WO2012002511A1 - Agent d'alignement de cristaux liquides, film à alignement de cristaux liquides, élément d'affichage à cristaux liquides et procédé de production d'éléments d'affichage à cristaux liquides - Google Patents

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

Info

Publication number
WO2012002511A1
WO2012002511A1 PCT/JP2011/065101 JP2011065101W WO2012002511A1 WO 2012002511 A1 WO2012002511 A1 WO 2012002511A1 JP 2011065101 W JP2011065101 W JP 2011065101W WO 2012002511 A1 WO2012002511 A1 WO 2012002511A1
Authority
WO
WIPO (PCT)
Prior art keywords
liquid crystal
group
aligning agent
crystal aligning
polymerizable compound
Prior art date
Application number
PCT/JP2011/065101
Other languages
English (en)
Japanese (ja)
Inventor
亮一 芦澤
ダニエルアントニオ 櫻葉汀
欣也 松本
洋一 山之内
Original Assignee
日産化学工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日産化学工業株式会社 filed Critical 日産化学工業株式会社
Priority to JP2012522704A priority Critical patent/JP5761532B2/ja
Priority to KR1020137001733A priority patent/KR101831006B1/ko
Priority to CN201180041448.2A priority patent/CN103080152B/zh
Publication of WO2012002511A1 publication Critical patent/WO2012002511A1/fr

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/58—One oxygen atom, e.g. butenolide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F24/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a heterocyclic ring containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • 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
    • 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
    • G02F1/133715—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films by first depositing a monomer

Definitions

  • the present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film, a liquid crystal display element, and a liquid crystal display element that can be used in the manufacture of a liquid crystal display element of a vertical alignment method that is manufactured by irradiating ultraviolet rays with voltage applied to liquid crystal molecules It relates to a manufacturing method.
  • a liquid crystal display element of a method in which liquid crystal molecules aligned perpendicular to a substrate are responded by an electric field also referred to as a vertical alignment (VA) method
  • an ultraviolet ray is applied while applying a voltage to the liquid crystal molecules in the manufacturing process.
  • VA vertical alignment
  • a photopolymerizable compound is added to a liquid crystal composition in advance and used together with a vertical alignment film such as polyimide to irradiate ultraviolet rays while applying a voltage to a liquid crystal cell.
  • a technique for increasing the response speed of liquid crystal for example, see Patent Document 1 and Non-Patent Document 1 is known (PSA (Polymer Sustained Alignment) type liquid crystal display).
  • PSA Polymer Sustained Alignment
  • the direction in which the liquid crystal molecules tilt in response to an electric field is controlled by protrusions provided on the substrate or slits provided on the display electrode, but a liquid crystal composition is added with a photopolymerizable compound.
  • the solubility of the polymerizable compound added to the liquid crystal is low, and there is a problem that when the addition amount is increased, it precipitates at a low temperature.
  • the addition amount of the polymerizable compound is reduced, a good alignment state cannot be obtained.
  • the unreacted polymerizable compound remaining in the liquid crystal becomes an impurity (contamination) in the liquid crystal, there is a problem that the reliability of the liquid crystal display element is lowered.
  • the UV irradiation treatment necessary in the PSA mode is large, the components in the liquid crystal are decomposed and the reliability is lowered.
  • Non-Patent Document 2 the response speed of the liquid crystal display element is increased by adding the photopolymerizable compound to the liquid crystal alignment film instead of the liquid crystal composition (SC-PVA liquid crystal display) (for example, Non-Patent Document 2).
  • An object of the present invention is to solve the above-described problems of the prior art, and a liquid crystal aligning agent, a liquid crystal alignment film, a liquid crystal display element, and a liquid crystal display capable of improving the response speed of a vertical alignment type liquid crystal display element.
  • the object is to provide a method for manufacturing an element.
  • the liquid crystal aligning agent of the present invention that solves the above problems comprises a side chain for vertically aligning liquid crystals and a photoreactive side chain containing at least one selected from a methacryl group, an acrylic group, a vinyl group, and a cinnamoyl group.
  • a polyimide precursor having, at least one polymer selected from polyimides obtained by imidizing this polyimide precursor, and a polymerizable compound each having a photopolymerizable or photocrosslinkable group at two or more terminals, And a solvent.
  • the photoreactive side chain preferably contains a group selected from the following formula (I).
  • R 11 is H or a methyl group
  • the photopolymerization or photocrosslinking group is preferably selected from the following formula (II).
  • R 12 is H or an alkyl group having 1 to 4 carbon atoms
  • Z 1 is a divalent alkyl group optionally having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms
  • Z 2 is a monovalent aromatic ring or heterocyclic ring optionally substituted by an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms.
  • the liquid crystal alignment film of the present invention is obtained by applying the above liquid crystal aligning agent to a substrate and baking it.
  • the liquid crystal display element of the present invention is produced by applying a liquid crystal layer by contacting the liquid crystal aligning agent obtained above by applying the liquid crystal aligning agent to a substrate and baking it, and irradiating ultraviolet rays while applying a voltage to the liquid crystal layer.
  • the liquid crystal cell is provided.
  • the manufacturing method of the liquid crystal display element of this invention provides the liquid crystal layer by making it contact with the liquid crystal aligning film obtained by apply
  • the present invention it is possible to provide a vertical alignment type liquid crystal display device having a high response speed. And in this liquid crystal aligning agent, even if it is a case where the addition amount of a polymeric compound is small, a response speed can fully be improved.
  • the liquid crystal aligning agent of the present invention is a polyimide precursor having a side chain for vertically aligning a liquid crystal and a photoreactive side chain containing at least one selected from a methacryl group, an acrylic group, a vinyl group and a cinnamoyl group, And at least one polymer selected from polyimides obtained by imidizing this polyimide precursor, a polymerizable compound each having a photopolymerizable or photocrosslinking group at two or more terminals, and a solvent It is.
  • the liquid crystal aligning agent is a solution for forming a liquid crystal aligning film, and the liquid crystal aligning film is a film for aligning liquid crystals in a predetermined direction, in the present invention, in the vertical direction.
  • the liquid crystal aligning agent of this invention contains the polymeric compound which has the group respectively photopolymerized or photocrosslinked in two or more terminal. That is, the polymerizable compound contained in the liquid crystal aligning agent of the present invention is a compound having two or more terminals having groups that undergo photopolymerization or photocrosslinking.
  • the polymerizable compound having a photopolymerizable group is a compound having a functional group that causes polymerization upon irradiation with light.
  • the compound having a photocrosslinking group is at least one selected from a polymer of a polymerizable compound, a polyimide precursor, and a polyimide obtained by imidizing the polyimide precursor by irradiating light. It is a compound having a functional group capable of reacting with the polymer and crosslinking with these polymers.
  • a compound having a photocrosslinkable group also reacts with a compound having a photocrosslinkable group.
  • Such a polymerizable compound has a side chain for vertically aligning a liquid crystal, which will be described in detail later, and a photoreactive side chain containing at least one selected from a methacryl group, an acrylic group, a vinyl group, and a cinnamoyl group.
  • a liquid crystal display of a vertical alignment system such as an SC-PVA liquid crystal display, which is contained in a liquid crystal aligning agent together with a polyimide precursor and at least one polymer selected from polyimides obtained by imidizing the polyimide precursor.
  • the response speed is dramatically improved. The response speed can be sufficiently improved even with a small addition amount of the polymerizable compound.
  • Examples of the group that undergoes photopolymerization or photocrosslinking include monovalent groups represented by the above formula (II).
  • the polymerizable compound examples include a compound having a photopolymerizable group at each of two ends represented by the following formula (III), and a photopolymerizable group represented by the following formula (IV).
  • examples thereof include a compound having a terminal having a terminal that has a photocrosslinkable group and a compound having a group that is photocrosslinked to each of two terminals represented by the following formula (V).
  • R 12, Z 1 and Z 2 are the same as R 12, Z 1 and Z 2 in the formula (II), Q 1 is a divalent organic group is there.
  • Q 1 has a ring structure such as a phenylene group (—C 6 H 4 —), a biphenylene group (—C 6 H 4 —C 6 H 4 —), a cyclohexylene group (—C 6 H 10 —), and the like. Preferably it is. This is because the interaction with the liquid crystal tends to increase.
  • the polymerizable compound represented by the formula (III) include a polymerizable compound represented by the following formula (1).
  • V is a single bond or —R 1 O—
  • R 1 is a linear or branched alkylene group having 1 to 10 carbon atoms, preferably —R 1 O—.
  • R 1 is a linear or branched alkylene group having 2 to 6 carbon atoms.
  • W represents a single bond or —OR 2 —
  • R 2 represents a linear or branched alkylene group having 1 to 10 carbon atoms, and preferably represents —OR 2 — and R 2 represents a linear or A branched alkylene group having 2 to 6 carbon atoms.
  • V and W may be the same or different, but if they are the same, synthesis is easy.
  • about the polymeric compound represented by following formula (1) since it applied for separately, you may remove from this invention.
  • the polymerizable compound represented by the above formula (1) is a compound having a specific structure having an ⁇ -methylene- ⁇ -butyrolactone group which is a polymerizable group (photopolymerizable group) at both ends.
  • at least one kind selected from a polyimide precursor and a polyimide obtained by imidizing this polyimide precursor The response speed can be particularly greatly improved by using the polymer for manufacturing a vertical alignment type liquid crystal display element such as an SC-PVA type liquid crystal display using the liquid crystal alignment film as a material.
  • the process of forming the liquid crystal alignment film includes a step of baking at a high temperature to completely remove the solvent.
  • a polymerizable group such as an acrylate group, a methacrylate group, a vinyl group, a vinyloxy group, or an epoxy group is added.
  • the compounds that are possessed have poor thermal stability and are difficult to withstand firing at high temperatures.
  • the polymerizable compound represented by the above formula (1) can sufficiently withstand a high temperature, for example, a firing temperature of 200 ° C. or higher, because of its poor thermal polymerizability.
  • the photopolymerization or photocrosslinking group is a polymerizable compound having an acrylate group or a methacrylate group instead of an ⁇ -methylene- ⁇ -butyrolactone group
  • the acrylate group or methacrylate group is a spacer such as an oxyalkylene group.
  • the response speed is greatly improved, as in the case of the polymerizable compound having an ⁇ -methylene- ⁇ -butyrolactone group at both ends. be able to.
  • the polymerizable compound has a structure in which an acrylate group or a methacrylate group is bonded to a phenylene group via a spacer such as an oxyalkylene group, the stability to heat is improved, or a high temperature, for example, 200 ° C. or higher. Can sufficiently withstand the firing temperature.
  • a compound represented by the following formula is a novel compound.
  • the method for producing such a polymerizable compound is not particularly limited, and for example, it can be produced according to the synthesis examples described later.
  • the polymerizable compound represented by the above formula (1) can be synthesized by combining techniques in organic synthetic chemistry.
  • taraga and the like represented by the following reaction formula are prepared by the method proposed by P. Talaga, M. Schaeffer, C. Benezra and JLStampf, Synthesis, 530 (1990) using SnCl 2 and 2- (bromomethyl) acrylic acid. It can be synthesized by reacting (2- (bromomethyl) propenoic acid) with aldehyde or ketone.
  • Amberlyst 15 is a strongly acidic ion exchange resin manufactured by Rohm and Haas.
  • R ′ represents a monovalent organic group.
  • 2- (bromomethyl) acrylic acid is represented by the following reaction formula: K. Ramarajan, K. Kamalingam, DJO 'Donnell and KDBerlin, Organic Synthesis, vol.61, 56-59 (1983) It can be synthesized by the method proposed in.
  • the liquid crystal aligning agent of the present invention is at least one selected from a polyimide precursor and a polyimide obtained by imidizing the polyimide precursor, and a side chain and a photoreactive side for vertically aligning liquid crystals.
  • a polymer having a chain examples include polyamic acid (also referred to as polyamic acid), polyamic acid ester, and the like.
  • the side chain for vertically aligning the liquid crystal of the polymer is not limited as long as the liquid crystal can be aligned vertically with respect to the substrate.
  • a long chain alkyl group or a middle of a long chain alkyl group may be used.
  • the side chain for vertically aligning the liquid crystal may be directly bonded to a polyimide precursor such as polyamic acid or polyamic acid ester or a main chain of polyimide, that is, a polyamic acid skeleton, a polyimide skeleton, or the like. You may couple
  • a polyimide precursor such as polyamic acid or polyamic acid ester or a main chain of polyimide, that is, a polyamic acid skeleton, a polyimide skeleton, or the like. You may couple
  • Examples of the side chain for vertically aligning the liquid crystal include a hydrocarbon group having 8 to 30 carbon atoms, preferably 8 to 22 carbon atoms in which hydrogen atoms may be substituted with fluorine, specifically, alkyl groups, fluoro Examples thereof include an alkyl group, an alkenyl group, a phenethyl group, a styrylalkyl group, a naphthyl group, and a fluorophenylalkyl group.
  • Examples of the side chain for vertically aligning other liquid crystals include those represented by the following formula (a).
  • l, m and n each independently represents an integer of 0 or 1
  • R 3 represents an alkylene group having 2 to 6 carbon atoms, —O—, —COO—, —OCO—, —NHCO—.
  • R 4 , R 5 and R 6 each independently represents a phenylene group or a cycloalkylene group
  • R 7 is a hydrogen atom
  • 2 to 24 represents an alkyl group or a fluorine-containing alkyl group, a monovalent aromatic ring, a monovalent aliphatic ring, a monovalent heterocyclic ring, or a monovalent macrocyclic substituent comprising them.
  • R 3 in the above formula (a) is preferably —O—, —COO—, —CONH—, or an alkylene-ether group having 1 to 3 carbon atoms from the viewpoint of ease of synthesis.
  • R 4 , R 5 and R 6 in the formula (a) are l, m, n, R 4 and R 5 shown in Table 1 below from the viewpoint of ease of synthesis and ability to align liquid crystals vertically. And a combination of R 6 is preferred.
  • R 7 in the formula (a) is preferably a hydrogen atom, an alkyl group having 2 to 14 carbon atoms or a fluorine-containing alkyl group, more preferably A hydrogen atom, an alkyl group having 2 to 12 carbon atoms, or a fluorine-containing alkyl group.
  • R 7 is preferably an alkyl group having 12 to 22 carbon atoms or a fluorine-containing alkyl group, a monovalent aromatic ring, a monovalent aliphatic ring, a monovalent Heterocycles and monovalent macrocyclic substituents composed of these are preferred, and alkyl groups having 12 to 20 carbon atoms or fluorine-containing alkyl groups are more preferred.
  • the amount of the side chain that vertically aligns the liquid crystal is not particularly limited as long as the liquid crystal alignment film can align the liquid crystal vertically.
  • the amount of side chains that vertically align the liquid crystal is possible within a range that does not impair the display characteristics of the element such as voltage holding ratio and accumulation of residual DC voltage. As few as possible is preferable.
  • the ability of a polymer having side chains for vertically aligning liquid crystals to align liquid crystals vertically varies depending on the structure of the side chains for vertically aligning liquid crystals, but in general, the side chains for vertically aligning liquid crystals. As the amount increases, the ability to align the liquid crystal vertically increases, and as the amount decreases, it decreases. Moreover, when it has a cyclic structure, compared with what does not have a cyclic structure, there exists a tendency for the capability to orientate a liquid crystal vertically.
  • the polymer composed of at least one of polyimide precursors such as polyamic acid and polyamic acid ester and polyimide contained in the liquid crystal aligning agent of the present invention has a photoreactive side chain.
  • the photoreactive side chain is a side chain having a functional group (hereinafter also referred to as a photoreactive group) that can react by irradiation with light such as ultraviolet rays (UV) to form a covalent bond.
  • a photoreactive group a side chain having a functional group (hereinafter also referred to as a photoreactive group) that can react by irradiation with light such as ultraviolet rays (UV) to form a covalent bond.
  • UV ultraviolet rays
  • a polymer comprising at least one of polyimide precursors and polyimides such as polyamic acid and polyamic acid ester contained in the liquid crystal aligning agent is at least one selected from methacrylic group, acrylic group, vinyl group and cinnamoyl group.
  • the photoreactive side chain may be directly bonded to the polyimide precursor or the main chain of the polyimide, or may be bonded via an appropriate bonding group.
  • Examples of the photoreactive side chain include those represented by the following formula (b).
  • R 8 is a single bond or —CH 2 —, —O—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, —CH 2 O—, —N Represents any one of (CH 3 ) —, —CON (CH 3 ) —, —N (CH 3 ) CO—, and R 9 is a single bond, or unsubstituted or substituted with a fluorine atom.
  • R 10 Represents a methacryl group, an acrylic group, a vinyl group, or a cinnamoyl group.
  • R 8 in the above formula (b) can be formed by an ordinary organic synthetic method, but from the viewpoint of ease of synthesis, —CH 2 —, —O—, —COO—, —NHCO —, —NH— and —CH 2 O— are preferred.
  • divalent carbocycle or divalent heterocycle carbocycle or heterocycle for replacing any —CH 2 — in R 9 include the following structures, but are not limited thereto. Is not to be done.
  • R 10 is preferably a methacryl group, an acryl group or a vinyl group from the viewpoint of photoreactivity.
  • the above formula (b) is more preferably a structure containing a group selected from the above formula (I).
  • the amount of the photoreactive side chain is preferably within a range in which the response speed of the liquid crystal can be increased by reacting with ultraviolet irradiation to form a covalent bond. In order to further increase the response speed of the liquid crystal As many as possible are preferable as long as other characteristics are not affected.
  • the method for producing at least one polymer selected from polyimides obtained by imidizing the body is not particularly limited.
  • a liquid crystal is used.
  • Photoreactivity including a diamine having a vertically aligned side chain or a tetracarboxylic dianhydride having a vertically aligned liquid crystal or at least one selected from a methacrylic group, an acrylic group, a vinyl group and a cinnamoyl group Diamine or methacryl group, acrylic group, vinyl group and cinnamo having side chains of The tetracarboxylic acid dianhydride having photoreactive side chain containing at least one selected from the Le group it is sufficient to copolymerization.
  • Examples of the diamine having a side chain for vertically aligning the liquid crystal include a long chain alkyl group, a group having a ring structure or a branched structure in the middle of the long chain alkyl group, a hydrocarbon group such as a steroid group, and the hydrogen of these groups.
  • a diamine having a side chain with a group in which some or all of the atoms are replaced with fluorine atoms for example, a diamine having a side chain represented by the above formula (a) can be mentioned.
  • a diamine having a hydrocarbon group having 8 to 30 carbon atoms in which a hydrogen atom may be substituted with fluorine or the following formulas (2), (3), (4), (5
  • the diamine represented by this can be mentioned, However, It is not limited to this.
  • a 10 represents —COO—, —OCO—, —CONH—, —NHCO—, —CH 2 —, —O—, —CO—, or —NH—.
  • a 11 represents a single bond or a phenylene group
  • a represents the same structure as a side chain for vertically aligning the liquid crystal represented by the above formula (a)
  • a ′ is represented by the above formula (a). (This represents a divalent group having a structure in which one element such as hydrogen is removed from the same structure as the side chain that vertically aligns the liquid crystal.)
  • a 14 is an alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom
  • a 15 is a 1,4-cyclohexylene group, or 1,4- A phenylene group
  • a 16 is an oxygen atom or —COO— * (where a bond marked with “*” is bonded to A 15 )
  • a 17 is an oxygen atom or —COO — * ( However, bond marked with "*” is (CH 2) binds to a 2.) is.
  • a 1 is 0, or an integer 1
  • a 2 is an integer from 2 to 10
  • a 3 is 0 or an integer of 1.
  • Binding positions of the two amino group (-NH 2) in equation (2) is not limited. Specifically, with respect to the linking group of the side chain, 2, 3 position, 2, 4 position, 2, 5 position, 2, 6 position, 3, 4 position on the benzene ring, 3, 4 position, 5 positions. Among these, from the viewpoint of reactivity when synthesizing a polyamic acid, positions 2, 4, 2, 5, or 3, 5 are preferable. Considering the ease in synthesizing the diamine, the positions 2, 4 or 3, 5 are more preferable.
  • a 1 is an alkyl group having 2 to 24 carbon atoms or a fluorine-containing alkyl group.
  • a 2 represents —O—, —OCH 2 —, —CH 2 O—, —COOCH 2 —, or —CH 2 OCO—
  • 3 is an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group.
  • a 4 represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, —OCH 2 —, or —CH 2 —
  • a 5 represents an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group, or a fluorine-containing alkoxy group.
  • a 6 represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, —OCH 2 —, —CH 2 —, —O—, or —NH—
  • a 7 represents fluorine group, cyano group, trifluoromethane group, nitro group, azo group, formyl group, acetyl group, acetoxy Group or hydroxyl group.
  • a 8 is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer. .
  • a 9 is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer. .
  • diamine represented by the formula (3) include diamines represented by the following formulas [A-25] to [A-30], but are not limited thereto.
  • a 12 represents —COO—, —OCO—, —CONH—, —NHCO—, —CH 2 —, —O—, —CO—, or —NH—
  • a 13 represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group.
  • diamine represented by the formula (4) examples include diamines represented by the following formulas [A-31] to [A-32], but are not limited thereto.
  • the above-mentioned diamines can be used alone or in combination of two or more depending on the properties such as liquid crystal orientation, pretilt angle, voltage holding property, and accumulated charge when the liquid crystal alignment film is used.
  • the diamine having a side chain for vertically aligning the liquid crystal is preferably used in an amount of 5 to 50 mol% of the diamine component used for the synthesis of the polyamic acid, more preferably 10 to 40 mol% of the diamine component.
  • a diamine having a side chain for vertically aligning the liquid crystal particularly preferably 15 to 30 mol%.
  • the diamine having a side chain for vertically aligning the liquid crystal is used in an amount of 5 to 50 mol% of the diamine component used for the synthesis of the polyamic acid, it is particularly excellent in terms of improving the response speed and fixing the alignment of the liquid crystal. .
  • Examples of the diamine having a photoreactive side chain containing at least one selected from a methacryl group, an acryl group, a vinyl group, and a cinnamoyl group include a diamine having a side chain represented by the above formula (b). Can do. More specifically, examples include diamines represented by the following general formula (6), but are not limited thereto.
  • the bonding position of the two amino groups (—NH 2 ) in Formula (6) is not limited. Specifically, with respect to the linking group of the side chain, 2, 3 position, 2, 4 position, 2, 5 position, 2, 6 position, 3, 4 position on the benzene ring, 3, 4 position, 5 positions. Among these, from the viewpoint of reactivity when synthesizing a polyamic acid, positions 2, 4, 2, 5, or 3, 5 are preferable. Considering the ease in synthesizing the diamine, the positions 2, 4 or 3, 5 are more preferable.
  • diamine having a photoreactive side chain including at least one selected from a methacryl group, an acryl group, a vinyl group, and a cinnamoyl group include the following compounds, but are not limited thereto. It is not a thing.
  • X 1 and X 2 are each independently a single bond or a linking group selected from —O—, —COO—, —NHCO—, —NH—, Y is unsubstituted or substituted by a fluorine atom
  • the diamine having a photoreactive side chain containing at least one selected from the methacryl group, acryl group, vinyl group and cinnamoyl group is liquid crystal alignment property, pretilt angle, voltage holding property, accumulation when used as a liquid crystal alignment film.
  • One type or a mixture of two or more types can be used depending on characteristics such as electric charge, response speed of liquid crystal when a liquid crystal display element is used, and the like.
  • such a diamine having a photoreactive side chain containing at least one selected from a methacryl group, an acrylic group, a vinyl group and a cinnamoyl group is 10 to 70 mol% of the diamine component used for the synthesis of polyamic acid. Is preferably used, more preferably 20 to 60 mol%, particularly preferably 30 to 50 mol%.
  • diamines other than the diamine having a side chain for vertically aligning the liquid crystal and the diamine having a photoreactive group are used as a diamine component. be able to.
  • p-phenylenediamine 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl- m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2, 4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl 3,3′-dihydroxy-4,4′-diaminobiphenyl, 3,3′-dicarboxy-4,
  • the above-mentioned other diamines can be used alone or in combination of two or more according to properties such as liquid crystal orientation, pretilt angle, voltage holding property, and accumulated charge when the liquid crystal alignment film is used.
  • the tetracarboxylic dianhydride to be reacted with the diamine component in the synthesis of polyamic acid is not particularly limited. Specifically, pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2, 3,6,7-anthracenetetracarboxylic acid, 1,2,5,6-anthracenetetracarboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3,3 ′, 4-biphenyltetra Carboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxy) Phenyl) methan
  • a known synthesis method can be used.
  • the diamine component and tetracarboxylic dianhydride are reacted in an organic solvent.
  • the reaction between the diamine component and tetracarboxylic dianhydride is advantageous in that it proceeds relatively easily in an organic solvent and no by-products are generated.
  • the organic solvent used in the above reaction is not particularly limited as long as the generated polyamic acid is soluble. Furthermore, even if it is an organic solvent in which a polyamic acid does not melt
  • organic solvent used in the reaction examples include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, N-methylformamide, N-methyl-2-pyrrolidone, N-ethyl-2- Pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N, N-dimethylpropanamide, N-methylcaprolactam, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide , ⁇ -butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, e
  • the solution in which the diamine component is dispersed or dissolved in the organic solvent is stirred, and the tetracarboxylic dianhydride component is used as it is or in an organic solvent.
  • a method of adding by dispersing or dissolving in a solvent a method of adding a diamine component to a solution in which a tetracarboxylic dianhydride component is dispersed or dissolved in an organic solvent, and a tetracarboxylic dianhydride component and a diamine component.
  • the method of adding alternately etc. is mentioned, You may use any of these methods.
  • the diamine component or tetracarboxylic dianhydride component when they are composed of a plurality of types of compounds, they may be reacted in a premixed state, may be individually reacted sequentially, or may be further reacted individually.
  • the body may be mixed and reacted to form a high molecular weight body.
  • the temperature at the time of reacting the diamine component and the tetracarboxylic dianhydride component can be selected arbitrarily, and is, for example, in the range of ⁇ 20 ° C. to 150 ° C., preferably ⁇ 5 ° C. to 100 ° C.
  • the reaction can be carried out at any concentration.
  • the total amount of the diamine component and the tetracarboxylic dianhydride component is 1 to 50% by mass, preferably 5 to 30% by mass, based on the reaction solution.
  • the ratio of the total number of moles of the tetracarboxylic dianhydride component to the total number of moles of the diamine component can be selected according to the molecular weight of the polyamic acid to be obtained. Similar to the normal polycondensation reaction, the molecular weight of the polyamic acid produced increases as the molar ratio approaches 1.0. If it shows a preferable range, it is 0.8 to 1.2.
  • the method for synthesizing the polyamic acid used in the present invention is not limited to the above-described method, and in the same manner as the general polyamic acid synthesis method, instead of the tetracarboxylic dianhydride, a tetracarboxylic acid having a corresponding structure is used.
  • the corresponding polyamic acid can also be obtained by reacting by a known method using a tetracarboxylic acid derivative such as acid or tetracarboxylic acid dihalide.
  • Examples of the method for imidizing the polyamic acid to obtain a polyimide include thermal imidization in which the polyamic acid solution is heated as it is, and catalytic imidization in which a catalyst is added to the polyamic acid solution.
  • the imidation ratio from polyamic acid to polyimide is not necessarily 100%.
  • the temperature at which the polyamic acid is thermally imidized in the solution is 100 ° C. to 400 ° C., preferably 120 ° C. to 250 ° C., and is preferably carried out while removing water generated by the imidization reaction from the outside of the system.
  • the catalytic imidation of polyamic acid can be carried out by adding a basic catalyst and an acid anhydride to a polyamic acid solution and stirring at -20 to 250 ° C., preferably 0 to 180 ° C.
  • the amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times of the amic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol of the amido acid group. Is double.
  • the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Among them, pyridine is preferable because it has an appropriate basicity for proceeding with the reaction.
  • Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated.
  • the imidization rate by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.
  • the polyamic acid ester is a reaction of a tetracarboxylic acid diester dichloride with a diamine similar to the synthesis of the polyamic acid, a suitable condensing agent with a diamine similar to the synthesis of the tetracarboxylic acid diester and the polyamic acid, It can be produced by reacting in the presence of a base or the like. Alternatively, it can also be obtained by previously synthesizing a polyamic acid by the above method and esterifying the carboxylic acid in the amic acid using a polymer reaction. Specifically, for example, tetracarboxylic acid diester dichloride and diamine in the presence of a base and an organic solvent at ⁇ 20 ° C.
  • a polyamic acid ester By reacting for ⁇ 4 hours, a polyamic acid ester can be synthesized.
  • the polyimide can also be obtained by heating the polyamic acid ester at a high temperature to promote dealcoholization and ring closure.
  • the reaction solution is poured into a poor solvent and precipitated.
  • the poor solvent used for precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and water.
  • the polymer precipitated in a poor solvent and collected by filtration can be dried by normal temperature or 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 liquid crystal aligning agent of the present invention includes a side chain for vertically aligning the liquid crystal and a photoreactive side chain containing at least one selected from a methacryl group, an acrylic group, a vinyl group, and a cinnamoyl group.
  • a polyimide precursor having, at least one polymer selected from polyimides obtained by imidizing this polyimide precursor, and a polymerizable compound each having a photopolymerizable or photocrosslinkable group at two or more terminals,
  • the amount of the polymerizable compound is not particularly limited as long as it has a solvent, but the content of the polymerizable compound having a photopolymerizable or photocrosslinkable group at two or more terminals respectively aligns the liquid crystal vertically.
  • Polyimide precursor having a side chain and a photoreactive side chain containing at least one selected from a methacryl group, an acryl group, a vinyl group and a cinnamoyl group
  • it is preferably 1 to 50 parts by mass, more preferably 5 to 30 parts by mass with respect to 100 parts by mass of at least one polymer selected from polyimides obtained by imidizing this polyimide precursor. is there.
  • a polyimide precursor having a side chain for vertically aligning a liquid crystal contained in a liquid crystal aligning agent, and a photoreactive side chain containing at least one selected from a methacryl group, an acrylic group, a vinyl group, and a cinnamoyl group
  • the content of at least one polymer selected from polyimides obtained by imidizing this polyimide precursor is preferably 1% by mass to 20% by mass, more preferably 3% by mass to 15% by mass, and particularly preferably. 3% by mass to 10% by mass.
  • the liquid crystal aligning agent of the present invention is a polyimide precursor having a side chain for vertically aligning a liquid crystal and a photoreactive side chain containing at least one selected from a methacryl group, an acryl group, a vinyl group, and a cinnamoyl group. And a polymer other than at least one polymer selected from polyimides obtained by imidizing this polyimide precursor.
  • the content of the other polymer in all the polymer components is preferably 0.5% by mass to 15% by mass, more preferably 1% by mass to 10% by mass.
  • the molecular weight of the polymer of the liquid crystal aligning agent is determined by considering the strength of the liquid crystal aligning film obtained by applying the liquid crystal aligning agent, the workability at the time of forming the coating film, and the uniformity of the coating film, GPC (Gel Permeation Chromatography).
  • the weight average molecular weight measured by the above method is preferably 5,000 to 1,000,000, and more preferably 10,000 to 150,000.
  • the solvent contained in the liquid crystal aligning agent is not particularly limited, and includes a side chain that vertically aligns the liquid crystal, and a photoreactive side chain that includes at least one selected from a methacryl group, an acrylic group, a vinyl group, and a cinnamoyl group.
  • combination of said polyamic acid can be mentioned.
  • N-methyl-2-pyrrolidone, ⁇ -butyrolactone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and 3-methoxy-N, N-dimethylpropanamide are from the viewpoint of solubility.
  • two or more kinds of mixed solvents may be used.
  • Solvents that improve the uniformity and smoothness of the coating include, for example, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol Thor, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol-tert
  • the liquid crystal aligning agent may contain components other than those described above. Examples thereof include compounds that improve the film thickness uniformity and surface smoothness when a liquid crystal aligning agent is applied, and compounds that improve the adhesion between the liquid crystal aligning film and the substrate.
  • Examples of compounds that improve film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. More specifically, for example, F-top EF301, EF303, EF352 (manufactured by Tochem Products), MegaFuck F171, F173, R-30 (manufactured by Dainippon Ink), Florard FC430, FC431 (manufactured by Sumitomo 3M) Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.) and the like.
  • the ratio of use thereof is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 2 parts by mass with respect to 100 parts by mass of the total amount of the polymer contained in the liquid crystal aligning agent. 1 part by mass.
  • compounds that improve the adhesion between the liquid crystal alignment film and the substrate include functional silane-containing compounds and epoxy group-containing compounds.
  • a phenol compound such as 2,2′-bis (4-hydroxy-3,5-dihydroxymethylphenyl) propane or tetra (methoxymethyl) bisphenol may be added.
  • the amount is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the total amount of the polymer contained in the liquid crystal aligning agent.
  • liquid crystal aligning agent is added with a dielectric or conductive material for changing the electrical properties such as the dielectric constant and conductivity of the liquid crystal aligning film, as long as the effects of the present invention are not impaired. May be.
  • the liquid crystal aligning agent of the present invention is a polyimide precursor having a side chain for vertically aligning a liquid crystal and a photoreactive side chain containing at least one selected from a methacryl group, an acrylic group, a vinyl group and a cinnamoyl group, And at least one polymer selected from polyimides obtained by imidizing this polyimide precursor and a polymerizable compound each having a photopolymerizable group or a photocrosslinkable group at two or more terminals, and thus obtained liquid crystal
  • the response speed of the liquid crystal display element using the alignment film can be increased.
  • a cured film obtained by applying the liquid crystal aligning agent of the present invention to a substrate and then drying and baking as necessary can be used as a liquid crystal aligning film as it is.
  • the cured film is rubbed, irradiated with polarized light or light of a specific wavelength, or treated with an ion beam, or a voltage is applied to the liquid crystal display element after filling the liquid crystal as a PSA alignment film It is also possible to irradiate with UV. In particular, it is useful to use as an alignment film for PSA.
  • the substrate to be used is not particularly limited as long as it is a highly transparent substrate, glass plate, polycarbonate, poly (meth) acrylate, polyethersulfone, polyarylate, polyurethane, polysulfone, polyether, polyetherketone, Plastic substrates such as trimethylpentene, polyolefin, polyethylene terephthalate, (meth) acrylonitrile, triacetyl cellulose, diacetyl cellulose, and acetate butyrate cellulose can be used.
  • a substrate on which an ITO electrode or the like for driving liquid crystal is formed from the viewpoint of simplifying the process.
  • an opaque material such as a silicon wafer can be used as long as the substrate is only on one side, and in this case, a material that reflects light such as aluminum can be used.
  • the method for applying the liquid crystal aligning agent is not particularly limited, and examples thereof include screen printing, offset printing, flexographic printing, and other printing methods, ink jet methods, spray methods, roll coating methods, dip, roll coaters, slit coaters, and spinners. From the standpoint of productivity, the transfer printing method is widely used industrially, and is preferably used in the present invention.
  • the coating film formed by applying the liquid crystal aligning agent by the above method can be baked to obtain a cured film.
  • the drying process after applying the liquid crystal aligning agent is not necessarily required, but if the time from application to baking is not constant for each substrate, or if baking is not performed immediately after application, the drying process is performed. It is preferable.
  • the drying is not particularly limited as long as the solvent is removed to such an extent that the shape of the coating film is not deformed by transporting the substrate or the like. For example, a method of drying on a hot plate at a temperature of 40 ° C. to 150 ° C., preferably 60 ° C. to 100 ° C., for 0.5 minutes to 30 minutes, preferably 1 minute to 5 minutes.
  • the firing temperature of the coating film formed by applying the liquid crystal aligning agent is not limited, and can be performed at any temperature of, for example, 100 to 350 ° C., preferably 120 ° C. to 300 ° C., more preferably 150 to 250 ° C. Firing can be performed at an arbitrary time of 5 minutes to 240 minutes. The time is preferably 10 minutes to 90 minutes, more preferably 20 minutes to 90 minutes. Heating can be performed by a generally known method such as a hot plate, a hot air circulating furnace, an infrared furnace, or the like.
  • the thickness of the liquid crystal alignment film obtained by firing is not particularly limited, but is preferably 5 to 300 nm, more preferably 10 to 100 nm.
  • the liquid crystal display element of this invention can produce a liquid crystal cell by a well-known method after forming a liquid crystal aligning film in a board
  • the liquid crystal display element include two substrates disposed so as to face each other, a liquid crystal layer provided between the substrates, and a liquid crystal aligning agent provided between the substrate and the liquid crystal layer.
  • a vertical alignment type liquid crystal display device comprising a liquid crystal cell having the above-described liquid crystal alignment film.
  • the liquid crystal aligning agent of the present invention is applied onto two substrates and baked to form a liquid crystal aligning film, and the two substrates are arranged so that the liquid crystal aligning films face each other.
  • a liquid crystal layer composed of liquid crystal is sandwiched between two substrates, that is, a liquid crystal layer is provided in contact with the liquid crystal alignment film, and ultraviolet rays are applied while applying a voltage to the liquid crystal alignment film and the liquid crystal layer.
  • This is a vertical alignment type liquid crystal display device including a liquid crystal cell to be manufactured.
  • the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention is used to irradiate ultraviolet rays while applying voltage to the liquid crystal alignment film and the liquid crystal layer to polymerize the polymerizable compound, and the light possessed by the polymer.
  • a liquid crystal display device in which the alignment of the liquid crystal is more efficiently fixed and the response speed is remarkably improved by reacting the reactive side chains or the photoreactive side chain of the polymer with the polymerizable compound. It becomes.
  • the substrate used in the liquid crystal display element of the present invention is not particularly limited as long as it is a highly transparent substrate, but is usually a substrate on which a transparent electrode for driving liquid crystal is formed.
  • a substrate on which a transparent electrode for driving liquid crystal As a specific example, the thing similar to the board
  • a substrate provided with a conventional electrode pattern or protrusion pattern may be used, but in the liquid crystal display element of the present invention, the liquid crystal aligning agent of the present invention is used as the liquid crystal aligning agent for forming the liquid crystal aligning film. It is possible to operate even in a structure in which a line / slit electrode pattern of 1 to 10 ⁇ m, for example, is formed on one side substrate and a slit pattern or projection pattern is not formed on the opposite substrate. This process can be simplified and high transmittance can be obtained.
  • a high-performance element such as a TFT type element
  • an element in which an element such as a transistor is formed between an electrode for driving a liquid crystal and a substrate is used.
  • a substrate In the case of a transmissive liquid crystal display element, it is common to use a substrate as described above. However, in a reflective liquid crystal display element, if only one substrate is used, an opaque substrate such as a silicon wafer may be used. Is possible. At that time, a material such as aluminum that reflects light may be used for the electrode formed on the substrate.
  • the liquid crystal alignment film is formed by applying the liquid crystal aligning agent of the present invention on this substrate and baking it, and the details are as described above.
  • the liquid crystal material constituting the liquid crystal layer of the liquid crystal display element of the present invention is not particularly limited, and a liquid crystal material used in a conventional vertical alignment method, for example, a negative type liquid crystal such as MLC-6608 or MLC-6609 manufactured by Merck Can be used.
  • a known method can be exemplified. For example, a pair of substrates on which a liquid crystal alignment film is formed is prepared, and spacers such as beads are dispersed on the liquid crystal alignment film on one substrate so that the surface on which the liquid crystal alignment film is formed is on the inside. Then, the other substrate is bonded, and liquid crystal is injected under reduced pressure to seal.
  • a liquid crystal cell can also be produced by a method in which the other substrate is bonded to the inside so as to be inside and sealed.
  • the thickness of the spacer at this time is preferably 1 to 30 ⁇ m, more preferably 2 to 10 ⁇ m.
  • the step of producing a liquid crystal cell by irradiating ultraviolet rays while applying a voltage to the liquid crystal alignment film and the liquid crystal layer includes, for example, applying an electric field between the electrodes installed on the substrate to apply an electric field to the liquid crystal alignment film and the liquid crystal layer. And applying ultraviolet rays while maintaining this electric field.
  • the voltage applied between the electrodes is, for example, 5 to 30 Vp-p, preferably 5 to 20 Vp-p.
  • the irradiation amount of ultraviolet rays is, for example, 1 to 60 J, preferably 40 J or less, and the smaller the irradiation amount of ultraviolet rays, the lowering of reliability caused by the destruction of the members constituting the liquid crystal display element can be suppressed, and the irradiation time of ultraviolet rays can be reduced. This is preferable because the manufacturing efficiency is improved.
  • the polymerizable compound when ultraviolet rays are applied while applying a voltage to the liquid crystal alignment film and the liquid crystal layer, the polymerizable compound reacts to form a polymer, and the direction in which the liquid crystal molecules are tilted is memorized by this polymer.
  • the response speed of the obtained liquid crystal display element can be increased.
  • a photoreaction including a side chain that vertically aligns liquid crystal when applied with voltage to the liquid crystal alignment film and the liquid crystal layer, and at least one selected from a methacryl group, an acrylic group, a vinyl group, and a cinnamoyl group
  • the liquid crystal aligning agent is not only useful as a liquid crystal aligning agent for producing a vertical alignment type liquid crystal display element such as a PSA type liquid crystal display or an SC-PVA type liquid crystal display, but also by a rubbing process or a photo-alignment process. It can also be suitably used for applications of the liquid crystal alignment film to be produced.
  • the separated organic layer was dried over anhydrous magnesium sulfate, filtered, and then the solvent was distilled off under reduced pressure to obtain a yellow solid.
  • the result of having measured the obtained white solid by NMR is shown below.
  • the obtained solid was dissolved in deuterated chloroform (CDCl 3 ) and measured at 300 MHz using a nuclear magnetic resonance apparatus (manufactured by Diol). From this result, it was confirmed that this white solid was a compound (RM2-A) represented by the following reaction formula. The yield was 92%.
  • the compound (RM4-B) (5.0 g, 14.0 mmol) obtained above was dissolved in 30 ml of THF together with 3.2 g of triethylamine and a small amount of 2,6-di-tert-butyl-p-cresol (BHT) at room temperature.
  • BHT 2,6-di-tert-butyl-p-cresol
  • dissolved 3.3 g (32 mmol) of methacryloyl chloride in 20 ml of THF was dripped over 15 minutes under cooling by a water bath. After dropping, the mixture was stirred for 30 minutes, and the water bath was removed and stirring was continued overnight while returning to room temperature. After completion of the reaction, the reaction solution was poured into 200 ml of pure water and filtered to obtain a white solid.
  • Polymerizable compound (RM5) A known polymerizable compound represented by the following formula was designated as a polymerizable compound (RM5).
  • the solvent of the obtained solution was distilled off to obtain 1.3 g of a colorless solid.
  • the result of having measured this solid by NMR is shown below. From this result, it was confirmed that this colorless solid was a compound (RM6-B) represented by the following reaction formula. The yield was 50%.
  • the precipitated DCC urea was filtered off, and the filtrate was washed twice with 100 ml of 0.5N HCl, 100 ml of saturated aqueous sodium hydrogen carbonate solution and 150 ml of saturated brine successively, dried over magnesium sulfate, and then under reduced pressure.
  • the solvent was distilled off to obtain a yellow solid.
  • the solvent of the solution obtained here was distilled off to obtain 4.3 g of a polymerizable compound (RM7) represented by the following reaction formula.
  • reaction solution was filtered, the filtrate was concentrated under reduced pressure to a volume of 3/4, and 100 ml of methylene chloride was added.
  • This solution was washed with 100 ml of saturated sodium carbonate solution, 100 ml of 0.5N hydrochloric acid and 100 ml of saturated brine in that order, and dried over magnesium sulfate, and then the solvent was distilled off to obtain a yellow solid.
  • reaction solution was filtered under reduced pressure and mixed with 60 ml of pure water, and 50 ml of diethyl ether was added thereto for extraction. Extraction was performed three times. The organic layer after extraction was dried by adding anhydrous magnesium sulfate, and the solvent was distilled off from the solution after filtration under reduced pressure to obtain a light brown solid.
  • the precipitated DCC urea was filtered off, and the filtrate was washed twice with 100 ml of 0.5N HCl, 100 ml of saturated aqueous sodium hydrogen carbonate solution and 150 ml of saturated brine successively, dried over magnesium sulfate, and then under reduced pressure.
  • the solvent was distilled off to obtain a yellow solid.
  • This solid was purified by recrystallization (ethanol) to obtain 6.1 g of a polymerizable compound (RM19) represented by the following reaction formula.
  • the result measured by NMR is shown below. The yield was 51%.
  • Polymerizable compound (RM20) A known polymerizable compound represented by the following formula was designated as a polymerizable compound (RM20).
  • Polymerizable compound (RM21) A known polymerizable compound represented by the following formula was designated as a polymerizable compound (RM21).
  • Polymerizable compound (RM22) A known polymerizable compound represented by the following formula was designated as a polymerizable compound (RM22).
  • Polymerizable compound (RM23) A known polymerizable compound represented by the following formula was designated as a polymerizable compound (RM23).
  • m-PDA m-phenylenediamine
  • p-PDA p-phenylenediamine
  • PCH 1,3-diamino-4- [4- (4-heptylcyclohexyl) phenoxy] benzene
  • DA-1 2-represented by the following formula (Methacryloyloxy) ethyl 3,5-diaminobenzoate
  • DA-2 N 1 , N 1 -diallylbenzene-1,2,4-triamine represented by the following formula
  • DA-3 Cholestanyl 3,5-diaminobenzoate represented by the following formula
  • NMP N-methyl-2-pyrrolidone
  • BCS Butyl cellosolve
  • the molecular weight measurement conditions of polyimide are as follows. Apparatus: Room temperature gel permeation chromatography (GPC) apparatus (SSC-7200) manufactured by Senshu Scientific Co., Ltd. Column: Column made by Shodex (KD-803, KD-805) Column temperature: 50 ° C Eluent: N, N′-dimethylformamide (as additives, lithium bromide-hydrate (LiBr ⁇ H 2 O) is 30 mmol / L, phosphoric acid / anhydrous crystal (o-phosphoric acid) is 30 mmol / L, Tetrahydrofuran (THF) 10ml / L) Flow rate: 1.0 ml / min.
  • GPC room temperature gel permeation chromatography
  • Standard sample for preparing a calibration curve TSK standard polyethylene oxide (molecular weight of about 900,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation, and polyethylene glycol (manufactured by Polymer Laboratories) Molecular weight about 12,000, 4,000, 1,000).
  • the imidation ratio of polyimide was measured as follows. Add 20 mg of polyimide powder to an NMR sample tube (NMR sampling tube standard ⁇ 5 by Kusano Kagaku Co., Ltd.), add 1.0 ml of deuterated dimethyl sulfoxide (DMSO-d 6 , 0.05% TMS mixture), and apply ultrasonic waves. To dissolve completely. This solution was measured for proton NMR at 500 MHz with an NMR measuring instrument (JNW-ECA500) manufactured by JEOL Datum.
  • the imidation rate is determined based on protons derived from structures that do not change before and after imidation as reference protons, and the peak integrated value of these protons and proton peaks derived from NH groups of amic acid appearing in the vicinity of 9.5 to 10.0 ppm. It calculated
  • x is the proton peak integrated value derived from the NH group of the amic acid
  • y is the peak integrated value of the reference proton
  • ⁇ is the proton of the NH group of the amic acid in the case of polyamic acid (imidation rate is 0%). This is the ratio of the number of reference protons to one.
  • Imidization rate (%) (1 ⁇ ⁇ x / y) ⁇ 100
  • Example 1 BODA (6.01 g, 24.0 mmol), p-PDA (2.60 g, 24.0 mmol), PCH (6.85 g, 18.0 mmol), DA-1 (4.76 g, 18.0 mmol) were added to NMP ( 81.5 g), and after reacting at 80 ° C. for 5 hours, CBDA (6.94 g, 35.4 mmol) and NMP (27.2 g) were added and reacted at 40 ° C. for 10 hours to obtain a polyamic acid solution. Obtained.
  • NMP (74.0 g) was added to the obtained polyimide powder (A) (6.0 g), and the mixture was dissolved by stirring at 50 ° C. for 12 hours.
  • BCS (20.0g) was added to this solution, and the liquid crystal aligning agent (B) was obtained by stirring at 50 degreeC for 5 hours.
  • Example 2 0.06 g (10% by mass with respect to the solid content) of the polymerizable compound (RM2) obtained above was added to 10.0 g of the liquid crystal aligning agent (B), and the mixture was dissolved by stirring at room temperature for 3 hours. A liquid crystal aligning agent (B2) was prepared.
  • Example 3 0.06 g (10% by mass with respect to the solid content) of the polymerizable compound (RM3) obtained above was added to 10.0 g of the liquid crystal aligning agent (B), and the mixture was dissolved by stirring at room temperature for 3 hours. A liquid crystal aligning agent (B3) was prepared.
  • Example 4 0.06 g (10% by mass with respect to the solid content) of the polymerizable compound (RM4) obtained above was added to 10.0 g of the liquid crystal aligning agent (B), and the mixture was dissolved by stirring at room temperature for 3 hours. A liquid crystal aligning agent (B4) was prepared.
  • Example 5 0.06 g (10% by mass with respect to the solid content) of the polymerizable compound (RM5) obtained above was added to 10.0 g of the liquid crystal aligning agent (B), and the mixture was dissolved by stirring at room temperature for 3 hours. A liquid crystal aligning agent (B5) was prepared.
  • NMP (74.0 g) was added to the obtained polyimide powder (C) (6.0 g), and the mixture was dissolved by stirring at 50 ° C. for 12 hours.
  • BCS (20.0 g) was added to this solution, and the polyimide solution (D) was obtained by stirring at 50 degreeC for 5 hours.
  • Example 6 Using the liquid crystal aligning agent (B1) obtained in Example 1, a liquid crystal cell was prepared according to the procedure shown below.
  • the liquid crystal aligning agent (B1) obtained in Example 1 was spin-coated on the ITO surface of an ITO electrode substrate on which an ITO electrode pattern having a pixel size of 100 ⁇ m ⁇ 300 ⁇ m and a line / space of 5 ⁇ m was formed, After drying for 90 seconds on this hot plate, baking was performed in a hot air circulation oven at 200 ° C. for 30 minutes to form a liquid crystal alignment film having a thickness of 100 nm.
  • Liquid crystal MLC-6608 (trade name, manufactured by Merck & Co., Inc.) was injected into the empty cell by a reduced pressure injection method, and was subjected to Isotropic treatment (realignment treatment of liquid crystal by heating) in an oven at 120 ° C. to produce a liquid crystal cell.
  • the response speed immediately after production of the obtained liquid crystal cell was measured by the following method. After that, with a voltage of 20 Vp-p applied to the liquid crystal cell, 20 J UV irradiation through a 313 nm band pass filter was applied from the outside of the liquid crystal cell. Thereafter, the response speed was measured again, and the response speed before and after UV irradiation was compared. Table 2 shows the results of the response speed immediately after the production of the liquid crystal cell (initial stage) and after UV irradiation with 20 J (after UV 20 J).
  • a liquid crystal cell was arranged between a pair of polarizing plates in a measuring device configured in the order of a backlight, a set of polarizing plates in a crossed Nicol state, and a light amount detector.
  • the ITO electrode pattern in which the line / space was formed was at an angle of 45 ° with respect to the crossed Nicols.
  • a rectangular wave with a voltage of ⁇ 4 V and a frequency of 1 kHz is applied to the liquid crystal cell, and the change until the luminance observed by the light quantity detector is saturated is captured by an oscilloscope, and the luminance when no voltage is applied is obtained.
  • a voltage of 0% and ⁇ 4 V was applied, the saturated luminance value was set to 100%, and the time taken for the luminance to change from 10% to 90% was defined as the response speed.
  • Example 7 Except for changing the firing temperature from 200 ° C. to 140 ° C., the same operation as in Example 6 was performed, and the response speed before and after UV irradiation was compared.
  • Example 8 The response speed before and after UV irradiation was compared by performing the same operation as in Example 6 except that the liquid crystal aligning agent (B2) was used instead of the liquid crystal aligning agent (B1).
  • Example 9 Except for changing the firing temperature from 200 ° C. to 140 ° C., the same operation as in Example 8 was performed to compare the response speed before and after UV irradiation.
  • Example 10 The same operation as in Example 6 was performed except that the liquid crystal aligning agent (B3) was used instead of the liquid crystal aligning agent (B1), and the response speeds before and after UV irradiation were compared.
  • the liquid crystal aligning agent (B3) was used instead of the liquid crystal aligning agent (B1), and the response speeds before and after UV irradiation were compared.
  • Example 11 Except for changing the firing temperature from 200 ° C. to 140 ° C., the same operation as in Example 10 was performed to compare the response speed before and after UV irradiation.
  • Example 12 The response speed before and after UV irradiation was compared by performing the same operation as in Example 6 except that the liquid crystal aligning agent (B4) was used instead of the liquid crystal aligning agent (B1).
  • Example 13 Except for changing the firing temperature from 200 ° C. to 140 ° C., the same operation as in Example 12 was performed, and the response speed before and after UV irradiation was compared.
  • Example 14 The response speed before and after UV irradiation was compared by performing the same operation as in Example 6 except that the liquid crystal aligning agent (B5) was used instead of the liquid crystal aligning agent (B1).
  • Example 15 Except for changing the firing temperature from 200 ° C. to 140 ° C., the same operation as in Example 14 was performed to compare the response speed before and after UV irradiation.
  • Example 2 Comparative Example 2 Except that the liquid crystal aligning agent (B) was used instead of the liquid crystal aligning agent (B1), the same operation as in Example 6 was performed, and the response speed before and after UV irradiation was compared.
  • Comparative Example 3 Except for changing the firing temperature from 200 ° C. to 140 ° C., the same operation as in Comparative Example 2 was performed to compare the response speed before and after UV irradiation.
  • Example 4 The same operation as in Example 6 was performed except that the liquid crystal aligning agent (D1) was used instead of the liquid crystal aligning agent (B1), and the response speeds before and after UV irradiation were compared.
  • Comparative Example 5 Except for changing the firing temperature from 200 ° C. to 140 ° C., the same operation as in Comparative Example 4 was performed to compare the response speed before and after UV irradiation.
  • Examples 6 to 15 are Comparative Examples 4 and 5 using a liquid crystal aligning agent containing a polymerizable compound but not containing a polymer having a photoreactive side chain, a photoreactive side chain containing a methacryl group and Compared with Comparative Examples 2 and 3 using a liquid crystal aligning agent B containing a polymer (polyimide) having a side chain for vertically aligning liquid crystal but not adding a polymerizable compound, response speed before and after UV irradiation The improvement rate was significantly higher.
  • the response speed is higher than using each independently. It has been confirmed that the response speed can be improved drastically and the response speed can be sufficiently improved even with a small amount of the polymerizable compound added.
  • Examples 12 to 13 using a liquid crystal aligning agent containing a polymerizable compound having a structure in which is bonded to a phenylene group through an oxyalkylene group the firing temperature is low (140 ° C.) or high (200 ° C.). (C) also dramatically improved the response speed.
  • the improvement rate of the response speed is 140 ° C. when baked at 200 ° C. It was lower than the case of firing with In Examples 6 to 7 using a polymerizable compound that differs from the polymerizable compound used in Examples 14 to 15 only in the polymerization group, the firing temperature dependency was hardly confirmed, and thus the methacryl group was bonded. It is presumed that the thermal stability of the polymerizable compound is improved when the carbon atom takes the sp 3 hybrid orbital, and the dependency of the response speed improvement rate on the firing temperature is reduced.
  • Example 16 0.06 g (10% by mass with respect to the solid content) of the polymerizable compound (RM6) obtained above was added to 10.0 g of the liquid crystal aligning agent (B), and dissolved by stirring at room temperature for 3 hours. A liquid crystal aligning agent (B6) was prepared.
  • Example 17 0.06 g (10% by mass with respect to the solid content) of the polymerizable compound (RM7) obtained above is added to 10.0 g of the liquid crystal aligning agent (B), and the mixture is dissolved by stirring at room temperature for 3 hours. A liquid crystal aligning agent (B7) was prepared.
  • Example 18 0.06 g (10% by mass with respect to the solid content) of the polymerizable compound (RM8) obtained above was added to 10.0 g of the liquid crystal aligning agent (B), and dissolved by stirring at room temperature for 3 hours. A liquid crystal aligning agent (B8) was prepared.
  • Example 19 0.06 g (10% by mass with respect to the solid content) of the polymerizable compound (RM9) obtained above was added to 10.0 g of the liquid crystal aligning agent (B), and dissolved by stirring at room temperature for 3 hours. A liquid crystal aligning agent (B9) was prepared.
  • Example 20 0.06 g (10% by mass based on the solid content) of the polymerizable compound (RM10) obtained above was added to 10.0 g of the liquid crystal aligning agent (B), and the mixture was dissolved by stirring at room temperature for 3 hours. A liquid crystal aligning agent (B10) was prepared.
  • Example 21 0.06 g (10% by mass based on the solid content) of the polymerizable compound (RM11) obtained above was added to 10.0 g of the liquid crystal aligning agent (B), and the mixture was dissolved by stirring at room temperature for 3 hours. A liquid crystal aligning agent (B11) was prepared.
  • Example 22 0.06 g (10% by mass with respect to the solid content) of the polymerizable compound (RM12) obtained above was added to 10.0 g of the liquid crystal aligning agent (B), and the mixture was dissolved by stirring at room temperature for 3 hours. A liquid crystal aligning agent (B12) was prepared.
  • Example 23 0.06 g (10% by mass with respect to the solid content) of the polymerizable compound (RM13) obtained above was added to 10.0 g of the liquid crystal aligning agent (B), and the mixture was dissolved by stirring at room temperature for 3 hours. A liquid crystal aligning agent (B13) was prepared.
  • Example 24 0.06 g (10% by mass with respect to the solid content) of the polymerizable compound (RM14) obtained above is added to 10.0 g of the liquid crystal aligning agent (B), and the mixture is dissolved by stirring at room temperature for 3 hours. A liquid crystal aligning agent (B14) was prepared.
  • Example 25 0.06 g (10% by mass with respect to the solid content) of the polymerizable compound (RM15) obtained above is added to 10.0 g of the liquid crystal aligning agent (B), and the mixture is dissolved by stirring at room temperature for 3 hours. A liquid crystal aligning agent (B15) was prepared.
  • Example 26 0.06 g (10% by mass with respect to the solid content) of the polymerizable compound (RM16) obtained above was added to 10.0 g of the liquid crystal aligning agent (B), and dissolved by stirring at room temperature for 3 hours. A liquid crystal aligning agent (B16) was prepared.
  • Example 27 0.06 g (10% by mass with respect to the solid content) of the polymerizable compound (RM17) obtained above is added to 10.0 g of the liquid crystal aligning agent (B), and the mixture is dissolved by stirring at room temperature for 3 hours. A liquid crystal aligning agent (B17) was prepared.
  • Example 28 0.06 g (10% by mass with respect to the solid content) of the polymerizable compound (RM18) obtained above was added to 10.0 g of the liquid crystal aligning agent (B), and the mixture was dissolved by stirring at room temperature for 3 hours. A liquid crystal aligning agent (B18) was prepared.
  • Example 29 0.06 g (10% by mass with respect to the solid content) of the polymerizable compound (RM19) obtained above is added to 10.0 g of the liquid crystal aligning agent (B), and the mixture is dissolved by stirring at room temperature for 3 hours. A liquid crystal aligning agent (B19) was prepared.
  • Example 30 0.06 g (10% by mass based on the solid content) of the polymerizable compound (RM20) obtained above was added to 10.0 g of the liquid crystal aligning agent (B), and the mixture was dissolved by stirring at room temperature for 3 hours. A liquid crystal aligning agent (B20) was prepared.
  • Example 31 0.06 g (10% by mass with respect to the solid content) of the polymerizable compound (RM21) obtained above was added to 10.0 g of the liquid crystal aligning agent (B), and dissolved by stirring at room temperature for 3 hours. A liquid crystal aligning agent (B21) was prepared.
  • Example 32 0.06 g (10% by mass with respect to the solid content) of the polymerizable compound (RM22) obtained above was added to 10.0 g of the liquid crystal aligning agent (B), and the mixture was dissolved by stirring at room temperature for 3 hours. A liquid crystal aligning agent (B22) was prepared.
  • Example 33 0.06 g (10% by mass with respect to the solid content) of the polymerizable compound (RM23) obtained above was added to 10.0 g of the liquid crystal aligning agent (B), and the mixture was dissolved by stirring at room temperature for 3 hours. A liquid crystal aligning agent (B23) was prepared.
  • Example 34 The same operation as in Example 6 was performed except that the liquid crystal aligning agent (B6) was used instead of the liquid crystal aligning agent (B1), and the response speeds before and after UV irradiation were compared.
  • Example 35 The response speed before and after UV irradiation was compared by performing the same operation as in Example 6 except that the liquid crystal aligning agent (B7) was used instead of the liquid crystal aligning agent (B1).
  • Example 36 The same operation as in Example 6 was performed except that the liquid crystal aligning agent (B8) was used instead of the liquid crystal aligning agent (B1), and the response speeds before and after UV irradiation were compared.
  • Example 37 The response speed before and after UV irradiation was compared by performing the same operation as in Example 6 except that the liquid crystal aligning agent (B9) was used instead of the liquid crystal aligning agent (B1).
  • Example 38 The response speed before and after UV irradiation was compared by performing the same operation as in Example 6 except that the liquid crystal aligning agent (B10) was used instead of the liquid crystal aligning agent (B1).
  • Example 39 The response speed before and after UV irradiation was compared by performing the same operation as in Example 6 except that the liquid crystal aligning agent (B11) was used instead of the liquid crystal aligning agent (B1).
  • Example 40 Except for using the liquid crystal aligning agent (B12) instead of the liquid crystal aligning agent (B1), the same operation as in Example 6 was performed, and the response speeds before and after UV irradiation were compared.
  • Example 41 The response speed before and after UV irradiation was compared by performing the same operation as in Example 6 except that the liquid crystal aligning agent (B13) was used instead of the liquid crystal aligning agent (B1).
  • Example 42 The response speed before and after UV irradiation was compared by performing the same operation as in Example 6 except that the liquid crystal aligning agent (B14) was used instead of the liquid crystal aligning agent (B1).
  • Example 43 The response speed before and after UV irradiation was compared by performing the same operation as in Example 6 except that the liquid crystal aligning agent (B15) was used instead of the liquid crystal aligning agent (B1).
  • Example 44 The response speed before and after UV irradiation was compared by performing the same operation as in Example 6 except that the liquid crystal aligning agent (B16) was used instead of the liquid crystal aligning agent (B1).
  • Example 45 The response speed before and after UV irradiation was compared by performing the same operation as in Example 6 except that the liquid crystal aligning agent (B17) was used instead of the liquid crystal aligning agent (B1).
  • Example 46 The response speed before and after UV irradiation was compared by performing the same operation as in Example 6 except that the liquid crystal aligning agent (B18) was used instead of the liquid crystal aligning agent (B1).
  • Example 47 The response speed before and after UV irradiation was compared by performing the same operation as in Example 6 except that the liquid crystal aligning agent (B19) was used instead of the liquid crystal aligning agent (B1).
  • Example 48 The response speed before and after UV irradiation was compared by performing the same operation as in Example 6 except that the liquid crystal aligning agent (B20) was used instead of the liquid crystal aligning agent (B1).
  • Example 49 The response speed before and after UV irradiation was compared by performing the same operation as in Example 6 except that the liquid crystal aligning agent (B21) was used instead of the liquid crystal aligning agent (B1).
  • Example 50 The response speed before and after UV irradiation was compared by performing the same operation as in Example 6 except that the liquid crystal aligning agent (B22) was used instead of the liquid crystal aligning agent (B1).
  • Example 51 The response speed before and after UV irradiation was compared by performing the same operation as in Example 6 except that the liquid crystal aligning agent (B23) was used instead of the liquid crystal aligning agent (B1).
  • TCA (3.36 g, 15.0 mmol), p-PDA (1.30 g, 12.0 mmol), DA-3 (3.14 g, 6.0 mmol), DA-1 (3.17 g, 12.0 mmol) were added.
  • CBDA (2.88 g, 14.7 mmol) and NMP (13.9 g) were added and reacted at 40 ° C. for 10 hours to polyamic acid.
  • a solution was obtained.
  • NMP (74.0 g) was added to the obtained polyimide powder (E) (6.0 g), and the mixture was dissolved by stirring at 50 ° C. for 12 hours.
  • BCS (20.0g) was added to this solution, and the liquid crystal aligning agent (F) was obtained by stirring at 50 degreeC for 5 hours.
  • RM2 0.06g (10 wt% with respect to solid content) was added with respect to 10.0g of said liquid crystal aligning agent (F), and it stirred and melt
  • Example 53 The same operation as in Example 6 was performed except that the liquid crystal aligning agent (F1) was used instead of the liquid crystal aligning agent (B1), and the response speeds before and after UV irradiation were compared.
  • Example 54 The response speed before and after UV irradiation was compared by performing the same operation as in Example 6 except that the liquid crystal aligning agent (F2) was used instead of the liquid crystal aligning agent (B1).
  • BODA (5.00 g, 20.0 mmol), p-PDA (0.87 g, 8.0 mmol), PCH (3.04 g, 8.0 mmol), DA-2 (4.88 g, 24.0 mmol) were added to NMP ( 52.7 g), and after reacting at 80 ° C. for 5 hours, CBDA (3.77 g, 19.2 mmol) and NMP (17.56 g) were added and reacted at 40 ° C. for 10 hours to obtain a polyamic acid solution. Obtained.
  • NMP (74.0 g) was added to the obtained polyimide powder (G) (6.0 g), and the mixture was dissolved by stirring at 50 ° C. for 12 hours.
  • BCS (20.0g) was added to this solution, and the liquid crystal aligning agent (G1) was obtained by stirring at 50 degreeC for 5 hours.
  • Example 56 The response speed before and after UV irradiation was compared by performing the same operation as in Example 6 except that the liquid crystal aligning agent (G2) was used instead of the liquid crystal aligning agent (B1).
  • Table 3 shows the results of Examples 34 to 51, 53, 54, and 56.
  • Example 34 using a polymer (polyimide) having a photoreactive side chain containing a methacryl group and the like and a side chain for vertically aligning liquid crystal and a liquid crystal aligning agent containing a polymerizable compound.
  • the polymerizable compounds and the polymers are different, but the improvement rate of the response speed before and after UV irradiation was remarkably high as in Examples 6 to 15.

Abstract

L'invention concerne un agent d'alignement de cristaux liquides qui comprend un précurseur de polyimide avec des chaînes latérales qui orientent verticalement les cristaux liquides et des chaînes latérales photoréactives qui contiennent au moins une sorte sélectionnée parmi les groupes méthacrylique, acrylique, vinyle et cinnamoyle, ainsi qu'au moins une sorte de polymère sélectionné parmi des polyimides obtenus par imidation desdits précurseurs de polyimide, un composé polymérisable ayant des groupes de photopolymérisation ou de photo-réticulation sur chacune de deux ou plus de deux extrémités, et un solvant.
PCT/JP2011/065101 2010-06-30 2011-06-30 Agent d'alignement de cristaux liquides, film à alignement de cristaux liquides, élément d'affichage à cristaux liquides et procédé de production d'éléments d'affichage à cristaux liquides WO2012002511A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2012522704A JP5761532B2 (ja) 2010-06-30 2011-06-30 液晶配向剤、液晶配向膜、液晶表示素子及び液晶表示素子の製造方法
KR1020137001733A KR101831006B1 (ko) 2010-06-30 2011-06-30 액정 배향제, 액정 배향막, 액정 표시 소자 및 액정 표시 소자의 제조 방법
CN201180041448.2A CN103080152B (zh) 2010-06-30 2011-06-30 液晶取向剂、液晶取向膜、液晶显示元件及液晶显示元件的制造方法

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2010150126 2010-06-30
JP2010-150126 2010-06-30
JP2011-080763 2011-03-31
JP2011080763 2011-03-31

Publications (1)

Publication Number Publication Date
WO2012002511A1 true WO2012002511A1 (fr) 2012-01-05

Family

ID=45402214

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2011/065101 WO2012002511A1 (fr) 2010-06-30 2011-06-30 Agent d'alignement de cristaux liquides, film à alignement de cristaux liquides, élément d'affichage à cristaux liquides et procédé de production d'éléments d'affichage à cristaux liquides

Country Status (5)

Country Link
JP (1) JP5761532B2 (fr)
KR (1) KR101831006B1 (fr)
CN (1) CN103080152B (fr)
TW (1) TWI525085B (fr)
WO (1) WO2012002511A1 (fr)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140072730A1 (en) * 2012-09-07 2014-03-13 Lg Chem, Ltd. Photoalignment Polyimide Copolymer and Liquid Crystal Alignment Layer
WO2014185410A1 (fr) * 2013-05-13 2014-11-20 日産化学工業株式会社 Procédé de production d'un substrat ayant une membrane d'orientation de cristaux liquides, pour utilisation dans un élément d'affichage à cristaux liquides à commutation dans le plan
WO2015050020A1 (fr) * 2013-10-04 2015-04-09 日産化学工業株式会社 Composé à cristaux liquides polymérisable, polymère à cristaux liquides, composition à cristaux liquides, et film horizontalement orienté à revêtement monocouche
JP2015148827A (ja) * 2010-06-30 2015-08-20 日産化学工業株式会社 重合性化合物及び液晶表示素子並びに液晶表示素子の製造方法
WO2015129890A1 (fr) * 2014-02-28 2015-09-03 日産化学工業株式会社 Composition pour formation de film dur, matériau d'orientation, et matériau de déphasage
KR20150115858A (ko) * 2013-02-01 2015-10-14 닛산 가가쿠 고교 가부시키 가이샤 액정 배향 처리제, 액정 배향막 및 액정 표시 소자
WO2016002722A1 (fr) * 2014-06-30 2016-01-07 日産化学工業株式会社 Substance d'alignement, matériau de déphasage et composition filmogène durcie
WO2016114312A1 (fr) * 2015-01-13 2016-07-21 日産化学工業株式会社 Procédé de traitement d'un composé de l'étain dans un mélange réactionnel
WO2017018501A1 (fr) * 2015-07-30 2017-02-02 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
CN107108541A (zh) * 2014-11-04 2017-08-29 日产化学工业株式会社 丁内酯化合物的制造方法
CN107108540A (zh) * 2014-11-04 2017-08-29 日产化学工业株式会社 丁内酯化合物和制造方法
JP2018055133A (ja) * 2012-10-05 2018-04-05 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
US9971202B2 (en) 2015-02-05 2018-05-15 Samsung Display Co., Ltd. Alignment layer, liquid crystal display including the same, and method of manufacturing liquid crystal display

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5943203B2 (ja) * 2010-06-30 2016-06-29 日産化学工業株式会社 液晶配向剤、液晶配向膜、液晶表示素子及び液晶表示素子の製造方法
JP6146100B2 (ja) * 2012-06-21 2017-06-14 Jsr株式会社 液晶配向剤、液晶配向膜、位相差フィルム、液晶表示素子及び位相差フィルムの製造方法
KR102143667B1 (ko) * 2012-08-21 2020-08-11 닛산 가가쿠 가부시키가이샤 액정 배향제, 액정 배향막 및 액정 표시 소자
KR102351459B1 (ko) * 2013-10-07 2022-01-13 닛산 가가쿠 가부시키가이샤 액정 배향제, 액정 배향막 및 액정 표시 소자
CN105849629B (zh) * 2013-10-07 2019-04-12 日产化学工业株式会社 液晶表示元件和液晶表示元件的制造方法
WO2015115588A1 (fr) * 2014-01-30 2015-08-06 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
CN106188540B (zh) * 2016-07-12 2019-01-22 深圳市华星光电技术有限公司 配向膜材料及配向膜的制作方法、液晶显示面板及其制作方法
TWI782997B (zh) * 2017-06-30 2022-11-11 日商日產化學工業股份有限公司 液晶晶胞之製造方法及液晶顯示元件

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09120069A (ja) * 1994-12-26 1997-05-06 Samsung Display Devices Co Ltd 液晶表示素子の配向膜形成方法
JP2004302272A (ja) * 2003-03-31 2004-10-28 Hong Kong Univ Of Science & Technology 液晶配向膜用組成物、液晶配向膜、液晶配向膜の製造方法、及びマレイミド化合物
JP2009102245A (ja) * 2007-10-22 2009-05-14 Adeka Corp 重合性化合物及び重合性組成物
JP2010031281A (ja) * 2002-05-31 2010-02-12 Elsicon Inc 液晶配向層用ハイブリッドポリマー材料
WO2010061490A1 (fr) * 2008-11-27 2010-06-03 シャープ株式会社 Écran à cristaux liquides et procédé de production correspondant

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1021479B1 (fr) 1997-09-25 2002-07-17 Rolic AG Polyimides photo-reticulables
KR100465446B1 (ko) * 2001-07-31 2005-01-13 삼성전자주식회사 액정배향막용 광배향재
CN1148608C (zh) * 2001-12-14 2004-05-05 中国科学院长春光学精密机械与物理研究所 一种双端光敏单体的光控取向膜制备方法
JP4175826B2 (ja) 2002-04-16 2008-11-05 シャープ株式会社 液晶表示装置
AU2003218476A1 (en) * 2002-05-31 2003-12-19 Elsicon, Inc. Hybrid polymer materials for liquid crystal alignment layers
US7862867B2 (en) 2006-10-05 2011-01-04 Nissan Chemical Industries, Ltd. Bifunctional polymerizable compound, polymerizable liquid crystal composition, and oriented film
JP5035517B2 (ja) 2007-02-16 2012-09-26 日産化学工業株式会社 液晶配向剤およびそれを用いた液晶表示素子
US8163199B2 (en) * 2008-06-30 2012-04-24 Chimei Innoloux Corporation Alignment treatment method of substrate for liquid crystal display device and manufacturing method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09120069A (ja) * 1994-12-26 1997-05-06 Samsung Display Devices Co Ltd 液晶表示素子の配向膜形成方法
JP2010031281A (ja) * 2002-05-31 2010-02-12 Elsicon Inc 液晶配向層用ハイブリッドポリマー材料
JP2004302272A (ja) * 2003-03-31 2004-10-28 Hong Kong Univ Of Science & Technology 液晶配向膜用組成物、液晶配向膜、液晶配向膜の製造方法、及びマレイミド化合物
JP2009102245A (ja) * 2007-10-22 2009-05-14 Adeka Corp 重合性化合物及び重合性組成物
WO2010061490A1 (fr) * 2008-11-27 2010-06-03 シャープ株式会社 Écran à cristaux liquides et procédé de production correspondant

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015148827A (ja) * 2010-06-30 2015-08-20 日産化学工業株式会社 重合性化合物及び液晶表示素子並びに液晶表示素子の製造方法
JP5776908B2 (ja) * 2010-06-30 2015-09-09 日産化学工業株式会社 液晶配向剤、液晶配向膜及び液晶表示素子並びに液晶表示素子の製造方法
US9791745B2 (en) * 2012-09-07 2017-10-17 Lg Chem, Ltd. Photoalignment polyimide copolymer and liquid crystal alignment layer
US20140072730A1 (en) * 2012-09-07 2014-03-13 Lg Chem, Ltd. Photoalignment Polyimide Copolymer and Liquid Crystal Alignment Layer
JP2018055133A (ja) * 2012-10-05 2018-04-05 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
KR102170065B1 (ko) 2013-02-01 2020-10-26 닛산 가가쿠 가부시키가이샤 액정 배향 처리제, 액정 배향막 및 액정 표시 소자
KR20150115858A (ko) * 2013-02-01 2015-10-14 닛산 가가쿠 고교 가부시키 가이샤 액정 배향 처리제, 액정 배향막 및 액정 표시 소자
JPWO2014185410A1 (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
WO2014185410A1 (fr) * 2013-05-13 2014-11-20 日産化学工業株式会社 Procédé de production d'un substrat ayant une membrane d'orientation de cristaux liquides, pour utilisation dans un élément d'affichage à cristaux liquides à commutation dans le plan
JPWO2015050020A1 (ja) * 2013-10-04 2017-03-09 日産化学工業株式会社 重合性液晶化合物、液晶性重合体、液晶性組成物、及び単層塗布型水平配向フィルム
KR102248600B1 (ko) * 2013-10-04 2021-05-06 닛산 가가쿠 가부시키가이샤 중합성 액정 화합물, 액정성 중합체, 액정성 조성물 및 단층 도포형 수평 배향 필름
KR20160067875A (ko) * 2013-10-04 2016-06-14 닛산 가가쿠 고교 가부시키 가이샤 중합성 액정 화합물, 액정성 중합체, 액정성 조성물 및 단층 도포형 수평 배향 필름
WO2015050020A1 (fr) * 2013-10-04 2015-04-09 日産化学工業株式会社 Composé à cristaux liquides polymérisable, polymère à cristaux liquides, composition à cristaux liquides, et film horizontalement orienté à revêtement monocouche
US10100201B2 (en) 2014-02-28 2018-10-16 Nissan Chemical Industries, Ltd. Cured film formation composition, orientation material and retardation material
WO2015129890A1 (fr) * 2014-02-28 2015-09-03 日産化学工業株式会社 Composition pour formation de film dur, matériau d'orientation, et matériau de déphasage
WO2016002722A1 (fr) * 2014-06-30 2016-01-07 日産化学工業株式会社 Substance d'alignement, matériau de déphasage et composition filmogène durcie
CN107108540A (zh) * 2014-11-04 2017-08-29 日产化学工业株式会社 丁内酯化合物和制造方法
CN107108541A (zh) * 2014-11-04 2017-08-29 日产化学工业株式会社 丁内酯化合物的制造方法
JPWO2016114312A1 (ja) * 2015-01-13 2017-10-19 日産化学工業株式会社 反応混合物中のスズ化合物の処理方法
KR20170102483A (ko) * 2015-01-13 2017-09-11 닛산 가가쿠 고교 가부시키 가이샤 반응 혼합물 중의 주석 화합물의 처리 방법
WO2016114312A1 (fr) * 2015-01-13 2016-07-21 日産化学工業株式会社 Procédé de traitement d'un composé de l'étain dans un mélange réactionnel
KR102621938B1 (ko) * 2015-01-13 2024-01-05 닛산 가가쿠 가부시키가이샤 반응 혼합물 중의 주석 화합물의 처리 방법
US9971202B2 (en) 2015-02-05 2018-05-15 Samsung Display Co., Ltd. Alignment layer, liquid crystal display including the same, and method of manufacturing liquid crystal display
CN107849365A (zh) * 2015-07-30 2018-03-27 日产化学工业株式会社 液晶取向剂、液晶取向膜和液晶表示元件
WO2017018501A1 (fr) * 2015-07-30 2017-02-02 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
US11111387B2 (en) 2015-07-30 2021-09-07 Nissan Chemical Industries, Ltd. Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element

Also Published As

Publication number Publication date
KR101831006B1 (ko) 2018-02-21
CN103080152A (zh) 2013-05-01
CN103080152B (zh) 2015-08-26
KR20130122931A (ko) 2013-11-11
TWI525085B (zh) 2016-03-11
JPWO2012002511A1 (ja) 2013-08-29
JP5761532B2 (ja) 2015-08-12
TW201219379A (en) 2012-05-16

Similar Documents

Publication Publication Date Title
JP5761532B2 (ja) 液晶配向剤、液晶配向膜、液晶表示素子及び液晶表示素子の製造方法
JP6108126B2 (ja) 重合性化合物
JP6172463B2 (ja) 液晶配向剤、液晶配向膜、液晶表示素子及び液晶表示素子の製造方法
JP6561833B2 (ja) 液晶配向剤、液晶配向膜及び液晶表示素子
JP5828329B2 (ja) 液晶配向剤
JP5967391B2 (ja) 重合性化合物及び液晶表示素子並びに液晶表示素子の製造方法
JP6361898B2 (ja) 重合性化合物
JP5975227B2 (ja) 液晶配向剤、液晶配向膜、液晶表示素子及び液晶表示素子の製造方法
JP5975226B2 (ja) 液晶配向剤、液晶配向膜、液晶表示素子及び液晶表示素子の製造方法
JP6478052B2 (ja) 液晶配向剤、液晶配向膜、液晶表示素子
JP6662306B2 (ja) 液晶配向剤、液晶表示素子及び液晶表示素子の製造方法
KR20160114645A (ko) 액정 배향제, 액정 배향막, 및 액정 표시 소자
WO2016125871A1 (fr) Agent d'orientation de cristaux liquides, film orienté de cristaux liquides, et élément d'affichage à cristaux liquides

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201180041448.2

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11800973

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2012522704

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20137001733

Country of ref document: KR

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 11800973

Country of ref document: EP

Kind code of ref document: A1