+

WO2012002513A1 - Composé polymérisable, agent d'alignement de cristaux liquides, film à alignement de cristaux liquides, dispositif d'affichage à cristaux liquides, et procédé de production de dispositif d'affichage à cristaux liquides - Google Patents

Composé polymérisable, agent d'alignement de cristaux liquides, film à alignement de cristaux liquides, dispositif d'affichage à cristaux liquides, et procédé de production de dispositif d'affichage à cristaux liquides Download PDF

Info

Publication number
WO2012002513A1
WO2012002513A1 PCT/JP2011/065103 JP2011065103W WO2012002513A1 WO 2012002513 A1 WO2012002513 A1 WO 2012002513A1 JP 2011065103 W JP2011065103 W JP 2011065103W WO 2012002513 A1 WO2012002513 A1 WO 2012002513A1
Authority
WO
WIPO (PCT)
Prior art keywords
liquid crystal
aligning agent
group
crystal aligning
polymerizable compound
Prior art date
Application number
PCT/JP2011/065103
Other languages
English (en)
Japanese (ja)
Inventor
ダニエルアントニオ 櫻葉汀
欣也 松本
賢一 元山
耕平 後藤
亮一 芦澤
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 CN201180041624.2A priority Critical patent/CN103080153B/zh
Priority to KR1020137002057A priority patent/KR101912955B1/ko
Priority to JP2012522706A priority patent/JP5776908B2/ja
Publication of WO2012002513A1 publication Critical patent/WO2012002513A1/fr

Links

Classifications

    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films

Definitions

  • the present invention relates to a polymerizable compound, 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.
  • the present invention relates to a method for manufacturing a liquid crystal display element.
  • a liquid crystal display element usually has an electrode and a liquid crystal on which a liquid crystal alignment film for aligning liquid crystals is formed.
  • materials for the liquid crystal alignment agent for forming this liquid crystal alignment film organic liquid crystal alignment film materials such as polyimide and polysiloxane liquid crystal alignment film materials obtained by polycondensation of alkoxysilane are known. (See Patent Document 1 and Patent Document 2).
  • As a display method of such a liquid crystal display element there is a method (also referred to as a vertical alignment (VA) method) in which liquid crystal molecules aligned perpendicular to a substrate are responded by an electric field.
  • Some manufacturing processes include a step of irradiating ultraviolet rays while applying a voltage to liquid crystal molecules.
  • 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 crystals 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.
  • An object of the present invention is to solve the above-described problems of the prior art, and a polymerizable compound, a liquid crystal aligning agent, a liquid crystal aligning film, and a liquid crystal display capable of improving the response speed of a vertical alignment type liquid crystal display element. It is providing the manufacturing method of an element and a liquid crystal display element.
  • the polymerizable compound of the present invention that solves the above problems is 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
  • W is a single bond or —OR 2 —.
  • R 2 is a linear or branched alkylene group having 1 to 10 carbon atoms.
  • the liquid crystal aligning agent of the present invention is characterized by having the above-described polymerizable compound, a polymer forming a liquid crystal alignment film for vertically aligning the liquid crystal, and a solvent.
  • the polymer forming the liquid crystal alignment film for vertically aligning the liquid crystal is at least one selected from a polyimide precursor having a side chain for vertically aligning the liquid crystal and a polyimide obtained by imidizing the polyimide precursor. May be included.
  • the polymer forming the liquid crystal alignment film for vertically aligning the liquid crystal may contain polysiloxane having a side chain for vertically aligning the liquid crystal. Furthermore, the polysiloxane preferably has a photoreactive side chain.
  • the polysiloxane is preferably obtained by polycondensation of at least one selected from alkoxysilanes and condensates thereof.
  • the alkoxysilane may contain an alkoxysilane represented by the following formula (7).
  • R 11 Si (OR 12 ) 3 (7) (R 11 is a hydrocarbon group having 8 to 30 carbon atoms in which a hydrogen atom may be substituted with a fluorine atom, and R 12 represents an alkyl group having 1 to 5 carbon atoms.)
  • the said alkoxysilane may contain following formula (8).
  • R 13 Si (OR 14 ) 3 (8) (R 13 represents an alkyl group in which a hydrogen atom is substituted with at least one selected from an acrylic group, a methacryl group, a vinyl group, an epoxy group, a vinyloxy group, and an acryloxy group, and R 14 represents an alkyl group having 1 to 5 carbon atoms. Represents.)
  • 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 comprises the above-mentioned polymerizable compound in a liquid crystal or a liquid crystal alignment film, and comprises a liquid crystal cell produced by irradiating ultraviolet rays while applying a voltage thereto. To do.
  • the method for producing a liquid crystal display device of the present invention is characterized in that the polymerizable compound is contained in a liquid crystal or a liquid crystal alignment film, and a liquid crystal cell is produced by irradiating ultraviolet rays while applying a voltage thereto. To do.
  • the present invention it is possible to provide a novel polymerizable compound capable of improving the response speed of a vertical alignment type liquid crystal display element.
  • this polymerizable compound By using this polymerizable compound, it is possible to provide a vertical alignment type liquid crystal display element having a high response speed. And in this liquid crystal aligning agent, even when the addition amount of a polymeric compound is small, or even when the irradiation amount of an ultraviolet-ray is small, a response speed can fully be improved.
  • V is represented by a single bond or —R 1 O—
  • R 1 is a linear or branched alkylene group having 1 to 10 carbon atoms, preferably represented by —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.
  • the polymerizable compound represented by the above formula (1) has a specific structure having ⁇ -methylene- ⁇ -butyrolactone groups which are polymerizable groups at both ends, the polymer has a rigid structure and has a liquid crystal structure. Because of its excellent alignment fixing ability, as shown in the examples to be described later, the response speed can be reduced by using it for the manufacture of vertical alignment type liquid crystal display elements such as PSA type liquid crystal displays and SC-PVA type liquid crystal displays. It can be greatly improved.
  • the polymerizable group at both ends must be an ⁇ -methylene- ⁇ -butyrolactone group, such as an acrylate group, a methacrylate group, a vinyl group, a vinyloxy group, and an epoxy group described in Patent Document 1.
  • 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) of the present invention can sufficiently withstand a high temperature, for example, a firing temperature of 200 ° C. or higher, because of its poor thermal polymerizability.
  • the polymerizable compound of the present invention represented by the above formula (1) can be synthesized by combining techniques in organic synthetic chemistry, and the synthesis method is not particularly limited.
  • 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 polymerizable compound represented by the above formula (1) can be contained in a liquid crystal aligning agent.
  • the liquid crystal aligning agent of this invention has the polymeric compound represented by the said Formula (1), the polymer which forms the liquid crystal aligning film which orientates a liquid crystal vertically, and a solvent.
  • a polymerizable compound represented by the above formula (1) is added to a known liquid crystal aligning agent for vertical alignment.
  • the liquid crystal alignment agent is a solution for forming a liquid crystal alignment film
  • the liquid crystal alignment film is a film for aligning liquid crystals in a predetermined direction, in the present invention, in the vertical direction.
  • the polymer that forms the liquid crystal alignment film that aligns the liquid crystal vertically is not particularly limited as long as the liquid crystal on the liquid crystal alignment film formed on the substrate can be aligned perpendicular to the substrate.
  • An organic liquid crystal alignment film material such as a polyimide obtained by imidizing the precursor or the polyimide precursor may be a polyester, (meth) acryloyl, or polysiloxane liquid crystal alignment film material. It is preferable that the polymer has a side chain that is aligned in the direction of, for example, a polyimide precursor having a side chain that aligns liquid crystal vertically, a polyimide obtained by imidizing the polyimide precursor, and a liquid crystal vertically.
  • Examples thereof include at least one selected from polysiloxanes having side chains to be oriented.
  • the polymer forming the liquid crystal alignment film for vertically aligning the liquid crystal may be only one type or two or more types.
  • Examples of the polyimide precursor include polyamic acid (also referred to as polyamic acid) and polyamic acid ester.
  • the side chain for vertically aligning the liquid crystal is not limited as long as the liquid crystal can be aligned vertically with respect to the substrate.
  • a long chain alkyl group, a ring structure or a branch in the middle of the long chain alkyl group may be used.
  • examples thereof include a group having a structure, a hydrocarbon group such as a steroid group, and a group in which some or all of the hydrogen atoms of these groups are replaced with fluorine atoms.
  • the side chain for vertically aligning the liquid crystal may be directly bonded to the main chain of the polymer such as polyimide precursor, polyimide or polysiloxane, that is, polyamic acid skeleton, polyimide skeleton or polysiloxane skeleton, 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 forming the liquid crystal alignment film for vertically aligning the liquid crystal preferably 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. If it has, the structure is not limited.
  • photoreactive side chains examples include vinyl groups, acrylic groups, methacryl groups, allyl groups, styryl groups, cinnamoyl groups, chalconyl groups, coumarin groups, maleimide groups, epoxy groups, vinyloxy groups, acryloxy groups as photoreactive groups. And the like, for example, these photoreactive groups themselves, and alkyl groups in which hydrogen atoms are substituted with these photoreactive groups.
  • the number of substituted hydrogen atoms is one or more, preferably one.
  • the number of carbon atoms of the alkyl group in which a hydrogen atom is substituted with a photoreactive group is preferably 1 to 30, more preferably 1 to 10, and still more preferably 1 to 5, from the viewpoints of response speed and vertical alignment. .
  • the photoreactive side chain may be directly bonded to the main chain of a polymer such as a polyimide precursor, polyimide or polysiloxane, or may be bonded via an appropriate bonding group.
  • a polymer such as a polyimide precursor, polyimide or polysiloxane
  • 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.
  • Represents an alkylene group of ⁇ 20, and —CH 2 — in the alkylene group may be optionally replaced by —CF 2 — or —CH ⁇ CH—, and when any of the following groups is not adjacent to each other: , may be substituted with these groups; -O -, - COO -, - OCO -, - NHCO -, - CONH -, - NH-, a divalent carbocyclic, divalent heterocyclic .R 10 Are vinyl, acrylic, methacrylic, allyl, styryl, (CH 2 CHCH 2) represents a 2, or represented by the following formula structure.)
  • 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 vinyl group, an acrylic group, a methacryl group, an allyl group, a styryl group, —N (CH 2 CHCH 2 ) 2 or a structure represented by the following formula from the viewpoint of photoreactivity.
  • 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 polymer forming the liquid crystal alignment film for vertically aligning the liquid crystal may have other side chains other than the side chain for vertically aligning the liquid crystal and the photoreactive side chain.
  • the other side chain include a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms which may be substituted with a hetero atom, a halogen atom, an amino group, a glycidoxy group, a mercapto group, an isocyanate group or a ureido group. It is done.
  • polysiloxane having these groups is used, the adhesion of the obtained liquid crystal alignment film to the substrate and the affinity with liquid crystal molecules can be improved.
  • a method for producing a polymer for forming a liquid crystal alignment film for vertically aligning such liquid crystals is not particularly limited.
  • diamine and tetra In a method of obtaining a polyamic acid by reaction with a carboxylic dianhydride, a method of copolymerizing a diamine having a side chain for vertically aligning a liquid crystal or a tetracarboxylic dianhydride having a side chain for vertically aligning a liquid crystal Convenient.
  • a polymer forming a liquid crystal alignment film for vertically aligning liquid crystals contains a photoreactive side chain
  • a diamine having a photoreactive side chain or a tetracarboxylic acid having a photoreactive side chain A dianhydride may be copolymerized.
  • 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. .
  • diamines having photoreactive side chains examples include vinyl groups, acrylic groups, methacryl groups, allyl groups, styryl groups, cinnamoyl groups, chalconyl groups, coumarin groups, maleimide groups, epoxy groups, vinyloxy groups, and acryloxy groups.
  • diamines having a reactive group as a side chain such as diamines having a side chain represented by the above formula (b). 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 examples include the following compounds, but are not limited thereto.
  • X is a single bond or a linking group selected from —O—, —COO—, —NHCO—, —NH—, Y is a single bond, or carbon that is unsubstituted or substituted by a fluorine atom. Represents an alkylene group of 1 to 20.
  • the diamine having the photoreactive group depends on the liquid crystal orientation when used as a liquid crystal alignment film, the pretilt angle, voltage holding characteristics, characteristics such as stored charge, the response speed of the liquid crystal when used as a liquid crystal display element, One type or a mixture of two or more types can also be used.
  • the diamine having such a photoreactive side chain is preferably used in an amount of 10 to 70 mol%, more preferably 20 to 60 mol%, particularly preferably diamine components used for the synthesis of polyamic acid. Is 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 side chain are used as a diamine component. Can be used together.
  • 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 method for producing the polysiloxane having a side chain for vertically aligning the liquid crystal is not particularly limited.
  • the polysiloxane can be produced by polycondensation of a condensate of alkoxysilane or alkoxysilane.
  • the alkoxysilane condensate is a multimer of alkoxysilane such as a dimer of alkoxysilane. If an alkoxysilane having a side chain for vertically aligning the liquid crystal is used as the alkoxysilane, a polysiloxane having a side chain for vertically aligning the liquid crystal can be formed.
  • an alkoxysilane having a photoreactive side chain or a condensate thereof may be used.
  • alkoxysilanes having side chains for vertically aligning liquid crystals include long-chain alkyl groups, groups having a ring structure or a branched structure in the middle of long-chain alkyl groups, hydrocarbon groups such as steroid groups, and the like of these groups.
  • alkoxysilanes having a group in which part or all of the hydrogen atoms are replaced with fluorine atoms as side chains for example, alkoxysilanes represented by the above formula (7).
  • R 11 is preferably an alkyl group or a fluoroalkyl group, and particularly preferably an alkyl group.
  • R 12 is preferably an alkyl group having 1 to 5 carbon atoms, and particularly preferably an alkyl group having 1 to 3 carbon atoms. More preferably, R 12 is a methyl group or an ethyl group.
  • alkoxysilane represented by the above formula (7) include, for example, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, dodecyltrimethoxysilane, and dodecyltriethoxysilane.
  • alkoxysilane having a side chain for vertically aligning other liquid crystals examples include an alkoxysilane having a side chain represented by the above formula (a).
  • An alkoxysilane having a side chain that vertically aligns a liquid crystal such as an alkoxysilane represented by the above formula (7) or an alkoxysilane having a side chain represented by the above formula (a) has good liquid crystal orientation.
  • 0.1 mol% or more is preferable, More preferably, it is 0.5 mol% or more, More preferably, it is 1 mol% or more.
  • 30 mol% or less is preferable, More preferably, it is 22 mol% or less.
  • alkoxysilane having a photoreactive side chain examples include a vinyl group, an acrylic group, a methacryl group, an allyl group, a styryl group, a cinnamoyl group, a chalcone group, a coumarin group, a maleimide group, an epoxy group, a vinyloxy group, and an acryloxy group.
  • a side chain having a photoreactive group such as, for example, these photoreactive groups themselves, or an alkoxysilane having, as a side chain, an alkyl group in which a hydrogen atom is substituted with these photoreactive groups, And alkoxysilanes represented by the above formula (8).
  • the number of hydrogen atoms substituted with R 13 is one or more, preferably one.
  • the carbon number of the alkyl group of R 13 is preferably 1 to 30, more preferably 1 to 10, and still more preferably 1 to 5.
  • R 14 is preferably an alkyl group having 1 to 5 carbon atoms, and particularly preferably an alkyl group having 1 to 3 carbon atoms. More preferably, R 14 is a methyl group or an ethyl group.
  • alkoxysilane represented by the above formula (8) include, for example, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltrimethylsilane.
  • Examples include ethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, acryloxyethyltrimethoxysilane, and acryloxyethyltriethoxysilane.
  • alkoxysilane having a photoreactive side chain examples include an alkoxysilane having a side chain represented by the above formula (b).
  • An alkoxysilane having a photoreactive side chain such as an alkoxysilane represented by the above formula (8) or an alkoxysilane having a side chain represented by the above formula (b) is sufficient to form a liquid crystal alignment film.
  • alkoxysilanes may be used.
  • examples of other alkoxysilanes include alkoxysilanes represented by the following formula (9).
  • R 15 represents a carbon atom having 1 to 6 carbon atoms which may be substituted with a hydrogen atom, a hetero atom, a halogen atom, an amino group, a glycidoxy group, a mercapto group, an isocyanate group or a ureido group.
  • a hydrogen group, R 16 is an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to 3.
  • R 15 is a hydrogen atom
  • specific examples when R 15 is a hydrogen atom include trimethoxysilane, triethoxysilane, tripropoxysilane, tributoxysilane and the like.
  • R 15 may be substituted with a hetero atom, a halogen atom, an amino group, a glycidoxy group, a mercapto group, an isocyanate group or a ureido group
  • the hydrogen group include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, methyltripropoxysilane, and 3-aminopropyl.
  • the alkoxysilane in which n is 0 is tetraalkoxysilane.
  • Tetraalkoxysilane is preferably used because it easily polycondenses with the alkoxysilane represented by the above formula (7) and the alkoxysilane represented by the above formula (8).
  • tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane or tetrabutoxysilane is preferable, and tetramethoxysilane or tetraethoxysilane is particularly preferable.
  • the amount of the alkoxysilane represented by the above formula (9) is 10 to 99.8 mol in the total alkoxysilane used for obtaining the polysiloxane. %, More preferably 35 to 96.9 mol%.
  • Examples of a method of polycondensing such alkoxysilane and its condensate include a method of hydrolyzing and condensing alkoxysilane and its condensate in a solvent such as alcohol or glycol.
  • the hydrolysis / condensation reaction may be either partial hydrolysis or complete hydrolysis.
  • complete hydrolysis it is theoretically necessary to add 0.5 moles of water of all alkoxy groups in the alkoxysilane or its condensate, but usually an excess of water is added in excess of 0.5 moles. Is preferred.
  • the amount of water used in the above reaction can be appropriately selected as desired, but it is usually preferably 0.5 to 2.5 times mol of all alkoxy groups in alkoxysilane.
  • acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, succinic acid, maleic acid, fumaric acid; alkalis such as ammonia, methylamine, ethylamine, ethanolamine, triethylamine
  • a metal salt such as hydrochloric acid, sulfuric acid or nitric acid
  • a method of polycondensation by heating a mixture of alkoxysilane, its condensate, solvent and oxalic acid can be mentioned.
  • oxalic acid is added to alcohol in advance to obtain an alcohol solution of oxalic acid, and then the alkoxysilane and its condensate are mixed while the solution is heated.
  • the amount of succinic acid used is preferably 0.2 to 2 mol with respect to 1 mol of all alkoxy groups contained in the alkoxysilane or its condensate.
  • Heating in this method can be performed at a liquid temperature of 50 to 180 ° C.
  • it is a method of heating for several tens of minutes to several tens of hours under reflux so that evaporation or volatilization of the liquid does not occur.
  • the alkoxysilane and its condensate may be mixed as a premixed mixture, or multiple types of alkoxysilane and its condensate are sequentially added. You may mix.
  • the solvent used for polycondensation of alkoxysilane and its condensate (hereinafter also referred to as polymerization solvent) is not particularly limited as long as it dissolves alkoxysilane and its condensate. Moreover, even if alkoxysilane and its condensate do not melt
  • Such a polycondensation solvent include alcohols such as methanol, ethanol, propanol, butanol, diacetone alcohol: ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol, 1,3-propanediol.
  • the polysiloxane polymerization solution (hereinafter, also referred to as polymerization solution) obtained by the above method is a concentration obtained by converting silicon atoms of all alkoxysilanes used as raw materials into SiO 2 (hereinafter referred to as SiO 2 conversion concentration). ) Is preferably 20% by mass or less, more preferably 5 to 15% by mass. By selecting an arbitrary concentration within this concentration range, gel formation can be suppressed and a homogeneous solution can be obtained.
  • the polymerization solution obtained by the above method may be contained in the liquid crystal aligning agent as it is, or the polysiloxane may be precipitated and contained as a solid in the liquid crystal aligning agent.
  • the solution obtained by the above method may be concentrated, diluted by adding a solvent, or substituted with another solvent and contained in the liquid crystal aligning agent.
  • the solvent to be used hereinafter also referred to as additive solvent
  • the additive solvent is not particularly limited as long as the polysiloxane is uniformly dissolved, and one kind or plural kinds can be arbitrarily selected and used.
  • Such an additive solvent include, in addition to the solvents mentioned as examples of the polymerization solvent described above, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as methyl acetate, ethyl acetate, and ethyl lactate. Can be mentioned. These solvents can improve the coating property when the liquid crystal aligning agent is applied onto the substrate by adjusting the viscosity of the liquid crystal aligning agent, or by spin coating, flexographic printing, ink jetting or the like.
  • the liquid crystal aligning agent of the present invention has the polymerizable compound represented by the above formula (1), the polymer forming the liquid crystal aligning film for vertically aligning the liquid crystal, and the solvent as described above.
  • the mixing ratio is not particularly limited, but the content of the polymerizable compound represented by the above formula (1) is based on 100 parts by mass of the polymer that forms the liquid crystal alignment film that aligns the liquid crystal vertically.
  • the amount is preferably 1 to 50 parts by mass, and more preferably 5 to 30 parts by mass.
  • the content of the polymer forming the liquid crystal alignment film for vertically aligning the liquid crystal contained in the liquid crystal aligning agent 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 may contain a polymer other than the polymer that forms the liquid crystal alignment film that vertically aligns the liquid crystal.
  • 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 there is no particular limitation on the solvent contained in the liquid crystal aligning agent, and it is possible to dissolve or disperse the components such as the polymerizable compound represented by the above formula (1) and the polymer that forms the liquid crystal alignment film that vertically aligns the liquid crystal. Anything is acceptable.
  • organic solvents as exemplified in the above synthesis of polyamic acid, polymerization solvents and additive solvents shown in the synthesis of polysiloxane 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 (manufactured by Asahi Glass Co., Ltd.).
  • 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.
  • liquid crystal aligning agent may contain inorganic fine particles, metalloxane oligomer, metalloxane polymer, leveling agent, surfactant and the like.
  • the inorganic fine particles fine particles such as silica fine particles, alumina fine particles, titania fine particles, or magnesium fluoride fine particles are preferable, and those in a colloidal solution state are particularly preferable.
  • This colloidal solution may be a dispersion of inorganic fine particles in a dispersion medium, or a commercially available colloidal solution.
  • the inclusion of inorganic fine particles makes it possible to impart the surface shape of the formed cured film and other functions.
  • the inorganic fine particles preferably have an average particle size of 0.001 to 0.2 ⁇ m, more preferably 0.001 to 0.1 ⁇ m. When the average particle diameter of the inorganic fine particles exceeds 0.2 ⁇ m, the transparency of the cured film formed using the prepared coating liquid may be lowered.
  • the dispersion medium for inorganic fine particles examples include water and organic solvents.
  • the colloidal solution it is preferable that the pH or pKa is adjusted to 1 to 10 from the viewpoint of the stability of the coating solution for forming a film. More preferably, it is 2-7.
  • organic solvent used for the dispersion medium of the colloidal solution examples include alcohols such as methanol, propanol, butanol, ethylene glycol, propylene glycol, butanediol, pentanediol, hexylene glycol, diethylene glycol, dipropylene glycol, and ethylene glycol monopropyl ether; Ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; esters such as ethyl acetate, butyl acetate and ⁇ -butyrolactone; Examples include ethers such as tetrahydrofuran and 1,4-dioxane. Of these, alcohols or ketones are preferred. These organic solvents can be used alone or in admixture of two or more as a dispersion
  • metalloxane oligomer and metalloxane polymer single or composite oxide precursors such as silicon, titanium, aluminum, tantalum, antimony, bismuth, tin, indium, and zinc are used.
  • the metalloxane oligomer or metalloxane polymer may be a commercially available product or may be obtained from a monomer such as a metal alkoxide, nitrate, hydrochloride, or carboxylate by a conventional method such as hydrolysis.
  • metalloxane oligomers and metalloxane polymers include siloxane oligomers or siloxanes such as methyl silicate 51, methyl silicate 53A, ethyl silicate 40, ethyl silicate 48, EMS-485, and SS-101 manufactured by Colcoat.
  • siloxane oligomers or siloxanes such as methyl silicate 51, methyl silicate 53A, ethyl silicate 40, ethyl silicate 48, EMS-485, and SS-101 manufactured by Colcoat.
  • titanoxane oligomers such as polymers and titanium-n-butoxide tetramer manufactured by Kanto Chemical Co., Inc. You may use these individually or in mixture of 2 or more types.
  • leveling agents and surfactants can be used, and commercially available products are particularly preferred because they are readily available.
  • the method for preparing the liquid crystal aligning agent of the present invention is not particularly limited. If the polymerizable compound represented by the above formula (1), the polymer forming the liquid crystal alignment film for vertically aligning the liquid crystal, and other components added as needed are mixed uniformly. Good. For example, since polysiloxane is usually polycondensed in a solvent as described above, it is convenient to use the polysiloxane solution as it is or to add other components to the polysiloxane solution as necessary. . Furthermore, the most convenient method is to use the polysiloxane polymerization solution as it is.
  • an organic solvent such as exemplified in the synthesis of the polyamic acid described above, or polymerization of polysiloxane is used.
  • a solvent selected from the group consisting of a solvent and an additive solvent can be used.
  • liquid crystal aligning agent of this invention By applying this liquid crystal aligning agent on a substrate and baking it, a liquid crystal alignment film for vertically aligning liquid crystals can be formed. Since the liquid crystal aligning agent of this invention has a polymeric compound represented by the said Formula (1), it can make the response speed of the liquid crystal display element using the obtained liquid crystal aligning film quick.
  • 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 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.
  • the coating film formed by applying the liquid crystal aligning agent by the above method can be baked to obtain a cured film.
  • the firing temperature of the coating film formed by applying the liquid crystal aligning agent is not limited, and can be performed at an arbitrary temperature of 100 to 350 ° C., for example.
  • the temperature is preferably 120 ° C. to 300 ° C., more preferably 150 ° C. °C -250 °C.
  • the liquid crystal aligning agent contains a polysiloxane having a side chain for vertically aligning the liquid crystal, it is preferably 140 ° 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, for example, a hot plate, a hot air circulating furnace, an infrared furnace, an IR oven, a belt furnace, or the like.
  • the polysiloxane in the liquid crystal alignment film undergoes polycondensation in this firing step.
  • firing is preferably performed at a temperature higher by 10 ° C. or more than the heat treatment temperature required for the liquid crystal cell production process, such as curing of the sealant.
  • the thickness of the liquid crystal alignment film obtained by firing is not particularly limited, but is preferably 5 nm or more, more preferably 10 nm or more because the reliability of the liquid crystal display element can be easily obtained. Further, since the power consumption of the liquid crystal display element does not become extremely large, the thickness of the liquid crystal alignment film is preferably 300 nm or less, more preferably 150 nm or less, and further preferably 100 nm or less.
  • 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 polymerizable compound represented by the above formula (1) is polymerized by irradiating ultraviolet rays while applying voltage to the liquid crystal aligning film and the liquid crystal layer. By doing so, a liquid crystal display element excellent in response speed is obtained.
  • 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, a polymerizable compound represented by the above formula (1) as a liquid crystal aligning agent for forming a liquid crystal aligning film.
  • liquid crystal aligning agent of the present invention having the above is used, 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 no slit pattern or projection pattern is formed on the opposite substrate
  • the liquid crystal display element having this structure can simplify the manufacturing process and obtain high transmittance.
  • 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 represented by the above formula (1) reacts to form a polymer, and the liquid crystal molecules are formed by this polymer. Since the tilt direction is stored, the response speed of the obtained liquid crystal display element can be increased.
  • the liquid crystal display element of this invention is liquid crystal. It may be prepared by containing a polymerizable compound represented by the above formula (1). Specifically, a vertical cell comprising a liquid crystal cell having two substrates arranged to face each other, a liquid crystal layer provided between the substrates, and a liquid crystal alignment film provided between the substrate and the liquid crystal layer.
  • An alignment type liquid crystal display element in which a liquid crystal alignment film is formed by applying and baking a liquid crystal alignment agent on two substrates, and the two substrates are arranged so that the liquid crystal alignment films face each other.
  • a liquid crystal layer composed of a liquid crystal containing a polymerizable compound represented by the above formula (1) is sandwiched between the two substrates, and is produced by irradiating ultraviolet rays while applying a voltage to the liquid crystal layer.
  • the liquid crystal display element is a vertical alignment type liquid crystal display device including a liquid crystal cell.
  • the substrate is the same as the above-described liquid crystal display element prepared by adding a polymerizable compound represented by the above formula (1) to a liquid crystal aligning agent that forms a liquid crystal aligning film.
  • the liquid crystal alignment film is formed by removing the polymerizable compound represented by the above formula (1) from the liquid crystal aligning agent of the present invention, for example, by applying a conventional liquid crystal aligning agent and baking it.
  • the liquid crystal alignment film can be formed by the same operation as described above.
  • the content of the polymerizable compound represented by the above formula (1) is, for example, 0.01 parts by mass to 0.10 parts by mass with respect to 100 parts by mass of the liquid crystal.
  • the response speed of the liquid crystal display element is sufficiently improved because the compound represented by the above formula (1) is used in the present invention. be able to.
  • a liquid crystal material used in a conventional vertical alignment method such as a negative type liquid crystal such as MLC-6608 or MLC-6609 manufactured by Merck Co., Ltd. can be used.
  • the method of sandwiching the liquid crystal layer between two substrates includes the liquid crystal display element prepared by adding a polymerizable compound represented by the above formula (1) to a liquid crystal aligning agent that forms a liquid crystal alignment film. It is the same.
  • the process of manufacturing a liquid crystal cell by irradiating ultraviolet rays while applying a voltage to the liquid crystal layer is applied, for example, by applying a voltage between the electrodes placed on the substrate to maintain this electric field. And a method of irradiating with ultraviolet rays.
  • 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 represented by the above formula (1) reacts to form a polymer, and the direction in which the liquid crystal molecules are tilted is memorized by this polymer. As a result, the response speed of the obtained liquid crystal display element can be increased.
  • liquid crystal aligning agent which forms a liquid crystal aligning film is made to contain the polymeric compound represented by the said Formula (1), and the liquid crystal is made to contain the polymeric compound represented by the said Formula (1).
  • a liquid crystal display element may be used.
  • both of the liquid crystal alignment films formed on the two substrates may be liquid crystal alignment films formed using a liquid crystal alignment agent containing the polymerizable compound represented by the above formula (1). Only the liquid crystal alignment film is formed using a liquid crystal aligning agent containing the polymerizable compound represented by the above formula (1), and the other liquid crystal alignment film is a polymerization represented by the above formula (1). It is good also as what was formed using the liquid crystal aligning agent which does not contain an ionic compound.
  • 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 an intermediate compound (RM1-A) represented by the following reaction formula. The yield was 92%.
  • this white solid was the target polymerizable compound (RM2) represented by the following formula.
  • the yield was 72%.
  • m-PDA m-phenylenediamine
  • p-PDA p-phenylenediamine
  • PCH 1,3-diamino-4- [4- (4-heptylcyclohexyl) phenoxy] benzene
  • DBA 3,5-diaminobenzoic acid
  • DA-1 2- (methacryloyloxy) ethyl 3,5-diaminobenzoate represented by the following formula
  • 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
  • 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 4 BODA (28.15 g, 112.5 mmol), m-PDA (4.86 g, 45 mmol), PCH (11.42 g, 30 mmol), DBA (11.41 g, 75 mmol) were mixed in NMP (187.8 g). After reacting at 80 ° C. for 5 hours, CBDA (6.77 g, 36 mmol) and NMP (62.6 g) were added and reacted at 40 ° C. for 10 hours to obtain a polyamic acid solution.
  • NMP (40.2 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. To this solution was added 5.0 wt% NMP solution (6.0 g) of 3-AMP (0.3 g as 3-AMP), NMP (27.9 g), and BCS (20.0 g) at 50 ° C.
  • the liquid crystal aligning agent (A1) was obtained by stirring for 5 hours.
  • Example 2 0.06 g (10% by mass with respect to the solid content) of the polymerizable compound RM1 obtained in Example 1 was added to 10.0 g of the liquid crystal aligning agent (A1), and the mixture was stirred at room temperature for 3 hours.
  • the liquid crystal aligning agent (A2) was prepared.
  • 0.18 g (30% by mass with respect to the solid content) of the polymerizable compound RM1 obtained in Example 1 was added to 10.0 g of the liquid crystal aligning agent (A1), and the mixture was stirred at room temperature for 3 hours.
  • a liquid crystal aligning agent (A3) was prepared.
  • NMP (74.0 g) was added to the obtained polyimide powder (B) (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 (B1) was obtained by stirring at 50 degreeC for 5 hours.
  • Liquid crystal aligning agent (B2) 0.06 g (10% by mass with respect to the solid content) of the polymerizable compound RM1 obtained in Example 1 was added to 10.0 g of the liquid crystal aligning agent (B1), and the mixture was stirred and dissolved at room temperature for 3 hours. Liquid crystal aligning agent (B2).
  • 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 (20.0g) was added to this solution, and the liquid crystal aligning agent (C1) 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 RM1 obtained in Example 1 was added to 10.0 g of the liquid crystal aligning agent (C1), and the mixture was stirred and dissolved at room temperature for 3 hours. Liquid crystal aligning agent (C2).
  • Example 7 BODA (3.13 g, 12.5 mmol), p-PDA (0.81 g, 7.5 mmol), PCH (1.90 g, 5 mmol), DA-1 (3.30 g, 12.5 mmol) and NMP (34. 5 g), the mixture was reacted at 80 ° C. for 5 hours, CBDA (2.35 g, 12 mmol) and NMP (11.5 g) were added, and the mixture was reacted at 40 ° C. for 10 hours to obtain a polyamic acid solution.
  • NMP (74.0 g) was added to the obtained polyimide powder (D) (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 liquid crystal aligning agent (D1) 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 RM1 obtained in Example 1 was added to 10.0 g of the liquid crystal aligning agent (D1), and the mixture was stirred and dissolved at room temperature for 3 hours.
  • Liquid crystal aligning agent (D2) 0.06 g (10% by mass with respect to the solid content) of the polymerizable compound RM1 obtained in Example 1 was added to 10.0 g of the liquid crystal aligning agent (D1), and the mixture was stirred and dissolved at room temperature for 3 hours.
  • Liquid crystal aligning agent (D2) Liquid crystal aligning agent (D2).
  • 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 (E1) 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 RM1 obtained in Example 1 was added to 10.0 g of the liquid crystal aligning agent (E1), and the mixture was stirred and dissolved at room temperature for 3 hours.
  • Liquid crystal aligning agent (E2) 0.06 g (10% by mass with respect to the solid content) of the polymerizable compound RM1 obtained in Example 1 was added to 10.0 g of the liquid crystal aligning agent (E1), and the mixture was stirred and dissolved at room temperature for 3 hours.
  • Liquid crystal aligning agent (E2) Liquid crystal aligning agent (E2).
  • Example 9 BODA (5.00 g, 20.0 mmol), p-PDA (2.16 g, 20.0 mmol), PCH (3.04 g, 8.0 mmol), DA-2 (2.44 g, 12.0 mmol) were added to NMP ( 49.2 g), and after reacting at 80 ° C. for 5 hours, CBDA (3.77 g, 19.2 mmol) and NMP (16.4 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 (F) (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 (F1) was obtained by stirring at 50 degreeC for 5 hours.
  • Liquid crystal aligning agent (F2) 0.06 g (10% by mass with respect to the solid content) of the polymerizable compound RM1 obtained in Example 1 was added to 10.0 g of the liquid crystal aligning agent (F1), and the mixture was stirred and dissolved at room temperature for 3 hours.
  • Liquid crystal aligning agent (F2) 0.06 g (10% by mass with respect to the solid content) of the polymerizable compound RM1 obtained in Example 1 was added to 10.0 g of the liquid crystal aligning agent (F1), and the mixture was stirred and dissolved at room temperature for 3 hours. Liquid crystal aligning agent (F2).
  • 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.
  • Liquid crystal aligning agent (G2) 0.06 g (10% by mass with respect to the solid content) of the polymerizable compound RM1 obtained in Example 1 was added to 10.0 g of the liquid crystal aligning agent (G1), and the mixture was stirred and dissolved at room temperature for 3 hours.
  • Liquid crystal aligning agent (G2) 0.06 g (10% by mass with respect to the solid content) of the polymerizable compound RM1 obtained in Example 1 was added to 10.0 g of the liquid crystal aligning agent (G1), and the mixture was stirred and dissolved at room temperature for 3 hours. Liquid crystal aligning agent (G2).
  • 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 (H) (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 (H1) was obtained by stirring at 50 degreeC for 5 hours.
  • 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 (I) (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 (I1) was obtained by stirring at 50 degreeC for 5 hours.
  • liquid crystal aligning agent (I1) 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 (I1) and dissolved by stirring at room temperature for 3 hours.
  • a liquid crystal aligning agent (I2) was prepared.
  • a liquid crystal containing a polymerizable compound was prepared as follows. 0.0147 g (3 ⁇ 10 ⁇ 5 mol) of the polymerizable compound RM1 obtained in Example 1 was added to 20 g of MLC-6608 (trade name, manufactured by Merck), and the mixture was stirred and dissolved at 80 ° C. for 3 hours. Liquid crystal 1 was prepared.
  • liquid crystal 1 liquid crystal 2 and liquid crystal 3, it was confirmed that the polymerizable compound was dissolved in liquid crystal material MLC-6608, and the polymerizable compound did not precipitate even after one month of refrigerated storage.
  • Example 13 Using the liquid crystal aligning agent (A1) obtained in Example 4, a liquid crystal cell was prepared according to the procedure shown below.
  • the liquid crystal aligning agent (A1) obtained in Example 4 was spin-coated on the ITO surface of the 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, and the temperature was 80 ° C. 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.
  • a sealant (solvent type thermosetting epoxy resin) was printed thereon.
  • the surface of the other substrate on which the liquid crystal alignment film was formed was faced inward and bonded to the previous substrate, and then the sealing agent was cured to produce an empty cell.
  • the liquid crystal 1 was injected into this 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., thereby producing 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, UV irradiation through a band-pass filter of 313 nm was irradiated from the outside of the liquid crystal cell at 5 J. 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 (after UV irradiation).
  • 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 14 The same operation as in Example 13 was performed except that the liquid crystal 2 was used in place of the liquid crystal 1, and the response speeds before and after UV irradiation were compared.
  • Example 2 Comparative Example 2 Except that the liquid crystal 3 was used instead of the liquid crystal 1, the same operation as in Example 13 was performed to compare the response speed before and after UV irradiation.
  • Example 15 The same operation as in Example 13 except that the liquid crystal aligning agent (A2) was used instead of the liquid crystal aligning agent (A1), MLC-6608 was used instead of the liquid crystal 1, and 20 J irradiation was performed instead of UV irradiation at 5 J. The response speed before and after UV irradiation was compared.
  • Example 16 Except for using the liquid crystal aligning agent (A3) instead of the liquid crystal aligning agent (A2), the same operation as in Example 15 was performed to compare the response speed before and after UV irradiation.
  • Example 3 The response speed before and after UV irradiation was compared by performing the same operation as in Example 15 except that the liquid crystal aligning agent (A1) was used instead of the liquid crystal aligning agent (A2).
  • Example 17 The response speed before and after UV irradiation was compared by performing the same operation as in Example 15 except that the liquid crystal aligning agent (B2) was used instead of the liquid crystal aligning agent (A2).
  • Example 4 Except for using the liquid crystal aligning agent (B1) instead of the liquid crystal aligning agent (A2), the same operation as in Example 15 was performed, and the response speeds before and after UV irradiation were compared.
  • Example 18 The response speed before and after UV irradiation was compared by performing the same operation as in Example 15 except that the liquid crystal aligning agent (C2) was used instead of the liquid crystal aligning agent (A2).
  • Example 5 Comparative Example 5 Except that the liquid crystal aligning agent (C1) was used instead of the liquid crystal aligning agent (A2), the same operation as in Example 15 was performed, and the response speed before and after UV irradiation was compared.
  • Example 19 Except that the liquid crystal aligning agent (D2) was used instead of the liquid crystal aligning agent (A2), the same operation as in Example 15 was performed, and the response speed before and after UV irradiation was compared.
  • Example 6 Comparative Example 6 Except for using the liquid crystal aligning agent (D1) instead of the liquid crystal aligning agent (A2), the same operation as in Example 15 was performed, and the response speeds before and after UV irradiation were compared.
  • Example 20 Except that the liquid crystal aligning agent (E2) was used instead of the liquid crystal aligning agent (A2), the same operation as in Example 15 was performed, and the response speed before and after UV irradiation was compared.
  • Example 7 The response speed before and after UV irradiation was compared by performing the same operation as in Example 15 except that the liquid crystal aligning agent (E1) was used instead of the liquid crystal aligning agent (A2).
  • Example 21 The response speed before and after UV irradiation was compared by performing the same operation as in Example 15 except that the liquid crystal aligning agent (F2) was used instead of the liquid crystal aligning agent (A2).
  • Example 22 Except for using the liquid crystal aligning agent (G2) instead of the liquid crystal aligning agent (A2), the same operation as in Example 15 was performed, and the response speeds before and after UV irradiation were compared.
  • Example 9 Except for using the liquid crystal aligning agent (G1) instead of the liquid crystal aligning agent (A2), the same operation as in Example 15 was performed, and the response speeds before and after UV irradiation were compared.
  • Example 23 The response speed before and after UV irradiation was compared by performing the same operation as in Example 15 except that the liquid crystal aligning agent (H2) was used instead of the liquid crystal aligning agent (A2).
  • Example 13 and Example 14 in which the polymerizable compound represented by the above formula (1) was contained in the liquid crystal showed a response speed after ultraviolet irradiation with respect to a response speed before ultraviolet irradiation.
  • the improvement rate of was significantly higher than that of Comparative Example 2 containing a conventional polymerizable compound. Therefore, it was confirmed that the response speed can be greatly improved by containing the polymerizable compound represented by the above formula (1) in the liquid crystal even if the amount of the polymerizable compound added to the liquid crystal is small.
  • Example 13 using the polymerizable compound in which V and W are oxyalkylene groups in the above formula (1) is an example using the polymerizable compound in which V and W are single bonds in the above formula (1).
  • the response rate improvement rate was significantly higher than 14.
  • Example 16 in which the addition amount of the polymerizable compound represented by the above formula (1) was 30% by mass had a higher response speed improvement rate than Example 15 in which the addition amount was 10% by mass. . Therefore, it was confirmed that the response speed was improved as the amount of the polymerizable compound represented by the formula (1) was increased.
  • Example 17 to 23 using polyimide having a photoreactive group the response speed was remarkably improved as compared with Example 15 using polyimide having no photoreactive group. It was confirmed that the response speed was further improved by using a polyimide having.
  • Example 24 0.06 g (10% by mass with respect to the solid content) of the polymerizable compound RM2 obtained in Example 2 was added to 10.0 g of the liquid crystal aligning agent (D1), and stirred and dissolved at room temperature for 3 hours. A liquid crystal aligning agent (D3) was prepared.
  • Comparative Example 10 0.06 g (10% by mass with respect to the solid content) of the polymerizable compound RM3 of Comparative Example 1 is added to 10.0 g of the liquid crystal aligning agent (D1), and the mixture is stirred and dissolved at room temperature for 3 hours. (D4) was prepared.
  • Example 25 The response speed before and after UV irradiation was compared by performing the same operation as in Example 19 except that the liquid crystal aligning agent (D3) was used instead of the liquid crystal aligning agent (D2). The results are shown in Table 3.
  • Example 26 The response speed before and after UV irradiation was compared by performing the same operation as in Example 25 except that the baking in the heat-circulating oven was performed at 200 ° C. for 30 minutes instead of 30 minutes at 160 ° C.
  • Comparative Example 12 The response speed before and after UV irradiation was compared by performing the same operation as in Comparative Example 11 except that the baking in the heat circulating oven was performed at 200 ° C. for 30 minutes instead of 30 minutes at 160 ° C.
  • Example 27 The response speed before and after UV irradiation was compared by performing the same operation as in Example 15 except that the liquid crystal aligning agent (I2) was used instead of the liquid crystal aligning agent (A2).
  • Example 28 Except for changing the baking temperature from 200 ° C. to 140 ° C., the same operation as in Example 27 was performed, and the response speed before and after UV irradiation was compared.
  • Example 13 Except for using the liquid crystal aligning agent (I1) instead of the liquid crystal aligning agent (I2), the same operation as in Example 27 was performed to compare the response speed before and after UV irradiation.
  • Comparative Example 14 Except for changing the firing temperature from 200 ° C. to 140 ° C., the same operation as in Comparative Example 13 was performed to compare the response speed before and after UV irradiation.
  • TEOS tetraethoxysilane
  • C18 octadecyltriethoxysilane
  • UPS 3-acryloxypropyltrimethoxysilane
  • MPMS 3-methacryloxypropyltrimethoxysilane
  • VTES triethoxyvinylsilane
  • NMP N-methyl -2-pyrrolidone
  • HG 2-methyl-2,4-pentanediol (also known as hexylene glycol)
  • BCS 2-butoxyethanol
  • the solution was stirred for 30 minutes and then refluxed for 30 minutes, and a mixed solution of methanol solution having a UPS content of 92% by mass and 0.44 g of BCS was added in advance.
  • the mixture was further refluxed for 30 minutes and then allowed to cool to obtain a polysiloxane solution having a SiO 2 equivalent concentration of 12% by mass.
  • Example 29 The polymerizable compound RM1 was added to the liquid crystal aligning agent (a) obtained in Comparative Example 15 so as to be 10% by mass and stirred at room temperature for 5 hours to prepare a varnish (liquid crystal aligning agent).
  • Example 30 The polymerizable compound RM1 was added to the liquid crystal aligning agent (a) obtained in Comparative Example 15 so as to be 20% by mass, and stirred at room temperature for 5 hours to prepare a varnish (liquid crystal aligning agent).
  • Example 31 The polymerizable compound RM2 was added to the liquid crystal aligning agent (a) obtained in Comparative Example 15 so as to be 10% by mass and stirred at room temperature for 5 hours to prepare a varnish (liquid crystal aligning agent).
  • Example 32 The polymerizable compound RM1 was added to the liquid crystal aligning agent (b) obtained in Comparative Example 16 so as to be 10% by mass, and stirred at room temperature for 5 hours to prepare a varnish (liquid crystal aligning agent).
  • Example 33 The polymerizable compound RM2 was added to the liquid crystal aligning agent (b) obtained in Comparative Example 16 so as to be 10% by mass, and stirred at room temperature for 5 hours to prepare a varnish (liquid crystal aligning agent).
  • Example 34 The polymerizable compound RM1 was added to the liquid crystal aligning agent (c) obtained in Comparative Example 17 so as to be 5% by mass, and stirred at room temperature for 5 hours to prepare a varnish (liquid crystal aligning agent).
  • Example 35 The polymerizable compound RM1 was added to the liquid crystal aligning agent (c) obtained in Comparative Example 17 so as to be 10% by mass, and the mixture was stirred at room temperature for 5 hours to prepare a varnish (liquid crystal aligning agent).
  • Example 36 The polymerizable compound RM1 was added to the liquid crystal aligning agent (d) obtained in Comparative Example 19 so as to be 5% by mass, and stirred at room temperature for 5 hours to prepare a varnish (liquid crystal aligning agent).
  • Example 37 Polymerizable compound RM1 was added to the liquid crystal aligning agent (d) obtained in Comparative Example 19 so as to be 10% by mass, and stirred at room temperature for 5 hours to prepare a varnish (liquid crystal aligning agent).
  • Example 38 Using the varnish (liquid crystal aligning agent) obtained in Example 29, a liquid crystal cell was prepared according to the procedure shown below. First, the varnish obtained in Example 29 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, and a hot plate at 80 ° C. After drying for 5 minutes, 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.
  • the liquid crystal aligning agent (a) obtained in Comparative Example 15 was spin-coated on the ITO surface on which no electrode pattern was formed, dried on an 80 ° C. hot plate for 5 minutes, and then heated at 200 ° C. in a hot air circulation oven. Was baked for 30 minutes to form a liquid crystal alignment film having a thickness of 100 nm.
  • a sealant (solvent type thermosetting epoxy resin) was printed thereon.
  • the surface of the other substrate on which the liquid crystal alignment film was formed was faced inward and bonded to the previous substrate, and then the sealing agent was cured to produce an empty cell.
  • Liquid crystal MLC-6608 (trade name, manufactured by Merck & Co., Inc.) was injected into this 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., thereby producing a liquid crystal cell.
  • the response speed immediately after production of the obtained liquid crystal cell was measured by the following method. After that, in the state where a voltage of 20 Vp-p was applied to the liquid crystal cell, 10 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 4 shows the response speed results immediately after the production of the liquid crystal cell (initial stage), after UV irradiation for 5 J (after UV 5 J) and after UV irradiation for 10 J (after UV 10 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 39 The same operation as in Example 38 was performed except that the varnish obtained in Example 30 was used instead of the varnish obtained in Example 29.
  • Example 40 The same operation as in Example 38 was performed except that the varnish obtained in Example 31 was used instead of the varnish obtained in Example 29.
  • Example 41 The same operation as in Example 38 was performed except that the varnish obtained in Example 32 was used instead of the varnish obtained in Example 29.
  • Example 42 The same operation as in Example 38 was performed except that the varnish obtained in Example 33 was used instead of the varnish obtained in Example 29.
  • Example 43 The same operation as in Example 38 was performed except that the varnish obtained in Example 34 was used in place of the varnish obtained in Example 29 and that 5J was irradiated instead of 10J with UV irradiation.
  • Example 44 The same operation as in Example 38 was performed except that the varnish obtained in Example 35 was used in place of the varnish obtained in Example 29 and that 5J was irradiated instead of 10J with UV irradiation.
  • Example 45 The same operation as in Example 38 was performed except that the varnish obtained in Example 36 was used in place of the varnish obtained in Example 29 and that 5J was irradiated instead of 10J with UV irradiation.
  • Example 46 The same operation as in Example 38 was performed except that the varnish obtained in Example 37 was used in place of the varnish obtained in Example 29 and that 5J was irradiated instead of 10J with UV irradiation.
  • Comparative Example 23 The same operation as in Example 38 was performed except that the liquid crystal aligning agent (c) obtained in Comparative Example 17 was used instead of the varnish obtained in Example 29, and that 5J was irradiated instead of 10J with UV irradiation. It was.
  • Comparative Example 24 The same operation as in Example 38 was performed except that the varnish obtained in Comparative Example 18 was used instead of the varnish obtained in Example 29, and 5 J was irradiated instead of 10 J with UV irradiation.
  • Comparative Example 25 The same procedure as in Example 38 was performed, except that the liquid crystal aligning agent (d) obtained in Comparative Example 19 was used instead of the varnish obtained in Example 29, and 5 J was irradiated instead of 10 J with UV irradiation. It was.
  • Comparative Example 26 The same operation as in Example 38 was performed except that the varnish obtained in Comparative Example 20 was used in place of the varnish obtained in Example 29 and that 5J was irradiated instead of 10J with UV irradiation.
  • Examples 41 to 46 using a polysiloxane having a photoreactive group the response speed is remarkably improved as compared with Examples 38 to 40 using a polysiloxane having no photoreactive group. It was confirmed that the response speed was further improved by using a polysiloxane having a photoreactive group.
  • liquid crystal aligning agent of the present invention containing the polymerizable compound represented by the above formula (1), it is confirmed that the response speed can be increased without including the polymerizable compound in the liquid crystal. It was. And in this liquid crystal aligning agent of this invention, even if it did not add a polymeric compound in large quantities, and it was also confirmed that a response speed can be made quick enough, without increasing the irradiation amount of an ultraviolet-ray. .
  • the liquid crystal display device manufactured using the liquid crystal aligning agent of the present invention is a liquid crystal capable of obtaining characteristics equivalent to those of the PSA method even when a liquid crystal to which no polymerizable compound is added is used in the PSA method.
  • a display element can be provided.
  • PSA type TFT Thin Film Transistor
  • TN Transmission Nematic liquid crystal display elements
  • VA VA liquid crystal display elements, and the like.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Nonlinear Science (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Optics & Photonics (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Liquid Crystal (AREA)
  • Furan Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un composé polymérisable représenté par la formule (1). Dans la formule (1), V représente une liaison simple ou -R1O-, où R1 représente un groupe alkylène à chaîne droite ou ramifiée ayant 1 à 10 atomes de carbone, et W représente une liaison simple ou -OR2-, où R2 représente un groupe alkylène à chaîne droite ou ramifiée ayant 1 à 10 atomes de carbone.
PCT/JP2011/065103 2010-06-30 2011-06-30 Composé polymérisable, agent d'alignement de cristaux liquides, film à alignement de cristaux liquides, dispositif d'affichage à cristaux liquides, et procédé de production de dispositif d'affichage à cristaux liquides WO2012002513A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201180041624.2A CN103080153B (zh) 2010-06-30 2011-06-30 聚合性化合物、液晶取向剂、液晶取向膜及液晶显示元件以及液晶显示元件的制造方法
KR1020137002057A KR101912955B1 (ko) 2010-06-30 2011-06-30 중합성 화합물, 액정 배향제, 액정 배향막 및 액정 표시 소자 그리고 액정 표시 소자의 제조 방법
JP2012522706A JP5776908B2 (ja) 2010-06-30 2011-06-30 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

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP2010-150126 2010-06-30
JP2010150126 2010-06-30
JP2010-195172 2010-08-31
JP2010195172 2010-08-31
JP2011-080763 2011-03-31
JP2011080763 2011-03-31

Publications (1)

Publication Number Publication Date
WO2012002513A1 true WO2012002513A1 (fr) 2012-01-05

Family

ID=45402216

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2011/065103 WO2012002513A1 (fr) 2010-06-30 2011-06-30 Composé polymérisable, agent d'alignement de cristaux liquides, film à alignement de cristaux liquides, dispositif d'affichage à cristaux liquides, et procédé de production de dispositif d'affichage à cristaux liquides

Country Status (5)

Country Link
JP (2) JP5776908B2 (fr)
KR (1) KR101912955B1 (fr)
CN (1) CN103080153B (fr)
TW (1) TWI564339B (fr)
WO (1) WO2012002513A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012141576A (ja) * 2010-12-15 2012-07-26 Jsr Corp 液晶表示素子の製造方法
WO2012115129A1 (fr) * 2011-02-25 2012-08-30 日産化学工業株式会社 Composé à cristaux liquides polymères, composition de cristaux liquides polymères et film orienté
WO2013115387A1 (fr) * 2012-02-03 2013-08-08 日産化学工業株式会社 Agent d'alignement des cristaux liquides, film d'alignement des cristaux liquides et élément d'affichage à cristaux liquides
WO2016072365A1 (fr) * 2014-11-04 2016-05-12 日産化学工業株式会社 Procédé de production de composé butyrolactone
WO2016072366A1 (fr) * 2014-11-04 2016-05-12 日産化学工業株式会社 Composé de butyrolactone et son procédé de production
WO2016093141A1 (fr) * 2014-12-12 2016-06-16 Dic株式会社 Élément d'affichage à cristaux liquides, et procédé de fabrication de celui-ci
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
WO2016125871A1 (fr) * 2015-02-06 2016-08-11 日産化学工業株式会社 Agent d'orientation de cristaux liquides, film orienté de cristaux liquides, et élément d'affichage à cristaux liquides
CN106575060A (zh) * 2014-06-17 2017-04-19 日产化学工业株式会社 液晶表示元件、液晶取向膜和液晶取向处理剂

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6375774B2 (ja) * 2013-11-15 2018-08-22 Jsr株式会社 液晶配向膜の製造方法、液晶表示素子用基板及びその製造方法、並びに液晶表示素子
JPWO2015115588A1 (ja) * 2014-01-30 2017-03-23 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
TWI560241B (en) * 2014-11-05 2016-12-01 Chi Mei Corp Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
TWI560242B (en) * 2014-11-05 2016-12-01 Chi Mei Corp Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
KR102352286B1 (ko) 2015-02-05 2022-01-18 삼성디스플레이 주식회사 배향막, 이를 포함한 액정 표시 장치 및 액정 표시 장치의 제조 방법
CN105647548B (zh) * 2016-02-23 2018-10-16 京东方科技集团股份有限公司 配向剂、配向膜的制作方法、显示面板及显示装置
WO2018066494A1 (fr) * 2016-10-07 2018-04-12 シャープ株式会社 Agent d'alignement de cristaux liquides pour substrats tft et procédé de production de panneau d'affichage à cristaux liquides
WO2020184424A1 (fr) * 2019-03-08 2020-09-17 日産化学株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003307720A (ja) * 2002-04-16 2003-10-31 Fujitsu Ltd 液晶表示装置
WO2008044536A1 (fr) * 2006-10-05 2008-04-17 Nissan Chemical Industries, Ltd. Composé polymérisable bifonctionnel, composition de cristaux liquides polymérisable et film orienté
WO2011068127A1 (fr) * 2009-12-02 2011-06-09 日産化学工業株式会社 Agent d'alignement de cristaux liquides et élément d'affichage à cristaux liquides l'utilisant
WO2011074546A1 (fr) * 2009-12-14 2011-06-23 日産化学工業株式会社 Agent d'alignement de cristaux liquides et élément d'affichage à cristaux liquides l'utilisant

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4522662B2 (ja) * 2003-03-31 2010-08-11 香港科技大学 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
CN103080823B (zh) * 2010-06-30 2015-09-30 日产化学工业株式会社 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以及聚合性化合物
WO2012002511A1 (fr) * 2010-06-30 2012-01-05 日産化学工業株式会社 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
WO2013099937A1 (fr) * 2011-12-28 2013-07-04 日産化学工業株式会社 Agent d'alignement de cristaux liquides, membrane d'alignement de cristaux liquides, élément d'écran à cristaux liquides, et procédé de fabrication d'élément d'écran à cristaux liquides

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003307720A (ja) * 2002-04-16 2003-10-31 Fujitsu Ltd 液晶表示装置
WO2008044536A1 (fr) * 2006-10-05 2008-04-17 Nissan Chemical Industries, Ltd. Composé polymérisable bifonctionnel, composition de cristaux liquides polymérisable et film orienté
WO2011068127A1 (fr) * 2009-12-02 2011-06-09 日産化学工業株式会社 Agent d'alignement de cristaux liquides et élément d'affichage à cristaux liquides l'utilisant
WO2011074546A1 (fr) * 2009-12-14 2011-06-23 日産化学工業株式会社 Agent d'alignement de cristaux liquides et élément d'affichage à cristaux liquides l'utilisant

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012141576A (ja) * 2010-12-15 2012-07-26 Jsr Corp 液晶表示素子の製造方法
WO2012115129A1 (fr) * 2011-02-25 2012-08-30 日産化学工業株式会社 Composé à cristaux liquides polymères, composition de cristaux liquides polymères et film orienté
KR102012060B1 (ko) 2012-02-03 2019-10-14 닛산 가가쿠 가부시키가이샤 액정 배향 처리제, 액정 배향막 및 액정 표시 소자
KR20140120353A (ko) * 2012-02-03 2014-10-13 닛산 가가쿠 고교 가부시키 가이샤 액정 배향 처리제, 액정 배향막 및 액정 표시 소자
JPWO2013115387A1 (ja) * 2012-02-03 2015-05-11 日産化学工業株式会社 液晶配向処理剤、液晶配向膜及び液晶表示素子
WO2013115387A1 (fr) * 2012-02-03 2013-08-08 日産化学工業株式会社 Agent d'alignement des cristaux liquides, film d'alignement des cristaux liquides et élément d'affichage à cristaux liquides
CN106575060B (zh) * 2014-06-17 2019-11-29 日产化学工业株式会社 液晶表示元件、液晶取向膜和液晶取向处理剂
TWI676846B (zh) * 2014-06-17 2019-11-11 日商日產化學工業股份有限公司 液晶顯示元件、液晶配向膜以及液晶配向處理劑
EP3159737A4 (fr) * 2014-06-17 2018-02-21 Nissan Chemical Industries, Ltd. Élément d'affichage à cristaux liquides, film d'alignement de cristaux liquides et agent de traitement d'alignement de cristaux liquides
CN106575060A (zh) * 2014-06-17 2017-04-19 日产化学工业株式会社 液晶表示元件、液晶取向膜和液晶取向处理剂
WO2016072365A1 (fr) * 2014-11-04 2016-05-12 日産化学工業株式会社 Procédé de production de composé butyrolactone
WO2016072366A1 (fr) * 2014-11-04 2016-05-12 日産化学工業株式会社 Composé de butyrolactone et son procédé de production
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
JP6011903B1 (ja) * 2014-12-12 2016-10-25 Dic株式会社 液晶表示素子及びその製造方法
WO2016093141A1 (fr) * 2014-12-12 2016-06-16 Dic株式会社 Élément d'affichage à cristaux liquides, et procédé de fabrication de celui-ci
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
KR20170113594A (ko) * 2015-02-06 2017-10-12 닛산 가가쿠 고교 가부시키 가이샤 액정 배향제, 액정 배향막, 및 액정 표시 소자
WO2016125871A1 (fr) * 2015-02-06 2016-08-11 日産化学工業株式会社 Agent d'orientation de cristaux liquides, film orienté de cristaux liquides, et élément d'affichage à cristaux liquides
KR20230011492A (ko) * 2015-02-06 2023-01-20 닛산 가가쿠 가부시키가이샤 액정 배향제, 액정 배향막, 및 액정 표시 소자
KR102529347B1 (ko) 2015-02-06 2023-05-04 닛산 가가쿠 가부시키가이샤 액정 배향제, 액정 배향막, 및 액정 표시 소자
KR102597729B1 (ko) 2015-02-06 2023-11-02 닛산 가가쿠 가부시키가이샤 액정 배향제, 액정 배향막, 및 액정 표시 소자

Also Published As

Publication number Publication date
KR20130135822A (ko) 2013-12-11
CN103080153B (zh) 2016-02-10
JPWO2012002513A1 (ja) 2013-08-29
CN103080153A (zh) 2013-05-01
JP5967391B2 (ja) 2016-08-10
TW201215640A (en) 2012-04-16
JP5776908B2 (ja) 2015-09-09
JP2015148827A (ja) 2015-08-20
TWI564339B (zh) 2017-01-01
KR101912955B1 (ko) 2018-10-29

Similar Documents

Publication Publication Date Title
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
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
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
JP5257548B2 (ja) 液晶表示素子および液晶配向剤
JP6108126B2 (ja) 重合性化合物
KR102115015B1 (ko) 액정 배향 처리제 및 그것을 사용한 액정 표시 소자
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
JP6387957B2 (ja) 光反応性基を有する架橋性化合物を含有する液晶配向剤
JP5716674B2 (ja) 液晶配向処理剤及びそれを用いた液晶表示素子
KR102597729B1 (ko) 액정 배향제, 액정 배향막, 및 액정 표시 소자

Legal Events

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

Ref document number: 201180041624.2

Country of ref document: CN

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

Ref document number: 11800975

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2012522706

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: 20137002057

Country of ref document: KR

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 11800975

Country of ref document: EP

Kind code of ref document: A1

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载