WO2016113930A1 - Agent d'alignement de cristaux liquides utilisant un cristal liquide polymère photoréactif à liaisons hydrogène, et pellicule d'alignement de cristaux liquides - Google Patents

Agent d'alignement de cristaux liquides utilisant un cristal liquide polymère photoréactif à liaisons hydrogène, et pellicule d'alignement de cristaux liquides Download PDF

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WO2016113930A1
WO2016113930A1 PCT/JP2015/070765 JP2015070765W WO2016113930A1 WO 2016113930 A1 WO2016113930 A1 WO 2016113930A1 JP 2015070765 W JP2015070765 W JP 2015070765W WO 2016113930 A1 WO2016113930 A1 WO 2016113930A1
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liquid crystal
group
component
atom
optically active
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PCT/JP2015/070765
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English (en)
Japanese (ja)
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悟志 南
隆之 根木
喜弘 川月
瑞穂 近藤
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日産化学工業株式会社
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Priority to CN201580077825.6A priority Critical patent/CN107636081B/zh
Priority to KR1020177022440A priority patent/KR102435082B1/ko
Priority to JP2016569215A priority patent/JPWO2016113930A1/ja
Publication of WO2016113930A1 publication Critical patent/WO2016113930A1/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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/06—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • C08L101/08—Carboxyl groups
    • 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
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • 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

Definitions

  • the present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, a liquid crystal display element using the same, and a polymer film suitable for the production of an optical element with controlled molecular alignment such as a retardation film and a polarization diffraction element. .
  • 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 wrinkle 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.
  • a rubbing method is conventionally known as an alignment treatment method for a liquid crystal alignment film for imparting alignment control ability.
  • 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.
  • As 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.
  • the main alignment methods are “photolytic type” that causes anisotropic decomposition of the molecular structure by irradiation with polarized UV light, and polyvinyl cinnamate is used to irradiate polarized UV light, and two sides parallel to the polarized light.
  • the polymer film obtained by this alignment amplification method exhibits birefringence due to molecular orientation, it can be used as various optical elements such as a retardation film in addition to the use of a liquid crystal alignment film. it can.
  • the optimal irradiation dose of polarized ultraviolet rays for introducing highly efficient anisotropy into liquid crystal alignment films used in alignment amplification methods is the irradiation dose of polarized ultraviolet rays that optimizes the amount of photoreactive reaction of photosensitive groups in the coating film.
  • the amount of photoreaction will not be sufficient. In that case, sufficient self-organization does not proceed even after heating.
  • the photoreactive side-chain photosensitive group becomes excessive, the resulting film may become rigid and hinder the progress of self-assembly by subsequent heating.
  • liquid crystal alignment films used in the alignment amplification method have a narrow range of the optimal amount of polarized ultraviolet light irradiation because of the high sensitivity of the photoreactive group in the polymer used. is there. As a result, a decrease in manufacturing efficiency of the liquid crystal display element is a problem.
  • the reliability of the liquid crystal display element may be lowered due to the influence of the residual solvent, etc., but the liquid crystal aligning agent obtained by the alignment amplification method is not suitable for polymer liquid crystals. Since baking cannot be performed at a temperature equal to or higher than the liquid crystal expression temperature, the baking temperature is generally low, and the residual solvent contributes to a decrease in reliability.
  • an object of the present invention is to provide a liquid crystal alignment film having a wide process margin that can be adjusted to an optimum polarized ultraviolet ray irradiation amount and an optimum baking temperature, with high efficiency and orientation control ability.
  • component and (B) component are contained, (A) component contains a photoreactive group, and (A) component and (B) component are liquid crystalline supramolecules through a hydrogen bond.
  • An optically active composition characterized by forming. (A) a polymer having a side chain containing a carboxylic acid group structure, and (B) at least one compound selected from compounds represented by the following formula (1).
  • T may be any carbon atom other than Q or X bonded to an oxygen atom, nitrogen atom or sulfur atom, and a hydrogen atom on any carbon atom other than Q or X bonded
  • X represents a single bond or alkylene having 1 to 12 carbon atoms
  • Y represents a single bond, ether, azo, thioether, or ester
  • Z represents an alkylene group having 1 to 36 carbon atoms in which any hydrogen atom may be substituted with fluorine, and any non-adjacent carbon atom may be substituted with an oxygen atom
  • a represents 1 or 2
  • Z is hydrogen, fluorine
  • a hydrogen atom on any carbon atom other than T in Formula (1) bonded to Q or X is substituted with a monovalent organic group. It may represent an aromatic ring having any structure of benzene, biphenyl, terphenyl, naphthalene, anthracene, pyrene, pyridine, furan, pyrrole, or thiophene.
  • a hydrogen atom on any carbon atom other than T in Formula (1) bonded to Q or X is a monovalent organic group. It may represent an aromatic ring having any structure of benzene, biphenyl, terphenyl, naphthalene, anthracene, or pyrene, which may be substituted.
  • the component (A) preferably contains a carboxylic acid group and a photoreactive group in one side chain structure.
  • ⁇ 5> The optically active composition according to any one of ⁇ 1> to ⁇ 4>, wherein the component (B) is 0.5% by weight to 70% by weight with respect to the weight of the polymer of the component (A). It should be contained.
  • the component (A) is any one carboxylic acid selected from the group consisting of the following formulas (2) and (3): It is preferable that the polymer has a side chain containing a group structure.
  • A represents a group selected from a single bond, —O—, —COO—, —CONH—, —NH—, and —CH ⁇ CH—COO—.
  • B represents a group selected from a single bond, —O—, —COO—, —CONH—, —NH—, and —CH ⁇ CH—COO—.
  • at least one of A and B is —CH ⁇ CH—COO—
  • Ar 1 and Ar 2 each independently represent a phenyl group or a naphthyl group
  • l and m are each independently an integer of 0 to 12.
  • the component (B) may be at least one compound selected from the following.
  • R represents an alkyl group having 1 to 36 carbon atoms in which any non-adjacent carbon atom may be substituted with an oxygen atom
  • R ′ represents an oxygen atom, a sulfur atom, or a nitrogen atom in which a hydrogen atom on nitrogen may be substituted with a monovalent organic group
  • the monovalent organic group in R ′ is an arbitrary hydrogen atom
  • a liquid crystal aligning agent comprising the optically active composition according to the above ⁇ 1> to ⁇ 7>.
  • the liquid crystal alignment film according to ⁇ 9> is provided. Liquid crystal display element.
  • an optically active composition which has high efficiency and orientation control ability, has a wide range of optimal polarized ultraviolet ray irradiation, or can suitably select a liquid crystal expression temperature of a polymer liquid crystal, and the composition
  • substrate can be provided.
  • a polymer film having a wide process margin (polarized ultraviolet ray irradiation amount or baking temperature) in the production of an optical element can be provided for a retardation film or the like.
  • FIG. 6 is a graph showing changes in absorbance with respect to an exposure dose at 314 nm when the optically active composition (A2-10) prepared in Example 1 is used.
  • 3 is a graph showing a change in dichroism with respect to an exposure amount at 314 nm when the optically active composition (A2-10) prepared in Example 1 is used. It is a graph showing the change in absorbance with respect to the exposure dose at 314 nm when the optically active composition (A3-10) is used. It is a graph showing the dichroic change with respect to the exposure amount in 314 nm at the time of using an optically active composition (A3-10).
  • FIG. 5 is a graph showing the in-plane order parameter (S) at each irradiation amount (exposure amount) obtained from Example 5 and Comparative Example 3.
  • the optically active composition of the present invention contains the following (A) component and (B) component, the (A) component contains a photoreactive group, the (A) component and the (B) component. And form liquid crystalline supramolecules through hydrogen bonds.
  • T may be any carbon atom other than Q or X bonded to an oxygen atom, nitrogen atom or sulfur atom, and a hydrogen atom on any carbon atom other than Q or X bonded
  • X represents a single bond or alkylene having 1 to 12 carbon atoms
  • Y represents a single bond, ether, azo, thioether, or ester
  • Z represents an alkylene group having 1 to 36 carbon atoms in which any hydrogen atom may be substituted with fluorine, and any non-adjacent carbon atom may be substituted with an oxygen atom
  • a represents 1 or 2
  • Z is hydrogen, fluorine
  • the polymer having a side chain containing a carboxylic acid group structure which is the component (A) in the present invention, is said to exhibit supramolecular liquid crystals due to hydrogen bonds between carboxylic acids.
  • the structure of the aromatic ring-carboxylic acid-carboxylic acid-aromatic ring forming a hydrogen bond has a mesogenic structure as shown below, and the temperature range exhibiting liquid crystallinity and ultraviolet light It is considered that most of the absorption band is determined at this mesogenic site.
  • the aromatic carboxylic acid which is the component (B) of the present invention is present, a carboxylic acid-carboxylic acid hydrogen bond between different kinds of molecules is formed with the component (A), and it consists only of the component (A). Physical properties different from the composition are given. As a result, the temperature range exhibiting liquid crystallinity, the ultraviolet absorption band, and the like change. In the present invention, by freely selecting these combinations, it is possible to adjust the temperature range of the liquid crystal, the sensitivity to ultraviolet rays, and the like in an arbitrary range. Note that these are theories and do not restrict the present invention.
  • the component (A) is a polymer having a side chain containing a carboxylic acid group structure.
  • the component (A) contains a photoreactive group.
  • a carboxylic acid group and a photoreactive group may be contained in one side chain structure, or another side chain containing a photoreactive group may be present in the polymer. From the viewpoint of physical reaction efficiency, it is preferable to contain a carboxylic acid group and a photoreactive group in one side chain structure.
  • a non-carboxylic acid component may be copolymerized together with a side chain component having a carboxylic acid structure at the terminal, but in order to obtain anisotropy (uniaxial orientation), at least the component having a terminal carboxylic acid structure is present. It is preferable to contain 50 mol% or more.
  • the general formula of the side chain (hereinafter also referred to as a specific side chain) is preferably the following formulas (2) and (3 ).
  • A is a group selected from the group consisting of a single bond, —O—, —COO—, —CONH—, —NH—, and —CH ⁇ CH—COO—.
  • —O— and —COO— are preferable from the viewpoint of liquid crystallinity.
  • B represents a group selected from the group consisting of a single bond, —O—, —COO—, —CONH—, —NH—, and —CH ⁇ CH—COO—.
  • -And -COO- are preferred.
  • at least one of A and B is —CH ⁇ CH—COO—.
  • Ar 1 and Ar 2 each independently represent a phenyl group or a naphthyl group.
  • L and m are each independently an integer of 0 to 12, preferably an integer of 2 to 12. Among these, an integer of 2 to 8 is preferable from the viewpoint of liquid crystallinity.
  • p represents an integer of 0 to 12.
  • the polymer of component (A) can be obtained by the polymerization reaction of the monomer containing the specific side chain described above. It can also be obtained by copolymerization of a monomer having a side chain containing a photoreactive group and a monomer having a side chain containing a carboxylic acid group. Furthermore, it can be copolymerized with other monomers as long as the liquid crystallinity is not impaired.
  • Examples of other monomers include industrially available monomers capable of radical polymerization reaction.
  • monomers include unsaturated carboxylic acid, acrylic ester compound, methacrylic ester compound, maleimide compound, acrylonitrile, maleic anhydride, styrene compound and vinyl compound.
  • unsaturated carboxylic acid examples include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and the like.
  • acrylic ester compound examples include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl.
  • methacrylic acid ester compound examples include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl.
  • (Meth) acrylate compounds having a cyclic ether group such as glycidyl (meth) acrylate, (3-methyl-3-oxetanyl) methyl (meth) acrylate, and (3-ethyl-3-oxetanyl) methyl (meth) acrylate are also used. be able to.
  • vinyl compound examples include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.
  • styrene compound examples include styrene, methyl styrene, chlorostyrene, bromostyrene, and the like.
  • maleimide compounds include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.
  • the method for producing the polymer of the component (A) is not particularly limited, and a general-purpose method that is handled industrially can be used. Specifically, it can be produced by cationic polymerization, radical polymerization, or anionic polymerization using a vinyl group of a specific side chain monomer. Among these, radical polymerization is particularly preferable from the viewpoint of ease of reaction control.
  • RAFT reversible addition-cleavage chain transfer
  • a radical thermal polymerization initiator is a compound that generates radicals when heated to a decomposition temperature or higher.
  • radical thermal polymerization initiators include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), hydroperoxides (peroxidation).
  • the radical photopolymerization initiator is not particularly limited as long as it is a compound that initiates radical polymerization by light irradiation.
  • examples of such radical photopolymerization initiators include benzophenone, Michler's ketone, 4,4′-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy -2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2 -Dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (
  • the radical polymerization method is not particularly limited, and an emulsion polymerization method, suspension polymerization method, dispersion polymerization method, precipitation polymerization method, bulk polymerization method, solution polymerization method and the like can be used.
  • the organic solvent used for the polymerization reaction is not particularly limited as long as the generated polymer is soluble. Specific examples are given below.
  • organic solvents may be used alone or in combination. Furthermore, even if it is a solvent which does not dissolve the polymer
  • the polymerization temperature at the time of radical polymerization can be selected from any temperature of 30 ° C. to 150 ° C., but is preferably in the range of 50 ° C. to 100 ° C.
  • the reaction can be carried out at any concentration, but if the concentration is too low, it is difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring is difficult. Therefore, the monomer concentration is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 30% by mass.
  • the initial stage of the reaction is carried out at a high concentration, and then an organic solvent can be added.
  • the molecular weight of the obtained polymer is decreased when the ratio of the radical polymerization initiator is large relative to the monomer, and the molecular weight of the obtained polymer is increased when the ratio is small, the ratio of the radical initiator is
  • the content is preferably 0.1 mol% to 10 mol% with respect to the monomer to be polymerized. Further, various monomer components, solvents, initiators and the like can be added during the polymerization.
  • the reaction solution is poured into a poor solvent to precipitate the polymer.
  • the poor solvent used for precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, and water.
  • the polymer deposited in a poor solvent and precipitated can be recovered by filtration and then dried at normal temperature or under reduced pressure at room temperature or by heating.
  • the polymer collected by precipitation is redissolved in an organic solvent and reprecipitation and collection is repeated 2 to 10 times, impurities in the polymer can be reduced.
  • the poor solvent at this time include alcohols, ketones, hydrocarbons and the like, and it is preferable to use three or more kinds of poor solvents selected from these because purification efficiency is further improved.
  • the molecular weight of the polymer of the component (A) of the present invention was measured by a GPC (Gel Permeation Chromatography) method in consideration of the strength of the obtained coating film, workability during coating film formation, and coating film uniformity.
  • the weight average molecular weight is preferably from 2,000 to 1,000,000, more preferably from 5,000 to 100,000.
  • the optically active composition of the present invention contains a compound represented by the following formula (1) as the component (B).
  • Q represents a single bond or alkylene having 1 to 12 carbon atoms, and preferably represents a single bond or alkylene having 1 to 6 carbon atoms. More preferably, the alkylene is an alkylene having 2 to 4 carbon atoms, and specific examples thereof include ethylene, propylene, butylene and the like.
  • T is an arbitrary carbon atom other than that bonded to Q or X may be substituted with an oxygen atom, a nitrogen atom or a sulfur atom, and any other than bonded to Q or X
  • 5- or 6-membered carbocyclic or heterocyclic ring means a 5- or 6-membered carbocyclic ring or a 5- or 6-membered heterocyclic ring.
  • a structure in which 2 to 4 of these rings are bonded or condensed means any 2 to 4 rings that can be selected from 5-membered or 6-membered carbon rings, 5-membered or 6-membered heterocycles Have a structure in which they are directly bonded to the binding site of the substituent, or the aforementioned 2 to 4 rings are condensed to form a 2 to 4 cyclic group structure.
  • Any carbon atom other than those bonded to Q or X may be substituted with an oxygen atom, a nitrogen atom or a sulfur atom, or a 5- or 6-membered carbocyclic or heterocyclic ring, or 2 of these rings
  • the aromatic ring having a structure in which ⁇ 4 are bonded or condensed include benzene, biphenyl, terphenyl, naphthalene, anthracene, pyrene, pyridine, furan, pyrrole, thiophene, pyrazine, pyrimidine and the like.
  • substitution is 1 or 2 or more, preferably 1 or 2, more preferably 1 carbon. Can be replaced with an atom.
  • the compound of formula (1) excludes compounds containing two or more pyridine structures.
  • containing two or more pyridine structures here means one containing two pyridine structures (bipyridine) or one containing two or more.
  • the pyridine structure is a carboxyl group in both ends of the compound (formula (1)). The one that comes to both ends after the group).
  • at least a is 2 and T is pyridine.
  • the compound of formula (1) excludes compounds containing one or more pyrazine structures, naphthyridine structures, and phenazine structures. According to one more preferred aspect of the present invention, the compound of formula (1) excludes compounds containing two or more pyridine structures, compounds containing one or more pyrazine structures, naphthyridine structures, and phenazine structures.
  • T is a benzene, biphenyl, terphenyl, naphthalene in which a hydrogen atom on any carbon atom other than Q or X may be substituted with a monovalent organic group
  • T is a benzene, biphenyl, terphenyl, naphthalene, anthracene, or pyrene in which a hydrogen atom on any carbon atom other than bonded to X may be substituted with a monovalent organic group.
  • An aromatic ring having any structure is represented.
  • the “monovalent organic group” in which a hydrogen atom on any carbon atom other than that bonded to Q or X may be substituted is preferably an alkyl group such as a methyl group or an ethyl group, Alkoxy groups such as methoxy group and ethoxy group, nitro group, cyano group, dimethylamino group, halogen atoms such as fluorine atom, more preferably methyl group, methoxy group, fluorine, cyano group, nitro group, or dimethylamino More preferably a methyl group, a methoxy group, or a cyano group.
  • X represents a single bond or alkylene having 1 to 12 carbon atoms, and preferably represents alkylene having 1 to 6 carbon atoms. More preferably, the alkylene is an alkylene having 2 to 4 carbon atoms, and specific examples thereof include ethylene, propylene, butylene and the like.
  • Y represents a single bond, ether, thioether, or ester, and preferably represents a single bond or ether.
  • Z has 1 to 36 carbon atoms in which any hydrogen atom may be substituted with fluorine, and any non-adjacent carbon atom may be substituted with an oxygen atom.
  • A represents 1 or 2.
  • Z is hydrogen, fluorine, iodine, bromine, chlorine, hydroxyl group, nitro group, hydrogen on nitrogen atom Atoms may be optionally substituted with one or two alkyl groups having 1 to 36 carbon atoms and optionally substituted with an amino group or a cyano group.
  • Z is a fluorine, a hydroxyl group or a cyano group. May be substituted.
  • R represents an alkyl group having 1 to 36 carbon atoms in which any non-adjacent carbon atom may be substituted with an oxygen atom, and preferably represents an alkyl group having 1 to 10 carbon atoms.
  • R ′ represents an oxygen atom, a sulfur atom, or a nitrogen atom in which a hydrogen atom on nitrogen may be substituted with a monovalent organic group, preferably an oxygen atom or a nitrogen atom.
  • “monovalent organic group” represents an alkyl group having 1 to 10 carbon atoms in which an arbitrary carbon atom may be replaced with an oxygen atom unless they are adjacent to each other, or a phenyl group. Examples include a methyl group, an ethyl group, a methoxyethyl group, and a phenyl group.
  • the component (B) is preferably contained in an amount of 0.5% to 70% by weight, more preferably 5% to 30% by weight, based on the weight of the polymer of the component (A). .
  • the optically active composition used in the present invention is preferably prepared as a coating solution so as to be suitable for forming a coating film. That is, it is preferably prepared as a solution in which the component (A), the component (B), and various additives that will be described later are added in an organic solvent.
  • the content of the component (A), the component (B) and the various additives added as necessary (hereinafter also referred to as a resin component) is preferably 1% by mass to 20% by mass, More preferably, the content is 3% by mass to 15% by mass, and particularly preferably 3% by mass to 10% by mass.
  • Organic solvent used in the optically active composition of the present invention is not particularly limited as long as it is an organic solvent that dissolves the resin component. Specific examples are given below.
  • the polymer contained in the optically active composition of the present invention may be a polymer having all of the side chains containing the carboxylic acid group structure described above, but as long as the liquid crystal expression ability and the photosensitive performance are not impaired. Other polymers other than these may be mixed. In that case, the content of the other polymer in the resin component is 0.5 to 80% by mass, preferably 1 to 50% by mass.
  • polymers examples include polymers that are made of poly (meth) acrylate, polyamic acid, polyimide, and the like and are not photosensitive side chain polymers that can exhibit liquid crystallinity.
  • the optically active composition of the present invention may contain components other than the components (A) and (B). Examples thereof include solvents and compounds that improve the film thickness uniformity and surface smoothness when a solution of the optically active composition is applied, and compounds that improve the adhesion between the coating film and the substrate. However, it is not limited to this.
  • solvents that improve film thickness uniformity and surface smoothness include the following.
  • solvents may be used alone or in combination.
  • it is preferably 5% by mass to 80% by mass with respect to the entire solvent so as not to significantly reduce the solubility of the entire solvent contained in the optically active composition of the present invention. More preferably, it is 20% by mass to 60% by mass.
  • Examples of compounds that improve film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.
  • Ftop (registered trademark) 301, EF303, EF352 (manufactured by Tochem Products), MegaFac (registered trademark) F171, F173, R-30 (manufactured by DIC), Florard FC430, FC431 (Manufactured by Sumitomo 3M), Asahi Guard (registered trademark) AG710 (manufactured by Asahi Glass Company), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimi Chemical Co., Ltd.) It is done.
  • the use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the resin component contained in the polymer composition. Part by mass.
  • Specific examples of the compound for improving the adhesion between the coating film and the substrate include the following functional silane-containing compounds.
  • additives such as the following phenoplasts and epoxy group-containing compounds are used for the purpose of preventing deterioration of electrical characteristics due to the backlight when a liquid crystal display element is constructed. May be contained in the optically active composition of the present invention. Specific phenoplast additives are shown below, but are not limited to this structure.
  • Specific epoxy group-containing compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ′, N ′,-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N ′,-tetraglycidyl-4 4'-diaminodipheny
  • the amount used is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the resin component contained in the optically active composition. More preferably, it is 1 to 20 parts by mass. If the amount used is less than 0.1 parts by mass, the effect of improving the adhesion cannot be expected, and if it exceeds 30 parts by mass, the orientation of the liquid crystal may deteriorate.
  • a photosensitizer can also be used as an additive. Colorless and triplet sensitizers are preferred.
  • Aromatic 2-hydroxyketones (2-hydroxybenzophenone, mono- or di-p- (dimethylamino) -2-hydroxybenzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, benzanthrone, thiazoline (2-benzoylmethylene-3 -Methyl- ⁇ -naphthothiazoline, 2- ( ⁇ -naphthoylmethylene) -3-methylbenzothiazoline, 2- ( ⁇ -naphthoylmethylene) -3-methylbenzothiazoline, 2- (4-biphenoylmethylene)- 3-methylbenzothi Zolin, 2- ( ⁇ -naphtho
  • aromatic 2-hydroxyketone (benzophenone), coumarin, ketocoumarin, carbonyl biscoumarin, acetophenone, anthraquinone, xanthone, thioxanthone, and acetophenone ketal.
  • a dielectric or conductive material is used for the purpose of changing the electrical properties such as the dielectric constant and conductivity of the coating film as long as the effects of the present invention are not impaired.
  • a crosslinkable compound may be added for the purpose of increasing the hardness and density of the substance and, further, the film when formed into a coating film.
  • the coating film obtained by coating and baking the optically active composition described above on a substrate can be used as a liquid crystal alignment film, for example.
  • the method for applying the liquid crystal aligning agent containing the optically active composition of the present invention onto a substrate having a conductive film for driving a lateral electric field is not particularly limited.
  • the application method is generally industrially performed by screen printing, offset printing, flexographic printing, or an inkjet method.
  • 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.
  • a liquid crystal display device using a liquid crystal aligning agent containing the optically active composition of the present invention is represented by the following steps [I] to [IV]. That is, first, a substrate having a liquid crystal alignment film can be produced by a method including the following [I] to [III].
  • Step [I] is a process of applying the liquid crystal aligning agent of the present invention on a substrate having a conductive film.
  • the solvent can be evaporated at 50 to 200 ° C., preferably 50 to 150 ° C. by a heating means such as a hot plate, a heat circulation oven or an IR (infrared) oven, and a coating film can be obtained.
  • the drying temperature at this time is preferably lower than the liquid crystal phase expression temperature of the side chain polymer.
  • the thickness of the coating film is preferably 5 nm to 300 nm, more preferably 10 nm to 150 nm. It is.
  • 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 290 nm to 400 nm can be selected and used so that the photocrosslinking reaction can be selectively induced.
  • the ultraviolet light for example, light emitted from a high-pressure mercury 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.
  • Heating can be performed using a heating means such as a hot plate, a heat circulation type oven, or an IR (infrared) type oven.
  • the heating temperature can be determined in consideration of the temperature at which the liquid crystallinity of the coating film used is developed.
  • the heating temperature is preferably within the temperature range of the temperature at which the side chain polymer exhibits liquid crystallinity (hereinafter referred to as liquid crystal expression temperature).
  • the liquid crystal expression temperature on the coating film surface is expected to be lower than the liquid crystal expression temperature when a photosensitive side chain polymer that can exhibit liquid crystallinity is observed in bulk.
  • the heating temperature is more preferably within the temperature range of the liquid crystal expression temperature on the coating film surface. That is, the temperature range of the heating temperature after irradiation with polarized ultraviolet rays is 10 ° C. lower than the lower limit of the temperature range of the liquid crystal expression temperature of the side chain polymer used, and 10 ° C.
  • the temperature of the range which makes an upper limit If the heating temperature is lower than the above temperature range, the anisotropic amplification effect due to heat in the coating film tends to be insufficient, and if the heating temperature is too higher than the above temperature range, the state of the coating film Tends to be close to an isotropic liquid state (isotropic phase), and in this case, self-organization may make it difficult to reorient in one direction.
  • the liquid crystal expression temperature is not less than the glass transition temperature (Tg) at which the side chain polymer or coating film surface undergoes a phase transition from the solid phase to the liquid crystal phase, and from the liquid crystal phase to the isotropic phase (isotropic phase). It means a temperature below the isotropic phase transition temperature (Tiso) that causes a phase transition.
  • 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
  • a substrate having a liquid crystal alignment film obtained in [III] is disposed oppositely so that both liquid crystal alignment films face each other through liquid crystal, and a liquid crystal cell is produced by a known method. And a step of manufacturing a liquid crystal display element.
  • liquid crystal cell or a liquid crystal display element two sheets of the above-mentioned substrate 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
  • Examples include a method in which the other substrate is bonded and liquid crystal is injected under reduced pressure, or a method in which liquid crystal is dropped on the liquid crystal alignment film surface on which spacers are dispersed, and then the substrate is bonded and sealed. can do.
  • 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.
  • a polymer composition is applied on a substrate to form a coated film, and then irradiated with polarized ultraviolet rays. Next, by heating, high-efficiency anisotropy is introduced into the side 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 realizes the introduction of highly efficient anisotropy into the coating film by utilizing the principle of molecular reorientation induced by the side chain photoreaction and liquid crystallinity. .
  • polarized ultraviolet rays are formed. After irradiation and then heating, a liquid crystal display element is formed.
  • 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 by the method of the present invention or the lateral electric field drive type liquid crystal display element having the substrate has excellent reliability, large screen and high definition. It can be suitably used for LCD TVs.
  • tetrahydrofuran is 10 ml / L
  • Flow rate 1.0 ml / standard curve preparation standard sample: Tosoh TSK standard polyethylene oxide (molecular weight about 9,000,150,000, 100,000, 30,000) and polymer laboratory polyethylene glycol ( Molecular weight about 12,000, 4,000 1,000).
  • Example 1 M6CA (12.41 g, 35.0 mmol) was dissolved in THF (111.7 g), and after deaeration with a diaphragm pump, AIBN (0.287 g, 1.8 mmol) was added and deaeration was performed again. It was. Thereafter, the mixture was reacted at 60 ° C. for 30 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to diethyl ether (500 ml), and the resulting precipitate was filtered. This precipitate was washed with diethyl ether and dried under reduced pressure in an oven at 40 ° C. to obtain methacrylate polymer powder (A). The number average molecular weight of this polymer was 11,000, and the weight average molecular weight was 26000.
  • NMP 29.29 g was added to the obtained methacrylate polymer powder (A) (6.0 g), and the mixture was dissolved by stirring at room temperature for 5 hours. NMP (14.7 g) and BC (50.0 g) were added to this solution and stirred for 5 hours to obtain a liquid crystal aligning agent (A1).
  • cinnamic acid-based additive 6MN2C (5% by mass with respect to the solid content) is added to 10.0 g of the liquid crystal aligning agent (A1), and the mixture is stirred for 3 hours at room temperature to be dissolved.
  • An aligning agent (A2-5) was prepared.
  • liquid crystal aligning agents A2-10 to A7-50 were prepared by changing the type and amount of cinnamic acid additive as shown in the table below.
  • Example 2 A liquid crystal cell was prepared using the liquid crystal aligning agent (A2-5) obtained in Example 1, and the orientation of the low molecular liquid crystal was confirmed. The conditions for obtaining the optimum orientation were confirmed by varying the irradiation amount of polarized UV in the alignment treatment and the heating temperature after polarized UV irradiation.
  • the substrate used was a glass substrate having a size of 30 mm ⁇ 40 mm and a thickness of 0.7 mm, on which comb-like pixel electrodes formed by patterning an ITO film were arranged.
  • the pixel electrode has a comb-like shape configured by arranging a plurality of dog-shaped electrode elements whose central portion is bent. The width in the short direction of each electrode element is 10 ⁇ m, and the distance between the electrode elements is 20 ⁇ m. Since the pixel electrode forming each pixel is formed by arranging a plurality of bent-shaped electrode elements in the central portion, the shape of each pixel is not rectangular, but in the central portion like the electrode elements.
  • Each pixel has a shape that bends and resembles a bold-faced koji.
  • 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 alignment processing direction of the liquid crystal alignment film described later is used as a reference, the electrode element of the pixel electrode is formed to form an angle of + 15 ° (clockwise) in the first region of the pixel, and in the second region of the pixel.
  • the electrode elements of the pixel electrode are formed so as to form an angle of ⁇ 15 ° (clockwise). That is, in the first region and the second region of each pixel, the directions of the rotation operation (in-plane switching) of the liquid crystal induced by the voltage application between the pixel electrode and the counter electrode are mutually in the substrate plane. It is comprised so that it may become a reverse direction.
  • the liquid crystal aligning agent (A2) obtained in Example 1 was spin-coated on the prepared substrate with electrodes. Subsequently, it dried for 90 second with a 70 degreeC hotplate, and formed the liquid crystal aligning film with a film thickness of 100 nm.
  • the coating surface was irradiated with 3 to 13 mJ / cm 2 of 313 nm ultraviolet rays via a polarizing plate and then heated on a hot plate at 140 to 170 ° C. for 10 minutes to obtain a substrate with a liquid crystal alignment film. Further, a coating film was similarly formed on a glass substrate having a columnar spacer having a height of 4 ⁇ m on which no electrode was formed as a counter substrate, and an orientation treatment was performed. A sealant (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) was printed on the liquid crystal alignment film of one substrate.
  • a liquid crystal cell having a configuration of an IPS (In-Plane Switching) mode liquid crystal display element was prepared by injecting liquid crystal MLC-2041 (manufactured by Merck Co., Ltd.) into the empty cell by a reduced pressure injection method, sealing the injection port. Obtained.
  • IPS In-Plane Switching
  • the obtained liquid crystal cell was placed between polarizing plates made of crossed Nicols, and the orientation of the liquid crystal was confirmed. Further, an AC voltage of 8 Vpp was applied between the electrodes, and it was confirmed whether or not the liquid crystal in the pixel portion was driven.
  • the table below shows the results of the liquid crystal orientation depending on the irradiation amount of polarized UV and the subsequent heating temperature.
  • X indicates that alignment failure such as fluid alignment is confirmed after liquid crystal injection
  • ⁇ indicates that liquid crystal alignment is confirmed without alignment failure.
  • Example 3 A liquid crystal cell was produced using the liquid crystal aligning agent (A2-10) in the same manner as in Example 2, and the orientation of the obtained liquid crystal cell was confirmed. Table 3 below shows the results of the liquid crystal alignment of the liquid crystal cell.
  • the heating temperature there is a concern about deterioration of the electrical characteristics of the liquid crystal display element due to the influence of the residual solvent and the like, and thus it is required to perform firing at as high a temperature as possible.
  • the ability to arbitrarily select the heating conditions to be obtained leads to a wider range of material selection.
  • Example 4 The optically active composition (A2-10) produced in Example 1 was applied to a 1.1 mm quartz substrate by spin coating so as to have a film thickness of 100 nm, and dried on a hot plate at 70 ° C.
  • This coating film was irradiated with 313 nm polarized UV light from 0 J / cm 2 to 30 J / cm 2 , and then heat-treated for 10 minutes on a hot plate at 170 ° C. (so-called orientation amplification treatment by self-organization of polymer liquid crystal). It was.
  • Dichroism ⁇ A A
  • the absorbance is a value of absorbance at 314 nm.
  • LPUV represents the result for the polarized UV irradiated substrate before heating at 170 ° C.
  • anneal represents the result for the polarized UV irradiated substrate after 170 ° C. heating.
  • Exposure energy on the horizontal axis in the figure means the exposure amount.
  • UV-3100 manufactured by Shimadzu Corporation was used for measurement of polarized UV-vis absorption spectrum.
  • Example 5 The same treatment as in Example 4 was also performed on the optically active composition (A2-5, A2-30, A2-50), and together with A2-10, an in-plane order parameter (degree of in-plane orientation) in each thin film was obtained. S) was tracked. The in-plane orientation degree S was measured by measuring a polarized UV-vis absorption spectrum and calculated by the following equation.
  • In-plane orientation degree S (A ⁇ A
  • the absorbance value at 314 nm was used.
  • FIG. 5 shows the in-plane orientation degree S at each dose obtained from Example 5 and Comparative Example 3.
  • Example 5 since all take positive values, it can be seen that they are oriented in the direction perpendicular to the light irradiation axis. In the figure, the larger the numerical value, the higher the degree of orientation.
  • Example 4 From the evaluation of Example 4 and Comparative Example 2, by adding a cinnamic acid-based additive, changes in absorbance and dichroism that are not manifested only by the liquid crystal aligning agent (A1) occur. It was confirmed that the dichroic size can be changed.
  • Example 5 Comparative Example 3
  • a cinnamic acid-based additive by adding a cinnamic acid-based additive, an in-plane alignment degree that cannot be expressed only by the liquid crystal aligning agent (A1) can be produced. It has been clarified that the optimum irradiation region for increasing the degree of in-plane orientation can be changed according to the added amount of the agent.

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Abstract

La présente invention concerne une pellicule d'alignement de cristaux liquides qui présente des performances de contrôle d'alignement d'efficacité élevée et de plage importante vis-à-vis de la quantité d'irradiation ultraviolette polarisée optimale de celle-ci. Le problème abordé par la présente invention est résolu par une composition optiquement active caractérisée en ce que : ladite composition optiquement active comprend le composant (A) et le composant (B) indiqués ci-après; le composant (A) comprend un groupement photoréactif; et le composant (A) et le composant (B) forment une supermolécule de cristaux liquides par l'intermédiaire d'une liaison hydrogène. Le composant (A) est un polymère qui porte une chaîne latérale comprenant une structure de groupement acide carboxylique. Le composant (B) est au moins un composé choisi parmi les composés aromatiques représentés par la formule (1) (où les symboles dans la formule sont tels que définis dans la description).
PCT/JP2015/070765 2015-01-15 2015-07-22 Agent d'alignement de cristaux liquides utilisant un cristal liquide polymère photoréactif à liaisons hydrogène, et pellicule d'alignement de cristaux liquides WO2016113930A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016194846A1 (fr) * 2015-06-02 2016-12-08 日産化学工業株式会社 Agent d'alignement de cristaux liquides pour photo-alignement, matériau d'alignement et matériau de retard
WO2017061541A1 (fr) * 2015-10-07 2017-04-13 日産化学工業株式会社 Composition de fabrication de film d'alignement de cristaux liquides, film d'alignement de cristaux liquides utilisant ladite composition et son procédé de fabrication, élément d'affichage à cristaux liquides ayant un film d'alignement de cristaux liquides et son procédé de fabrication
WO2022176555A1 (fr) * 2021-02-19 2022-08-25 株式会社フジクラ Élément diffractif optique, dispositif informatique optique et procédé de production d'un élément diffractif optique

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020111198A1 (fr) * 2018-11-29 2020-06-04 日産化学株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et matériel de retardement

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1160619A (ja) * 1997-08-07 1999-03-02 Jsr Corp 液晶性組成物、硬化物およびその製造方法
JP2007304215A (ja) * 2006-05-09 2007-11-22 Hayashi Telempu Co Ltd 光配向材および光学素子、液晶配向膜の製造方法
JP2008164925A (ja) * 2006-12-28 2008-07-17 Hayashi Telempu Co Ltd 位相差フィルムおよびその製造方法
JP2008276149A (ja) * 2007-04-27 2008-11-13 Hayashi Telempu Co Ltd 高分子フィルム、分子配向素子の作製方法、および液晶配向膜
WO2014054785A2 (fr) * 2012-10-05 2014-04-10 日産化学工業株式会社 Procédé de fabrication pour un substrat ayant un film d'alignement de cristaux liquides pour un élément d'affichage à cristaux liquides de type à commutation dans le plan
WO2014148569A1 (fr) * 2013-03-19 2014-09-25 日産化学工業株式会社 Procédé de fabrication d'élément d'affichage à cristaux liquides du type à commutation dans le plan
WO2015053232A1 (fr) * 2013-10-07 2015-04-16 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
WO2015114864A1 (fr) * 2014-01-30 2015-08-06 公立大学法人兵庫県立大学 Composition de cristaux liquides photoréactifs, élément d'affichage, élément optique, procédé de fabrication d'un élément d'affichage, et procédé de fabrication d'un élément optique

Family Cites Families (8)

* 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
GB9828124D0 (en) 1998-12-22 1999-02-17 Secr Defence Brit Photoactive propane derivatives and orientation layers
JP3979500B2 (ja) 2003-11-21 2007-09-19 独立行政法人科学技術振興機構 有機微結晶配向分散体、偏光蛍光材料、並びにその製造方法
WO2009081692A1 (fr) * 2007-12-26 2009-07-02 Jsr Corporation Agent d'alignement de cristal liquide et procédé de formation de film d'alignement de cristal liquide
JP5831674B2 (ja) * 2010-02-03 2015-12-09 Jsr株式会社 液晶配向剤
CN102934012B (zh) * 2010-03-31 2016-05-25 日产化学工业株式会社 液晶取向剂、液晶取向膜和液晶显示元件
JP6233304B2 (ja) * 2012-04-24 2017-11-22 Jnc株式会社 光配向用液晶配向膜を形成するための液晶配向剤、液晶配向膜およびこれを用いた液晶表示素子
JP6131730B2 (ja) * 2013-06-17 2017-05-24 富士通株式会社 半導体装置及びその冷却方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1160619A (ja) * 1997-08-07 1999-03-02 Jsr Corp 液晶性組成物、硬化物およびその製造方法
JP2007304215A (ja) * 2006-05-09 2007-11-22 Hayashi Telempu Co Ltd 光配向材および光学素子、液晶配向膜の製造方法
JP2008164925A (ja) * 2006-12-28 2008-07-17 Hayashi Telempu Co Ltd 位相差フィルムおよびその製造方法
JP2008276149A (ja) * 2007-04-27 2008-11-13 Hayashi Telempu Co Ltd 高分子フィルム、分子配向素子の作製方法、および液晶配向膜
WO2014054785A2 (fr) * 2012-10-05 2014-04-10 日産化学工業株式会社 Procédé de fabrication pour un substrat ayant un film d'alignement de cristaux liquides pour un élément d'affichage à cristaux liquides de type à commutation dans le plan
WO2014148569A1 (fr) * 2013-03-19 2014-09-25 日産化学工業株式会社 Procédé de fabrication d'élément d'affichage à cristaux liquides du type à commutation dans le plan
WO2015053232A1 (fr) * 2013-10-07 2015-04-16 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
WO2015114864A1 (fr) * 2014-01-30 2015-08-06 公立大学法人兵庫県立大学 Composition de cristaux liquides photoréactifs, élément d'affichage, élément optique, procédé de fabrication d'un élément d'affichage, et procédé de fabrication d'un élément optique

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
EMI UCHIDA ET AL.: "Photoinduced Orientation in Photoreactive Hydrogen-Bonding Liquid Crystalline Polymers and Liquid Crystal Alignment on the Resultant Films", MACROMOLECULES, vol. 39, no. 26, 2006, pages 9357 - 9364 *
NOBUHIRO KAWATSUKI ET AL.: "Photoinduced Cooperative Reorientation in Photoreactive Hydrogen-Bonded Copolymer Films and LC Alignment Using the Resultant Films", MACROMOLECULES, vol. 41, no. 13, 2008, pages 4642 - 4650 *
TAKASHI KATO ET AL.: "Functional liquid-crystalline assemblies: Self-organized soft materials", ANGEWANDTE CHEMIE , INTERNATIONAL EDITION, vol. 45, no. 1, 2006, pages 38 - 68 *
TAKASHI KATO ET AL.: "Stabilization of a liquid-crystalline phase through noncovalent interaction with a polymer side chain", MACROMOLECULES, vol. 22, no. 9, 1989, pages 3818 - 3819 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016194846A1 (fr) * 2015-06-02 2016-12-08 日産化学工業株式会社 Agent d'alignement de cristaux liquides pour photo-alignement, matériau d'alignement et matériau de retard
US10428274B2 (en) 2015-06-02 2019-10-01 Nissan Chemical Industries, Ltd. Liquid crystal alignment agent for photo-alignment, aligning member, and retardation member
WO2017061541A1 (fr) * 2015-10-07 2017-04-13 日産化学工業株式会社 Composition de fabrication de film d'alignement de cristaux liquides, film d'alignement de cristaux liquides utilisant ladite composition et son procédé de fabrication, élément d'affichage à cristaux liquides ayant un film d'alignement de cristaux liquides et son procédé de fabrication
WO2022176555A1 (fr) * 2021-02-19 2022-08-25 株式会社フジクラ Élément diffractif optique, dispositif informatique optique et procédé de production d'un élément diffractif optique

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KR20170105058A (ko) 2017-09-18
TWI689543B (zh) 2020-04-01
CN107636081B (zh) 2021-01-29
JPWO2016113930A1 (ja) 2017-10-26
CN107636081A (zh) 2018-01-26
TW201625744A (zh) 2016-07-16

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