absorbance in the direction perpendicular to the polarization direction of the polarized ultraviolet rays.
  • the maximum value of ⁇ A ( ⁇ Amax) realized in the coating film used in the present invention and the irradiation amount of polarized ultraviolet light that realizes it are obtained.
  • a preferable amount of polarized ultraviolet rays to be irradiated in the production of the liquid crystal alignment film can be determined on the basis of the amount of polarized ultraviolet rays to realize this ⁇ Amax.
  • the above-described main chain type polymer provides liquid crystal alignment stability as a reference, as described above.
  • a suitable heating temperature should be determined. Therefore, for example, the temperature range in which the main chain polymer used in the present invention provides liquid crystal alignment stability is determined in consideration of the temperature at which good liquid crystal alignment stability and electrical characteristics are exhibited in the coating film used. And can be set in a temperature range according to a liquid crystal alignment film made of a conventional polyimide or the like. That is, the heating temperature after irradiation with polarized ultraviolet rays is preferably 100 ° C. to 300 ° C., more preferably 150 ° C. to 250 ° C. By doing so, greater anisotropy is imparted to the coating film used in the present invention.
  • the liquid crystal display element provided by the present invention exhibits high reliability against external stresses such as light and heat.
  • the lateral electric field drive type liquid crystal display element substrate manufactured using the polymer of the present invention or the lateral electric field drive type liquid crystal display element having the substrate has excellent reliability and a large screen. And can be suitably used for high-definition liquid crystal televisions.
  • the liquid crystal alignment film manufactured by the method of the present invention has excellent liquid crystal alignment stability and reliability, it can be used for a variable phase shifter using liquid crystal. For example, it can be suitably used for an antenna that can vary the resonance frequency.
  • DA-1 compound represented by the following structural formula (DA-1)
  • DA-2 structural formula (DA- Compound DA-3 represented by 2): Compound CA-1 represented by the following structural formula (DA-3): Compound represented by the following structural formula (CA-1)
  • FT-NMR Fourier transform type superconducting nuclear magnetic resonance apparatus
  • INOVA-400 manufactured by Varian 400 MHz.
  • Solvent deuterated N, N-dimethyl sulfoxide (DMSO-d 6 ).
  • Standard substance Tetramethylsilane (TMS).
  • the viscosity of the polymer solution was measured using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.), a sample amount of 1.1 mL, cone rotor TE-1 (1 ° 34 ′, R24), temperature 25 Measured at ° C.
  • DA-1 is a novel compound that has not been published yet, and its synthesis method will be described in detail in Synthesis Example 1 below.
  • Second step Synthesis of 4- (2- (4-nitrophenoxy) ethoxy) phenethyl methanesulfonate (DA-1-2)
  • N-methyl-2- (4- (2- (4-nitrophenoxy) ethoxy) phenyl) ethanamine (10.0 g, 31.6 mmol) was dissolved in tetrahydrofuran (100.0 g), and 5% palladium-carbon (0 0.5 g) and stirred at 50 ° C. for 5 hours under a hydrogen atmosphere.
  • the disappearance of the raw materials was confirmed by HPLC, dissolved in tetrahydrofuran (50.0 g), the catalyst was removed by filtration, and the filtrate was concentrated. This was washed with heptane (50.0 g), and the precipitated solid was filtered and dried under reduced pressure at 50 ° C. to obtain DA-1 (white powder, yield: 9.0 g, yield: 98%).
  • a method for manufacturing a liquid crystal cell for evaluating the liquid crystal alignment will be described below.
  • a liquid crystal cell having a configuration of an FFS liquid crystal display element was manufactured.
  • a substrate with electrodes was prepared.
  • the substrate is a glass substrate having a size of 30 mm ⁇ 35 mm and a thickness of 0.7 mm.
  • an IZO electrode constituting the counter electrode as the first layer was formed on the entire surface.
  • a SiN (silicon nitride) film formed by the CVD method was formed as the second layer.
  • the second layer SiN film has a thickness of 500 nm and functions as an interlayer insulating film.
  • a comb-like pixel electrode formed by patterning an IZO film is arranged as a third layer, and two pixels, a first pixel and a second pixel, are formed. .
  • the size of each pixel is 10 mm long and about 5 mm wide.
  • the first-layer counter electrode and the third-layer pixel electrode are electrically insulated by the action of the second-layer SiN film.
  • the pixel electrode of the third layer is a comb tooth formed by arranging a plurality of U-shaped electrode elements whose central portion is bent, as in the figure described in Japanese Patent Application Laid-Open No. 2014-77845 (Japan Published Patent Publication). It has a shape. The width in the short direction of each electrode element is 3 ⁇ m, and the distance between the electrode elements is 6 ⁇ m. Since the pixel electrode forming each pixel is configured by arranging a plurality of bent-shaped electrode elements having a bent central portion, the shape of each pixel is not rectangular but bent at the central portion in the same manner as the electrode elements. It has a shape that is similar to a bold, Kumon character. Each pixel is divided into upper and lower portions with a central bent portion as a boundary, and has a first region on the upper side of the bent portion and a second region on the lower side.
  • the formation directions of the electrode elements of the pixel electrodes constituting them are different. That is, when the direction of a line segment projected onto the substrate with the polarization plane of polarized ultraviolet rays to be described later is used as a reference, in the first region of the pixel, the electrode element of the pixel electrode forms an angle of + 10 ° (clockwise). In the second region of the pixel, the electrode element of the pixel electrode is formed at an angle of ⁇ 10 ° (clockwise).
  • the direction of the rotation operation (in-plane switching) of the liquid crystal induced by the voltage application between the pixel electrode and the counter electrode in the substrate plane is It comprised so that it might become a mutually reverse direction.
  • the liquid crystal aligning agent obtained in the synthesis example and the comparative synthesis example was filtered through a 1.0 ⁇ m filter, and then applied to the prepared substrate with electrodes by spin coating. Subsequently, it was dried for 90 seconds on a hot plate set to 70 ° C. Next, using an exposure apparatus manufactured by Ushio Electric Co., Ltd .: APL-L050121S1S-APW01, the substrate was irradiated with linearly polarized ultraviolet light from a vertical direction through a wavelength selection filter and a polarizing plate.
  • the direction of the polarization plane was set so that the direction of the line segment obtained by projecting the polarization plane of polarized ultraviolet rays onto the substrate was inclined by 10 ° with respect to the third-layer IZO comb-teeth electrode. Subsequently, baking was performed for 30 minutes in an IR (infrared) oven set at 230 ° C., and a substrate with a polyimide liquid crystal alignment film having a film thickness of 100 nm subjected to alignment treatment was obtained.
  • IR infrared
  • substrate with a polyimide liquid crystal aligning film by which the alignment process was performed similarly to the above was also obtained for the glass substrate which has the columnar spacer of 4 micrometers in height with the ITO electrode formed in the back surface as a counter substrate.
  • a set of these two substrates with a liquid crystal alignment film is used as one set, and a sealing agent is printed on the other substrate leaving a liquid crystal injection port.
  • the polarizing planes were bonded and pressure-bonded so that the line segments projected onto the substrate were parallel. Thereafter, the sealing agent was cured to produce an empty cell having a cell gap of 4 ⁇ m.
  • Liquid crystal MLC-7026-100 (negative liquid crystal manufactured by Merck & Co., Inc.) was injected into the empty cell by a reduced pressure injection method, and the injection port was sealed to obtain an FFS liquid crystal cell. Thereafter, the obtained liquid crystal cell was heated at 120 ° C. for 30 minutes and allowed to stand at 23 ° C. overnight, and then used for evaluation of liquid crystal alignment.
  • the rotation angle when the liquid crystal cell was rotated from the angle at which the second region of the first pixel became darkest to the angle at which the first region became darkest was calculated as an angle ⁇ .
  • the second area was compared with the first area, and a similar angle ⁇ was calculated.
  • the average value of the angle ⁇ values of the first pixel and the second pixel was calculated as the angle ⁇ of the liquid crystal cell.
  • the voltage holding ratio was evaluated. Specifically, an alternating voltage of 2 VPP is applied to the liquid crystal cell obtained by the above method at a temperature of 70 ° C. for 60 ⁇ s, and the voltage after 1 second is measured to determine how much the voltage can be maintained. Calculated as retention (also referred to as VHR). The measurement was performed using a voltage holding ratio measuring device (VHR-1, manufactured by Toyo Technica Co., Ltd.) with settings of Voltage: ⁇ 1 V, Pulse Width: 60 ⁇ s, and Frame Period: 1000 ms. When the value of the voltage holding ratio of the liquid crystal cell was 80% or more, it was defined as “good”, and when the value of the voltage holding ratio was less than 80%, it was defined as “bad”.
  • VHR-1 voltage holding ratio measuring device
  • Example 1 Using the liquid crystal aligning agent (A-1) obtained in Synthesis Example 2, two types of liquid crystal cells were produced as described above. Irradiation with polarized ultraviolet rays was performed using a high pressure mercury lamp through a wavelength selection filter: 240LCF and a 254 nm type polarizing plate. The irradiation amount of polarized ultraviolet rays is measured by measuring the amount of light using an illuminometer UVD-S254SB manufactured by Ushio Electric Co., Ltd., and changing the wavelength in the range of 600 to 1800 mJ / cm 2. Three or more liquid crystal cells having different amounts were prepared.
  • the polarized UV irradiation amount with the best angle ⁇ was 1800 mJ / cm 2 , and the angle ⁇ was 0.15 °, which was good.
  • the voltage holding ratio was 92.4%, which was favorable.
  • Table 1 shows the results of evaluation of polarized UV irradiation amount, liquid crystal orientation evaluation, and evaluation of voltage holding ratio when the angle ⁇ was the best when using the liquid crystal aligning agents obtained in the synthesis examples and comparative synthesis examples. Indicates.
  • Example 1 As shown in Table 1, in Example 1, the angle ⁇ , which is the difference between the orientation azimuth angles before and after AC driving, is good when it is less than 0.3 °, and at the same time, the voltage holding ratio is good as 80% or more. Since both have good afterimage characteristics, the display quality of the liquid crystal display element is excellent. On the other hand, in Comparative Examples 1 and 2, the characteristics satisfying both the angle ⁇ and the voltage holding ratio were not confirmed. As described above, it was confirmed that the liquid crystal display device manufactured by the method of the present invention exhibits very excellent afterimage characteristics.
  • a substrate for a horizontal electric field drive type liquid crystal display element manufactured using the composition of the present invention or a horizontal electric field drive type liquid crystal display element having the substrate has excellent reliability, and has a large screen and a high definition liquid crystal television. It can utilize suitably for.
  • the liquid crystal alignment film manufactured by the method of the present invention has excellent liquid crystal alignment stability and reliability, it can be used for a variable phase shifter using liquid crystal. For example, it can be suitably used for an antenna that can vary the resonance frequency.

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

Abstract

La présente invention concerne : un agent d'alignement de cristaux liquides contenant un solvant organique et un polymère obtenu à partir d'une diamine ayant une structure représentée par la formule (1) ci-dessous; un film d'alignement de cristaux liquides; et un dispositif d'affichage à cristaux liquides.
PCT/JP2017/045625 2016-12-21 2017-12-20 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et dispositif d'affichage à cristaux liquides WO2018117133A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CN201780086602.5A CN110300922B (zh) 2016-12-21 2017-12-20 液晶取向剂、液晶取向膜以及液晶表示元件
JP2018558020A JP7151485B2 (ja) 2016-12-21 2017-12-20 液晶配向剤、液晶配向膜及び液晶表示素子
CN202210349222.9A CN114702393A (zh) 2016-12-21 2017-12-20 液晶取向剂、液晶取向膜以及液晶表示元件
KR1020197020490A KR102521135B1 (ko) 2016-12-21 2017-12-20 액정 배향제, 액정 배향막 및 액정 표시 소자
JP2022000347A JP7279823B2 (ja) 2016-12-21 2022-01-05 液晶配向剤、液晶配向膜及び液晶表示素子

Applications Claiming Priority (2)

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JP2016-248111 2016-12-21
JP2016248111 2016-12-21

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WO2018117133A1 true WO2018117133A1 (fr) 2018-06-28

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JP (2) JP7151485B2 (fr)
KR (1) KR102521135B1 (fr)
CN (2) CN110300922B (fr)
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WO (1) WO2018117133A1 (fr)

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KR20220100575A (ko) * 2019-11-14 2022-07-15 닛산 가가쿠 가부시키가이샤 액정 배향제, 액정 배향막 및 그것을 사용한 액정 표시 소자

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WO2008078796A1 (fr) * 2006-12-27 2008-07-03 Nissan Chemical Industries, Ltd. Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides utilisant celui-ci et élément d'affichage à cristaux liquides
WO2015050133A1 (fr) * 2013-10-01 2015-04-09 日産化学工業株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides les utilisant

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AU2003218476A1 (en) * 2002-05-31 2003-12-19 Elsicon, Inc. Hybrid polymer materials for liquid crystal alignment layers
JP2008176304A (ja) * 2006-12-22 2008-07-31 Jsr Corp 液晶配向剤、液晶配向膜、液晶表示素子および光学部材
TWI501998B (zh) * 2010-03-15 2015-10-01 Nissan Chemical Ind Ltd A liquid crystal aligning agent containing a polyamic acid ester, and a liquid crystal alignment film
KR102168590B1 (ko) * 2013-03-08 2020-10-21 닛산 가가쿠 가부시키가이샤 액정 배향제, 그들을 사용하여 얻어지는 액정 표시 소자 및 그 제조 방법
JPWO2014185412A1 (ja) * 2013-05-13 2017-02-23 日産化学工業株式会社 横電界駆動型液晶表示素子用液晶配向膜を有する基板の製造方法
KR102324602B1 (ko) * 2013-07-05 2021-11-09 닛산 가가쿠 가부시키가이샤 중합체 조성물 및 횡전계 구동형 액정 표시 소자용 액정 배향막
TWI746423B (zh) * 2014-05-29 2021-11-21 南韓商東進世美肯股份有限公司 二胺合成及用其製備的液晶配向劑
JP6676932B2 (ja) * 2014-11-12 2020-04-08 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
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WO2015050133A1 (fr) * 2013-10-01 2015-04-09 日産化学工業株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides les utilisant

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CN110300922A (zh) 2019-10-01
JPWO2018117133A1 (ja) 2019-10-31
JP7151485B2 (ja) 2022-10-12
TWI746743B (zh) 2021-11-21
JP2022050521A (ja) 2022-03-30
CN110300922B (zh) 2022-07-01
KR20190095392A (ko) 2019-08-14
JP7279823B2 (ja) 2023-05-23
CN114702393A (zh) 2022-07-05
KR102521135B1 (ko) 2023-04-12
TW201835316A (zh) 2018-10-01

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