[go: up one dir, main page]

WO2019208765A1 - 液晶調光素子 - Google Patents

液晶調光素子 Download PDF

Info

Publication number
WO2019208765A1
WO2019208765A1 PCT/JP2019/017917 JP2019017917W WO2019208765A1 WO 2019208765 A1 WO2019208765 A1 WO 2019208765A1 JP 2019017917 W JP2019017917 W JP 2019017917W WO 2019208765 A1 WO2019208765 A1 WO 2019208765A1
Authority
WO
WIPO (PCT)
Prior art keywords
liquid crystal
group
component
carbon atoms
light control
Prior art date
Application number
PCT/JP2019/017917
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
尚士 鉄谷
雅章 片山
悟志 南
耕平 後藤
Original Assignee
日産化学株式会社
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 日産化学株式会社 filed Critical 日産化学株式会社
Priority to CN201980028621.1A priority Critical patent/CN112041739B/zh
Priority to KR1020207030480A priority patent/KR20210005015A/ko
Priority to JP2020515600A priority patent/JP7355007B2/ja
Publication of WO2019208765A1 publication Critical patent/WO2019208765A1/ja
Priority to JP2023142490A priority patent/JP7548390B2/ja

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/12—Unsaturated polyimide precursors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • 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

Definitions

  • the present invention relates to a guest-host type liquid crystal light control device using a film substrate and a liquid crystal aligning agent suitable for the liquid crystal light control device.
  • a liquid crystal display element using a film substrate needs to be performed at a lower temperature than the case where a glass substrate is used in the element manufacturing process from the viewpoint of heat resistance of the substrate.
  • the guest-host type liquid crystal using the dichroic dye has a problem that the voltage holding ratio characteristic of the host liquid crystal material is greatly impaired due to the influence of the dichroic dye. (For example, see Patent Document 2)
  • a liquid crystal light control device using a film base material is generally produced by a roll-to-roll method, so the liquid crystal aligning agent is often applied to the entire surface of the base material.
  • a sealant for bonding the two substrates is applied on the liquid crystal alignment film.
  • Subsequent curing of the sealing agent is generally performed by ultraviolet rays and heat, but in the case of a film substrate, the thermal curing step of the sealing agent is omitted from the viewpoint of heat resistance or the curing treatment is performed at a low temperature. In some cases, the adhesion strength between the liquid crystal alignment film and the sealant is insufficient.
  • the guest host type liquid crystal element using the dichroic dye as described above has a problem that a good voltage holding ratio cannot be obtained.
  • the present invention aims at simultaneously improving the adhesion strength between the liquid crystal alignment film and the sealing agent and the voltage holding ratio of the liquid crystal display element in a guest-host type liquid crystal light control device using a film substrate.
  • the present invention achieves the above-described object, and includes a pair of substrates on which transparent electrodes are installed, and a liquid crystal layer sandwiched between the pair of substrates, and the liquid crystal layer includes a host liquid crystal and a dichroic dye.
  • the substrate is a transparent film material, the substrate has a liquid crystal alignment film on the surface in contact with the liquid crystal layer, and the liquid crystal alignment film is obtained from a liquid crystal alignment agent containing the following components (A) and (B):
  • a guest-host type liquid crystal light control device characterized by being a liquid crystal alignment film.
  • (A) component an imidized polymer of polyamic acid obtained from a diamine component and a tetracarboxylic dianhydride component, wherein the diamine component is at least a diamine having a group represented by the following formula (N-1) Contains one species.
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents —CH 2 —, —O—, —O—CO—, or phenylene
  • R 3 represents a hydrogen atom having 1 to 12 carbon atoms.
  • the obtained liquid crystal alignment film has excellent seal adhesion, has a desired voltage holding ratio, and has reliability.
  • a liquid crystal alignment film can be provided.
  • a liquid crystal aligning agent for forming the liquid crystal alignment film and a guest-host type liquid crystal light adjusting device including the liquid crystal alignment film can be provided.
  • a method for producing the liquid crystal alignment film can be provided in addition to or in addition to the above effects.
  • the liquid crystal aligning agent used for this invention contains (A) component; and (B) component.
  • ⁇ (A) component >> The component (A) is an imidized polymer of polyamic acid obtained from a diamine component and a tetracarboxylic dianhydride component, and the diamine component is a diamine having a group represented by the following formula (N-1). Contains at least one. (Wherein R 1 represents a hydrogen atom or a methyl group, R 2 represents —CH 2 —, —O—, —O—CO—, or phenylene, and R 3 represents a hydrogen atom having 1 to 12 carbon atoms.
  • the polyamic acid according to the present invention can be obtained by reacting a diamine compound with tetracarboxylic dianhydride.
  • the diamine used for the polymerization of the polyamic acid of the present invention can be represented by the following formula (1).
  • a 1 and A 2 in the above formula (1) are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms, Y 1 is a divalent organic group. From the viewpoint of liquid crystal orientation, A 1 and A 2 are preferably a hydrogen atom or a methyl group.
  • the diamine A1 used in the present invention is a diamine having a group represented by the following formula (N-1).
  • N-1 represents a hydrogen atom or a methyl group
  • R 2 represents —CH 2 —, —O—, —O—CO—, or phenylene
  • R 3 represents a hydrogen atom having 1 to 12 carbon atoms.
  • R 4 represents a hydrogen atom or a methyl group
  • * represents a bond.
  • the diamine A1 is at least one moiety selected from the group consisting of a methacryl group, an acryl group, a vinyl group, a substituted vinyl group substituted with a hydrocarbon group having 1 to 12 carbon atoms, and a cinnamoyl group. It has structure (p) in the side chain.
  • the partial structure (p) is more preferably at least one selected from a methacryl group, an acryl group, a vinyl group, and a substituted vinyl group substituted with a hydrocarbon group having 1 to 12 carbon atoms. At least one selected from the structures represented by 1) to (1-4) is more preferable.
  • R 1 represents a hydrogen atom or a methyl group
  • R 3 represents a hydrogen atom, a linear hydrocarbon group having 1 to 12 carbon atoms, or a branched hydrocarbon group having 1 to 12 carbon atoms
  • R 4 represents a hydrogen atom or a methyl group.
  • “* 1” indicates a bond.
  • Examples of the linear hydrocarbon group for R 3 in the formula (1-2) include an alkyl group and an alkenyl group, and an alkyl group is more preferable. More preferred is an alkyl group having 1 to 3 carbon atoms, and a methyl group is more preferred.
  • Examples of the branched hydrocarbon group for R 3 in the formula (1-2) include a branched alkyl group and a branched alkenyl group, and a branched alkyl group is preferable.
  • a branched alkyl group having 3 to 4 carbon atoms is more preferable, and i-isopropyl group, 2-methylpropyl group, or 1-methylpropyl group is more preferable.
  • Examples of the side chain having the partial structure (p) include those represented by the following formula (b).
  • R 8 represents a single bond or —CH 2 —, —O—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, —NHC ( ⁇ O) NH—, —CH.
  • R a represents a linear hydrocarbon group having 1 to 12 carbon atoms or a branched hydrocarbon group having 1 to 12 carbon atoms
  • R 9 represents a single bond or an alkylene group having 1 to 20 carbon atoms which is unsubstituted or substituted by a fluorine atom.
  • At least one —CH 2 CH 2 — may be replaced with —CH ⁇ CH—, and at least one —CH 2 — may be replaced with —CF 2 —,
  • these groups are not adjacent to each other, May be; -O -, - COO -, - OCO -, - NHCO -, - CONH -, - NH-, a divalent carbocyclic, divalent heterocyclic;
  • R 10 is the partial structure (p "* 1" represents a bond bonded to the main chain of the polymer.
  • R 8 can be formed by a general organic synthetic method, but from the viewpoint of ease of synthesis, —CH 2 —, —O—, —COO—, —NHCO—, —NH—, —CH 2 O—, —N (R a ) — (R a represents a linear hydrocarbon group having 1 to 12 carbon atoms or a branched hydrocarbon group having 1 to 12 carbon atoms) is preferable.
  • divalent carbocycle or divalent heterocycle for replacing any —CH 2 — in R 9 include cyclohexane, benzene, naphthalene, bicyclohexane, cyclohexylbenzene, biphenyl, 4-cyclohexylbiphenyl, gonane, Examples include, but are not limited to, a group in which two hydrogen atoms are removed from a compound such as pyridine, pyrrole, pyrimidine, thiophene, furan, carbazole, oxazole, and 1,3,5-triazine.
  • R 10 is the partial structure (p), and the preferred range is also as described above.
  • Examples of the diamine (I) having the partial structure (p) in the side chain include the following compound (1-D), but are not limited thereto.
  • Sp represents a single bond, —O— or —O—Q T —O— (where Q T represents a divalent group containing a phenylene group or a naphthalene group), and m is 0 or 1.
  • R 8, R 9, R 10 has the same meaning as R 8, R 9, R 10 in the formula (b).
  • Preferred embodiments of the diamine A1 having the partial structure (p) in the side chain include the following compounds (1-D1) to (1-D4).
  • Definition of R 8, R 9 and R 10 in the formula has the same meaning as R 8, R 9 and R 10 in the formula (b).
  • the diamine A1 As the diamine A1, the following formulas (1-D1-1) to (1-D1-8) are more preferable.
  • X 1 and X 2 each independently represent a single bond or a linking group selected from —O—, —COO—, —NHCO—, and —NH—
  • Y is unsubstituted or substituted by a fluorine atom
  • R a , R b and R c have the same meanings as R 3 , R 1 and R 4 in formula (1-2), respectively.
  • R d represents a linear hydrocarbon group having 1 to 12 carbon atoms or a branched hydrocarbon group having 1 to 12 carbon atoms.
  • n is an integer of 1 to 20, and R 1 represents a hydrogen atom or a methyl group.
  • the diamine A1 is more preferably the formula (1-D1-5) or (1-D1-9). Since the diamine component containing the above formulas (1-D1-5) to (1-D1-9) has high flexibility of the monomer, the crosslinking reaction easily proceeds, and the degree of crosslinking of the liquid crystal alignment film can be further improved. it can.
  • the carbon number of R a is preferably 6 or less, more preferably 3 or less, and particularly preferably R a is a hydrogen atom.
  • R b and R c are preferably hydrogen atoms.
  • R d is preferably a linear hydrocarbon group having 6 or less carbon atoms or a branched hydrocarbon group, more preferably a linear hydrocarbon group having 3 or less carbon atoms. It is a hydrocarbon group or a branched hydrocarbon group.
  • the preferred positions of the two amino groups are 2, 4 positions, 2, 5 positions or 3, 5 positions on the benzene ring with respect to the N-allyl group. is there.
  • diamine having the structure represented by the above formula (1-D1-5) are shown in the following formulas (1-D1-5b) to (1-D1-5g), but are not limited thereto.
  • the formula (1-D1-5b) or the formula (1-D1-5c) is preferable.
  • n is preferably an integer of 1 to 10.
  • Specific examples of the above formula (1-D1-9) are shown in the following formulas (1-D1-9a) to (1-D1-9b), but are not limited thereto.
  • the said diamine A1 can be used individually by 1 type in these or in combination of 2 or more types.
  • a diamine having a vertical alignment group when the vertical alignment is desired, a diamine having a vertical alignment group can be used.
  • the diamine A2 having such a vertical alignment group include diamines represented by the formulas [2-1] to [2-31] described in paragraphs [0033] to [0042] of International Publication WO2013 / 125595. These diamines are preferably 5% by mole or more, more preferably 10% by mole or more, and still more preferably 20% by mole or more based on the entire diamine component. From the viewpoint of increasing the curing rate, 90 mol% or less is preferable, and 80 mol% or less is more preferable. More preferred diamines are at least one selected from the following formulas [2a-24] to [2a-33].
  • each R 1 independently represents —O—, —OCH 2 —, —CH 2 O—, —COOCH 2 —.
  • at least one linking group selected from the group consisting of —CH 2 OCO— and when in the meta position with respect to two amino groups, R 1 represents —CONH— , —NHCO—, and —CH 2 —, each represents a bonding group selected from the group consisting of —CH 2 —, and each R 2 independently represents a linear or branched alkyl group having 1 to 22 carbon atoms, carbon Represents a linear or branched alkoxy group of 1 to 22, wherein Cy is a group selected from a 4,4′-biphenyldiyl group, a 4,4′-phenylcyclohexyl group, and a 4,4′-dicyclohexyl group; is there.
  • R 3 represents —O— or CH 2 O—
  • Cy 2 has the same meaning as Cy
  • R 7 each independently represents a linear or branched group having 3 to 12 carbon atoms.
  • the cis-trans isomerism of 1,4-cyclohexylene indicates the trans isomer.
  • each A 1 independently represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group having 1 to 22 carbon atoms.
  • the amount of the diamine A1 is preferably 10 to 100 mol% with respect to the entire diamine component.
  • the diamine A1 is contained in an amount of 40 to 80 mol% and the diamine A2 is contained in an amount of 20 to 60 mol% with respect to the entire diamine component.
  • the partial structures (p) form a cross-linked structure.
  • the film density of the polymer is improved by such an action, and even when a guest-host type liquid crystal containing a host liquid crystal and a dichroic dye is used, it has excellent seal adhesion and a desired voltage holding ratio (VHR). And a reliable liquid crystal alignment film can be obtained.
  • tetracarboxylic dianhydrides include aliphatic tetracarboxylic dianhydrides and alicyclic tetracarboxylic dianhydrides. Specific examples of these include the following groups [1] to [5].
  • Examples of the aliphatic tetracarboxylic dianhydride include 1,2,3,4-butanetetracarboxylic dianhydride;
  • R 3 to R 23 are each Independently, a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, or a monovalent having 1 to 6 carbon atoms containing a fluorine atom
  • An organic group or a phenyl group which may be the same or different,
  • RM is a hydrogen atom or a methyl group
  • Xa is a tetravalent organic group represented by the following formulas (Xa-1) to
  • the component containing at least 1 type of tetracarboxylic dianhydride chosen from the following as tetracarboxylic dianhydride.
  • the said tetracarboxylic dianhydride can be used individually by 1 type or in combination of 2 or more types.
  • the liquid crystal aligning agent containing the polymer even when a guest-host type liquid crystal containing a host liquid crystal and a dichroic dye is used, it has excellent seal adhesion and a desired voltage holding ratio (VHR). And a reliable liquid crystal alignment film can be obtained.
  • the polyamic acid which is a polyimide precursor used in the present invention can be synthesized by the following method. Specifically, the tetracarboxylic dianhydride component and the diamine component are added in the presence of an organic solvent at ⁇ 20 ° C. to 150 ° C., preferably 0 ° C. to 50 ° C., for 30 minutes to 24 hours, preferably 1 to 12 It can be synthesized by reacting for a time.
  • the organic solvent used in the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, or ⁇ -butyrolactone in view of the solubility of the monomer and polymer, and these may be used alone or in combination. May be.
  • the concentration of the polymer is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass from the viewpoint that polymer precipitation is difficult to occur and a high molecular weight body is easily obtained.
  • the polyamic acid obtained as described above can be recovered by precipitating the polymer by pouring into the poor solvent while thoroughly stirring the reaction solution. Moreover, the powder of polyamic acid refine
  • a poor solvent is not specifically limited, Water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene etc. are mentioned.
  • the polyimide used for this invention can be manufactured by imidating the said polyamic acid ester or polyamic acid which is a polyimide precursor.
  • a polyimide is produced from a polyamic acid ester
  • chemical imidization in which a basic catalyst is added to the polyamic acid ester solution or the polyamic acid ester solution obtained by dissolving the polyamic acid ester resin powder in an organic solvent is simple.
  • Chemical imidization is preferable because the imidization reaction proceeds at a relatively low temperature and the molecular weight of the polymer is unlikely to decrease during the imidization process.
  • Chemical imidation can be performed by stirring the polyamic acid ester to be imidized in an organic solvent in the presence of a basic catalyst.
  • a basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Of these, triethylamine is preferred because it has sufficient basicity to allow the reaction to proceed.
  • the temperature during the imidation reaction is ⁇ 20 ° C. to 140 ° C., preferably 0 ° C. to 100 ° C., and the reaction time can be 1 to 100 hours.
  • the amount of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the amic acid ester group.
  • the imidation ratio of the resulting polymer can be controlled by adjusting the amount of catalyst, temperature, and reaction time. Since the added catalyst or the like remains in the solution after the imidation reaction, the obtained imidized polymer is recovered by the means described below, redissolved in an organic solvent, and the liquid crystal alignment according to the present invention. A treating agent is preferred.
  • Chemical imidation which adds a catalyst to the solution of the said polyamic acid obtained by reaction of a diamine component and tetracarboxylic dianhydride is simple.
  • Chemical imidization is preferable because the imidization reaction proceeds at a relatively low temperature and the molecular weight of the polymer is unlikely to decrease during the imidization process.
  • Chemical imidation can be performed by stirring a polymer to be imidized in an organic solvent in the presence of a basic catalyst and an acid anhydride.
  • an organic solvent the solvent used at the time of the polymerization reaction mentioned above can be used.
  • Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Of these, 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 temperature during the imidation reaction is ⁇ 20 ° C. to 140 ° C., preferably 0 ° C. to 100 ° C., and the reaction time can be 1 to 100 hours.
  • the amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times the amic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol times the amic acid group. Is double.
  • the imidation ratio of the resulting polymer can be controlled by adjusting the amount of catalyst, temperature, and reaction time.
  • the liquid crystal aligning agent of the present invention is preferable.
  • the polyimide solution obtained as described above can be polymerized by pouring into a poor solvent while stirring well. Precipitation is performed several times, and after washing with a poor solvent, a purified polyamic acid ester powder can be obtained at room temperature or by heating and drying.
  • the poor solvent is not particularly limited, and examples thereof include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, and benzene.
  • the molecular weight of the polyamic acid and polyimide used in the present invention is preferably 2,000 to 500,000, more preferably 5,000 to 300,000, and still more preferably in terms of weight average molecular weight (hereinafter also referred to as Mw). 10,000 to 100,000.
  • the number average molecular weight (hereinafter also referred to as Mn) is preferably 1,000 to 250,000, more preferably 2,500 to 150,000, and still more preferably 5,000 to 50,000.
  • the component (A) may be 1 to 15% by mass, preferably 1 to 8% by mass, more preferably 1.5 to 7% by mass when the total amount of the liquid crystal aligning agent is 100% by mass.
  • the component (B) is a compound having two or more epoxy groups.
  • a compound represented by the following formula (N-2) is preferable.
  • R 11 and R 12 each independently represents a linear or branched alkylene group having 1 to 10 carbon atoms or a cycloalkylene group having 3 to 10 carbon atoms.
  • the alkylene group and / or the cycloalkylene group may have at least one group selected from the group consisting of ethers and tertiary amines.
  • the alkylene group may be a saturated or unsaturated alkylene group.
  • R 11 and R 12 may be a linear alkylene group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, and a saturated linear alkylene group having 1 to 2 carbon atoms is particularly preferable.
  • R 13 and R 14 each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms.
  • the alkyl group may have at least one group selected from the group consisting of ethers and tertiary amines.
  • the alkyl group may be a saturated or unsaturated alkyl group.
  • R 13 and R 14 may be a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, preferably a hydrogen atom.
  • R 15 represents a z-valent aliphatic hydrocarbon group having 1 to 24 carbon atoms or a z-valent alicyclic hydrocarbon group having 3 to 24 carbon atoms. Any of a cycloalkane group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having 5 to 12 carbon atoms, (thio) ether, carbonyl, or tertiary amine between carbon-carbon bonds in the aliphatic hydrocarbon group May be inserted, and this aliphatic hydrocarbon group may have one group selected from epoxy and halogen.
  • Any of (thio) ether, carbonyl, and tertiary amine may be inserted between the carbon-carbon bonds in the alicyclic hydrocarbon group, and one of the single bonds that do not constitute a ring is the number of carbon atoms. May be substituted with 1 to 12 alkylene groups; z is an integer of 1 to 6, preferably 1 to 4.
  • Examples of the cycloalkane group having 3 to 12 carbon atoms of R 15 include groups in which z-1 hydrogen atoms have been removed from any of cyclopropane, cyclobutane, cyclopentane, cyclohexane, cyclohexene, norbornane, and adamantane.
  • the aromatic hydrocarbon group having 5 to 12 carbon atoms of R 15 is a group obtained by removing z-1 hydrogen atoms from any one of benzene, biphenyl, pyridine, pyrazine, naphthalene, furan, imidazole, oxazole, thiazole and furan. Can be mentioned.
  • R 15 is an alkylene group having 1 to 12 carbon atoms, such as methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group, dodecylene group, vinylene. Group, propenylene group, butenylene group, pentenylene group, ethynylene group, propynylene group and the like.
  • R 15 When z is 1 and R 15 is a monovalent aliphatic hydrocarbon group having 1 to 24 carbon atoms, R 15 may be an alkyl group having 1 to 24 carbon atoms, an alkenyl group having 2 to 24 carbon atoms, carbon Examples thereof include alkynyl groups of 2 to 24.
  • z is equal to or greater than 2, if R 15 is a divalent or higher valent aliphatic hydrocarbon group having 1 to 24 carbon atoms, as R 15, z aliphatic hydrocarbon group of the monovalent carbon atoms 1-24 -1 hydrogen atoms are removed to form a bond.
  • R 15 is a monovalent alicyclic hydrocarbon group having 3 to 24 carbon atoms, as R 15, a cycloalkyl group, a decahydronaphthyl group, a monovalent group such as an adamantyl group Can be mentioned.
  • R 15 is z-1 from the monovalent alicyclic hydrocarbon group having 3 to 24 carbon atoms. The hydrogen atom is removed to form a bond.
  • epoxy compounds represented by the following formulas (N-2-1) to (N-2-4) are preferable.
  • X represents a single bond, a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, or a hexamethylene group.
  • Y represents a methylene group, an ethylene group, a trimethylene group, a vinylene group, an oxy group, or a thio group.
  • Z represents a cyclopentanediyl group, a cyclohexanediyl group, or a norbornanediyl group.
  • Compounds represented by the formula (N-2) include the following formulas (N-3-1) to (N-3-4), 1,3-bis (diglycidylaminomethyl) cyclohexane, 1,4-bis ( Diglycidylaminomethyl) cyclohexane, 2,5-bis (diglycidylaminomethyl) norbornane, or 2,6-bis (diglycidylaminomethyl) norbornane is preferred.
  • the content of the component (B) is 1 to 30% by mass, preferably 2 to 20% by mass, more preferably 2 to 15% by mass with respect to 100% by mass of the component (A). More preferably, the content is 2 to 10% by mass.
  • the liquid crystal aligning agent used for this invention may contain arbitrarily components other than the above-mentioned (A) component and (B) component suitably.
  • a-22, a-13 to a-21, a-24, a-26, a-27, a-31, a-34, a-37, or a- 38 is preferable, and a-22 or a-37 is more preferable.
  • Examples of components other than the component (A) and the component (B) include crosslinkable compounds.
  • the crosslinkable compound has, for example, at least one substituent selected from the group consisting of a crosslinkable compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group, and a lower alkoxyalkyl group.
  • a crosslinkable compound or a crosslinkable compound having a polymerizable unsaturated bond can be included, but is not limited thereto. In addition, it is good to have 2 or more of these substituents and polymerizable unsaturated bonds in the crosslinkable compound.
  • crosslinkable compound having an epoxy group or an isocyanate group examples include bisphenolacetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, tetraglycidylaminodiphenylene, tetraphenylglycidyl ether ethane, triphenylglycidyl.
  • the crosslinkable compound having an oxetane group is a compound having at least two oxetane groups represented by the following formula [4A]. Specific examples include crosslinkable compounds represented by the formulas [4a] to [4k] published on pages 58 to 59 of International Publication No. WO2011 / 132751.
  • the crosslinkable compound having a cyclocarbonate group is a crosslinkable compound having at least two cyclocarbonate groups represented by the following formula [5A]. Specific examples include crosslinkable compounds represented by the formulas [5-1] to [5-42] described on pages 76 to 82 of WO2012 / 014898.
  • Examples of the crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxyl group include an amino resin having a hydroxyl group or an alkoxyl group, such as a melamine resin, a urea resin, a guanamine resin, and a glycoluril.
  • a melamine derivative, a benzoguanamine derivative, or glycoluril in which a hydrogen atom of an amino group is substituted with a methylol group, an alkoxymethyl group, or both can be used.
  • the melamine derivative or benzoguanamine derivative can exist as a dimer or a trimer. These preferably have an average of 3 to 6 methylol
  • Examples of the melamine derivative or benzoguanamine derivative include MX-750, which has an average of 3.7 substituted methoxymethyl groups per triazine ring, and an average of 5.8 methoxymethyl groups per triazine ring.
  • MX-750 which has an average of 3.7 substituted methoxymethyl groups per triazine ring, and an average of 5.8 methoxymethyl groups per triazine ring.
  • MW-30 manufactured by Sanwa Chemical Co., Ltd.
  • Methoxymethylated ethoxyme Benzomethylamine methoxymethyl butoxymethylated benzoguanamine such as Cymel 1123-10, butoxymethylated benzoguanamine such as Cymel 1128, carboxymethyl-containing methoxymethylated ethoxymethylated benzoguanamine such as Cymel 1125-80 Cyanamide).
  • glycoluril include butoxymethylated glycoluril such as Cymel 1170, methylolated glycoluril such as Cymel 1172, and methoxymethylolated glycoluril such as Powderlink 1174.
  • Examples of the benzene or phenolic compound having a hydroxyl group or an alkoxyl group include 1,3,5-tris (methoxymethyl) benzene, 1,2,4-tris (isopropoxymethyl) benzene, 1,4-bis ( sec-butoxymethyl) benzene or 2,6-dihydroxymethyl-p-tert-butylphenol. More specifically, the crosslinkable compounds of the formulas [6-1] to [6-48], which are listed on pages 62 to 66 of International Publication No. WO2011 / 132751.
  • crosslinkable compound having a polymerizable unsaturated bond examples include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and tri (meth) acryloyloxyethoxytrimethylol.
  • Crosslinkable compounds having three polymerizable unsaturated groups in the molecule such as propane or glycerin polyglycidyl ether poly (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (Meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol Rudi (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide bisphenol A type di (meth) acrylate, propylene oxide bisphenol type di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin Di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl
  • E 1 represents a group selected from the group consisting of a cyclohexane ring, a bicyclohexane ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, a fluorene ring, an anthracene ring or a phenanthrene ring
  • E 2 Represents a group selected from the following formula [7a] or [7b], and n represents an integer of 1 to 4.
  • crosslinkable compound used for the liquid crystal aligning agent of this invention may be 1 type, or may combine 2 or more types.
  • the content of the crosslinkable compound in the liquid crystal aligning agent of the present invention is preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of all polymer components.
  • the amount is preferably 0.1 to 100 parts by mass with respect to 100 parts by mass of the polymer component. More preferred is 1 to 50 parts by mass.
  • the liquid crystal aligning agent of this invention can use the compound which improves the uniformity of the film thickness of a liquid crystal aligning film at the time of apply
  • the compound that improves the film thickness uniformity and surface smoothness of the liquid crystal alignment film include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. Specific examples of these include surfactants described in paragraph [0117] of International Publication No. WO2016 / 047771.
  • F-top EF301, EF303, EF352 (above, manufactured by Tochem Products), MegaFuck F171, F173, R-30 (above, manufactured by Dainippon Ink, Inc.), Florard FC430, FC431 (or above) And Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (above, manufactured by Asahi Glass Co., Ltd.).
  • the amount of the surfactant used is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of all the polymer components contained in the liquid crystal aligning agent.
  • the liquid crystal aligning agent includes a compound represented by the formula [M1] described on pages 69 to 73 of International Publication No. WO2011 / 132751 as a compound that promotes charge transfer in the liquid crystal alignment film and promotes charge release of the device.
  • a nitrogen-containing heterocyclic amine compound represented by the formula [M156] can also be added.
  • the amine compound may be added directly to the liquid crystal aligning agent, but it is preferable to add the amine compound after forming a solution having a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass.
  • the solvent is not particularly limited as long as the specific polymer (A) is dissolved.
  • the liquid crystal aligning agent of the present invention includes, in addition to the above-mentioned poor solvent, crosslinkable compound, resin film or compound that improves the film thickness uniformity and surface smoothness of the liquid crystal aligning film, and a compound that promotes charge removal.
  • An imidization accelerator or the like for the purpose may be added.
  • the liquid crystal aligning agent of this application has the form of the solution containing the above-mentioned (A) component and (B) component.
  • the concentration of the polymer of the liquid crystal aligning agent used in the present invention can be appropriately changed by setting the thickness of the coating film to be formed, but it is 1% by mass or more from the viewpoint of forming a uniform and defect-free coating film. It is preferable to be 10% by mass or less from the viewpoint of storage stability of the solution.
  • the liquid crystal aligning agent of this application can change suitably solid content concentration (ratio which the total mass of components other than the solvent of a liquid crystal aligning agent accounts to the total mass of a liquid crystal aligning agent) by the setting of the thickness of the coating film to form.
  • solid content concentration ratio which the total mass of components other than the solvent of a liquid crystal aligning agent accounts to the total mass of a liquid crystal aligning agent
  • it is preferably 1% by mass or more from the viewpoint of forming a uniform and defect-free coating film, and is preferably 10% by mass or less from the viewpoint of storage stability of the solution.
  • the particularly preferable solid content concentration range varies depending on the method of applying the liquid crystal aligning agent to the substrate.
  • the concentration of the polymer is particularly preferably in the range of 1.5 to 4.5% by mass.
  • the solid content concentration is in the range of 3 to 9% by mass, and thereby the solution viscosity is in the range of 12 to 50 mPa ⁇ s.
  • the solid content concentration is in the range of 1 to 5% by mass, and thereby the solution viscosity is in the range of 3 to 15 mPa ⁇ s.
  • the polymer which is the component (A) of the present application has a molecular weight of preferably 2,000 to 500,000, more preferably 5,000 to 300,000, and still more preferably 10,000 to 100 in terms of Mw. 000. Further, Mn is preferably 1,000 to 250,000, more preferably 2,500 to 150,000, and still more preferably 5,000 to 50,000.
  • a liquid crystal alignment film formed using the liquid crystal aligning agent of the present invention is provided.
  • the step of applying the liquid crystal aligning agent of the present invention on a substrate to form a coating film, and the coating film is not in contact with the liquid crystal layer or the liquid crystal layer There is provided a method for producing a liquid crystal alignment film, comprising a step of irradiating the coating film with light in contact.
  • a liquid crystal light control device comprising the liquid crystal alignment film according to the present invention or the liquid crystal alignment film obtained by the production method of the present invention. Details are shown below.
  • liquid crystal alignment film and liquid crystal light control device By using the liquid crystal alignment agent, a liquid crystal alignment film can be produced.
  • the liquid crystal light control element which concerns on this invention comprises the liquid crystal aligning film formed using the said liquid crystal aligning agent.
  • the operation mode of the liquid crystal light control device according to the present invention is applied to various operation modes such as TN (Twisted Nematic) type, STN type, vertical alignment type (including VA-MVA type, VA-PVA type, etc.). be able to.
  • the liquid crystal light control device can be manufactured, for example, by steps including the following steps (1-1) to (1-3).
  • the liquid crystal aligning agent of this invention is apply
  • a TN-type, STN-type, or VA-type liquid crystal light control device first, as a pair of two substrates provided with a patterned transparent conductive film, on each transparent conductive film formation surface, The liquid crystal aligning agent prepared above is preferably applied by an offset printing method, a spin coating method, a roll coater method or an ink jet printing method, respectively.
  • the substrate for example, glass such as float glass or soda glass; a transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, poly (cycloaliphatic olefin) can be used.
  • a transparent conductive film provided on one surface of the substrate, a NESA film (registered trademark of US PPG) made of tin oxide (SnO 2 ), an ITO film made of indium oxide-tin oxide (In 2 O 3 -SnO 2 ), etc. Can be used.
  • a method of forming a pattern by photo-etching a method of using a mask having a desired pattern when forming a transparent conductive film; And so on.
  • a functional silane compound or a functional titanium compound is formed on the surface of the substrate surface on which the coating film is formed. It is also possible to perform a pretreatment to apply the above in advance.
  • preheating is preferably performed for the purpose of preventing dripping of the applied liquid crystal aligning agent.
  • the prebake temperature is preferably 30 to 200 ° C., more preferably 40 to 150 ° C., and particularly preferably 40 to 100 ° C.
  • the prebake time is preferably 0.25 to 10 minutes, more preferably 0.5 to 5 minutes.
  • a baking (post-baking) process is implemented for the purpose of removing a solvent completely and heat imidating the amic acid structure which exists in a polymer as needed.
  • the firing temperature (post-bake temperature) at this time is preferably 80 to 300 ° C., more preferably 120 to 250 ° C.
  • the post-bake time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes.
  • the thickness of the film thus formed is preferably 0.001 to 1 ⁇ m, more preferably 0.005 to 0.5 ⁇ m.
  • a treatment for imparting liquid crystal alignment ability to the coating film formed in the step (1-1) is performed.
  • the orientation ability of liquid crystal molecules is imparted to the coating film to form a liquid crystal orientation film.
  • the alignment ability imparting treatment include a rubbing treatment in which a coating film is rubbed in a fixed direction with a roll wound with a cloth made of fibers such as nylon, rayon, and cotton, and photo-alignment in which the coating film is irradiated with polarized or non-polarized radiation. Processing.
  • the coating film formed in the above step (1-1) can be used as it is as a liquid crystal alignment film. Good.
  • ultraviolet rays and visible rays including light having a wavelength of 150 to 800 nm can be used as the radiation applied to the coating film.
  • the radiation When the radiation is polarized light, it may be linearly polarized light or partially polarized light.
  • irradiation may be performed from a direction perpendicular to the substrate surface, an oblique direction, or a combination thereof.
  • the direction of irradiation is an oblique direction.
  • a light source to be used for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, or the like can be used.
  • Ultraviolet rays in a preferable wavelength region can be obtained by means of using a light source in combination with, for example, a filter or a diffraction grating.
  • the radiation dose is preferably 10 to 5,000 mJ / cm 2 , more preferably 30 to 2,000 mJ / cm 2 .
  • the temperature at the time of heating is usually 30 to 250 ° C, preferably 40 to 200 ° C, more preferably 50 to 150 ° C.
  • the light irradiation film obtained in the above step can be used as a liquid crystal alignment film as it is. Also good.
  • the firing temperature at this time is preferably 80 to 300 ° C, more preferably 120 to 250 ° C.
  • the firing time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes.
  • the photo-alignment process here corresponds to a light irradiation process in a state where it is not in contact with the liquid crystal layer.
  • the liquid crystal alignment film after the rubbing treatment is further subjected to a process for changing the pretilt angle of a part of the liquid crystal alignment film by irradiating a part of the liquid crystal alignment film with ultraviolet rays or a surface of the liquid crystal alignment film.
  • a resist film is formed on the part, and a rubbing process is performed in a direction different from the previous rubbing process, followed by a process of removing the resist film, so that the liquid crystal alignment film has different liquid crystal alignment capabilities for each region. . In this case, it is possible to improve the visual field characteristics of the obtained liquid crystal light control device.
  • Step (1-3): Construction of liquid crystal cell Two substrates on which the liquid crystal alignment film is formed as described above are prepared, and a liquid crystal cell is manufactured by disposing a liquid crystal between the two substrates disposed to face each other.
  • the first method is a conventionally known method. First, two substrates are arranged opposite to each other through a gap (cell gap) so that the respective liquid crystal alignment films are opposed to each other, and the peripheral portions of the two substrates are bonded together using a sealant, and the substrate surface and the sealant are bonded.
  • a liquid crystal cell is manufactured by injecting and filling the liquid crystal into the cell gap partitioned by the step of sealing the injection hole.
  • the second method is a method called an ODF (One Drop Fill) method.
  • ODF One Drop Fill
  • an ultraviolet light curable sealant is applied to a predetermined location on one of the two substrates on which the liquid crystal alignment film is formed, and liquid crystal is dropped to a predetermined location on the liquid crystal alignment film surface.
  • the other substrate is bonded so that the liquid crystal alignment films face each other and the liquid crystal is spread over the entire surface of the substrate, and then the entire surface of the substrate is irradiated with ultraviolet light to cure the sealant, thereby manufacturing a liquid crystal cell.
  • the liquid crystal cell produced as described above is further heated to a temperature at which the liquid crystal used takes an isotropic phase and then gradually cooled to room temperature. It is desirable to remove.
  • an epoxy resin containing a curing agent and aluminum oxide spheres as a spacer can be used.
  • the liquid crystal include nematic liquid crystal and smectic liquid crystal. Among them, nematic liquid crystal is preferable.
  • Schiff base, azoxy, biphenyl, phenylcyclohexane, ester, terphenyl, biphenylcyclohexane, pyrimidine, dioxane, bicyclooctane, cubane, and the like can be used.
  • cholesteric liquid crystals such as cholestyl chloride, cholesteryl nonate, and cholesteryl carbonate; chiral agents sold as “C-15” and “CB-15” (trade name, manufactured by Merck); Ferroelectric liquid crystals such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate may be added and used.
  • the guest-host type liquid crystal used in the present invention contains an anisotropic dye in addition to the above liquid crystal.
  • the term “dye” can mean a substance capable of intensively absorbing or deforming light in the visible light region, for example, at least partly or entirely within the 400 nm to 700 nm wavelength range.
  • the “isotropic dye” may mean a substance capable of anisotropic absorption of light in at least a part or the entire range of the visible light region. ⁇ ⁇ ⁇ ⁇
  • the color sensation of the liquid crystal cell can be adjusted through the use of the above dyes.
  • the kind of anisotropic dye is not particularly limited, and for example, a black dye or a color dye can be used.
  • the ratio of the anisotropic dye to the liquid crystal is appropriately selected within a range that does not impair the intended physical properties.
  • the anisotropic dye is included at a ratio of 0.01 to 5 parts by mass with respect to 100 parts by mass of the liquid crystal compound, but the above ratio can be changed to an appropriate range if necessary.
  • a liquid crystal light control element can be obtained by bonding a polarizing plate on the outer surface of the liquid crystal cell.
  • a polarizing plate to be bonded to the outer surface of the liquid crystal cell a polarizing film in which a polarizing film called “H film” in which iodine is absorbed while polyvinyl alcohol is stretched and oriented is sandwiched between cellulose acetate protective films, or H film
  • H film a polarizing film in which iodine is absorbed while polyvinyl alcohol is stretched and oriented
  • the liquid crystal aligning agent of the present invention even when a guest host type liquid crystal containing a host liquid crystal and a dichroic dye is used, the voltage holding ratio becomes a desired value, and the seal adhesion A liquid crystal alignment film having excellent properties and reliability can be obtained.
  • Mn and Mw of polyimide precursor and polyimide are measured using a normal temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko KK) and columns (KD-803, KD-805) (manufactured by Shodex). The measurement was performed as follows.
  • the imidation rate is determined by determining a proton derived from a structure that does not change before and after imidation as a reference proton, and the peak integrated value of this proton and the proton peak derived from the NH group of amic acid that appears near 9.5 to 10.0 ppm. It calculated
  • Imidization rate (%) (1 ⁇ ⁇ x / y) ⁇ 100
  • x is a proton peak integrated value derived from NH group of amic acid
  • y is a peak integrated value of reference proton
  • ⁇ is one NH group proton of amic acid in the case of polyamic acid (imidation rate is 0%) Is the number ratio of the reference proton to.
  • ⁇ Viscosity measurement> The viscosity of the polyamic acid solution or the like was adjusted to a temperature of 25 ° C. using a E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.) with a sample volume of 1.1 mL and cone rotor TE-1 (1 ° 34 ′, R24). Measured.
  • the liquid crystal alignment treatment agent is spin-coated on the ITO surface of the substrate with 30 mm ⁇ 40 mm ITO electrode, and subjected to a heat treatment at 60 ° C. for 5 minutes on a hot plate and at 220 ° C. for 30 minutes in a heat circulation clean oven, An ITO substrate with a polyimide liquid crystal alignment film having a thickness of 100 nm was obtained.
  • the coated surface of the ITO substrate was rubbed using a rayon cloth with a rubbing apparatus having a roll diameter of 120 mm under the conditions of a roll rotation speed of 1000 rpm, a roll traveling speed of 50 mm / sec, and an indentation amount of 0.2 mm.
  • Liquid crystal prepared by mixing 0.4% by mass of a dye compound represented by the following formula with 100% by mass of MLC-6608 (manufactured by Merck Japan) into this empty cell by vacuum injection method. After injecting, the injection port was sealed to obtain a liquid crystal cell.
  • the liquid crystal alignment treatment agent is filtered through a filter having a pore size of 1.0 ⁇ m, spin-coated on a glass substrate with a transparent electrode, dried on a hot plate at 60 ° C. for 1 minute, and baked at 120 ° C. for 5 minutes to have a film thickness of 100 nm. Coating film was obtained. Two substrates thus obtained were prepared, and 4 ⁇ m diameter bead spacers (manufactured by JGC Catalysts & Chemicals Co., Ltd., true ball, SW-D1) were sprayed on the liquid crystal alignment film surface of one of the substrates. UV) curable adhesive was added dropwise.
  • a sample for evaluation of adhesiveness was prepared by irradiating 1.0 J of UV with a wavelength of 365 nm using a cut filter with a wavelength of 325 nm or less. Furthermore, it was heat-cured at 120 ° C. for 1 hour to prepare a sample for evaluating adhesiveness, and a sample irradiated with UV was compared with a sample subjected to both UV and thermosetting.
  • liquid crystal aligning agents obtained in Examples and Comparative Examples were filtered under pressure with a membrane filter having a pore size of 1 ⁇ m.
  • a liquid crystal aligning agent was applied on a 100 ⁇ 100 mm ITO film-attached PET film substrate (vertical: 100 mm, horizontal: 100 mm, thickness: 50 ⁇ m), and after heat treatment at 120 ° C. for 5 minutes on a hot plate, 100 Cut out to a size of ⁇ 20 mm, two ITO substrates with a liquid crystal alignment film with a film thickness of 100 nm were produced.
  • a bead spacer with a spacer diameter of 30 um is applied to one of the substrates, and a sealing agent (723K1 manufactured by Kyoritsu Chemical Co., Ltd.) is printed on the liquid crystal alignment film of the other substrate, and these substrates are laminated to overlap each other. It was. At that time, the amount of the sealant was adjusted so that the area of the sealant after bonding was 50 ⁇ 10 mm in width. After the two bonded substrates were fixed with a clip, ultraviolet light was irradiated at 3 J / cm 2 , and then heat cured at 120 ° C. for 1 hour to prepare a test sample substrate for this evaluation.
  • test sample substrate was fixed with the desktop precision universal testing machine (AGS-X 500N) (manufactured by Shimadzu Corporation), and the stress (N / 10 mm), that is, peel strength (N / 10 mm) was measured. Evaluation shows that the larger the value of the peel strength (N / 10 mm), the better the adhesion with the sealing agent and the base substrate).
  • Table 5 and Table 6 show the peel strength (N / 10 mm) values as evaluation results of the peel test.
  • PAA-1 polyamic acid solution having a resin solid content concentration of 20.0% by mass.
  • the viscosity of this polyamic acid solution was 660.1 mPa ⁇ s.
  • Mn of this polyamic acid was 12,426 and Mw was 41,548.
  • Example 1 GBL (10.0 g) and 38.5 g of PGME were added to the polyimide powder (PI-1) (1.50 g) obtained in Synthesis Example 6, and dissolved by stirring for 24 hours at room temperature. To this solution, 0.45 g of a mixed solution containing 10% by mass of TETRAD-C was added with stirring, and then stirred at room temperature for 2 hours to obtain a liquid crystal alignment agent (AL-1).
  • the liquid crystal alignment film obtained from the liquid crystal aligning agent of the example of the present invention contains a dye as compared with the liquid crystal alignment film obtained from the liquid crystal aligning agent of the comparative example.
  • the voltage holding ratio after 72 hours at 60 ° C. was high, the adhesion with the sealing material was good by curing by UV irradiation, and the curing by heat curing after UV irradiation was also good.
  • Comparative Example 2 not containing a specific amine compound, a specific amine compound and a specific additive has a low voltage holding ratio, poor adhesion with a sealant due to curing by UV irradiation, and poor curing by heat curing after UV irradiation. Met.
  • the adhesion with the sealing material and the film are cured by performing the thermosetting after the UV irradiation. While breakage between the materials was observed and was good, in the comparative example not containing the specific additive, breakage was observed at the boundary between the ITO and the organic film, which was poor.
  • Examples 3 and 4 and Comparative Example 1 are compared with Comparative Examples 2, 3 and 4.
  • liquid crystal aligning agent of the present invention By using the liquid crystal aligning agent of the present invention, it is possible to obtain a liquid crystal aligning film having excellent voltage holding ratio with respect to the liquid crystal containing the dye and excellent adhesion to the sealing agent even after undergoing a low temperature baking process.
  • the liquid crystal light control device using the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention can be suitably used for light control devices in various liquid crystal modes. These elements are also useful in liquid crystal displays for display purposes, and also in light control windows and optical shutters for controlling transmission and blocking of light.

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Nonlinear Science (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Mathematical Physics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Liquid Crystal (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
PCT/JP2019/017917 2018-04-27 2019-04-26 液晶調光素子 WO2019208765A1 (ja)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN201980028621.1A CN112041739B (zh) 2018-04-27 2019-04-26 液晶调光元件
KR1020207030480A KR20210005015A (ko) 2018-04-27 2019-04-26 액정 조광 소자
JP2020515600A JP7355007B2 (ja) 2018-04-27 2019-04-26 ゲストホスト型液晶調光素子用の液晶配向剤
JP2023142490A JP7548390B2 (ja) 2018-04-27 2023-09-01 液晶調光素子

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018086640 2018-04-27
JP2018-086640 2018-04-27

Publications (1)

Publication Number Publication Date
WO2019208765A1 true WO2019208765A1 (ja) 2019-10-31

Family

ID=68294115

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/017917 WO2019208765A1 (ja) 2018-04-27 2019-04-26 液晶調光素子

Country Status (5)

Country Link
JP (2) JP7355007B2 (zh)
KR (1) KR20210005015A (zh)
CN (1) CN112041739B (zh)
TW (1) TWI838370B (zh)
WO (1) WO2019208765A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024166693A1 (ja) * 2023-02-08 2024-08-15 日産化学株式会社 液晶配向剤、液晶配向膜、液晶表示素子、化合物、及び重合体

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011237755A (ja) * 2009-09-18 2011-11-24 Jnc Corp 液晶配向剤、液晶配向膜、液晶配向膜の製造方法および液晶表示素子
CN106978195A (zh) * 2015-11-17 2017-07-25 奇美实业股份有限公司 液晶配向膜、液晶显示组件以及其制造方法
WO2017146216A1 (ja) * 2016-02-26 2017-08-31 日産化学工業株式会社 液晶表示素子

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0940964A (ja) 1995-07-28 1997-02-10 Toshiba Corp 液晶表示素子
WO2008114846A1 (ja) 2007-03-19 2008-09-25 Jsr Corporation 液晶配向剤および液晶表示素子
JP5454754B2 (ja) * 2007-07-23 2014-03-26 Ｊｓｒ株式会社 液晶配向剤、液晶配向膜および液晶表示素子
JP6213281B2 (ja) * 2013-03-19 2017-10-18 Jnc株式会社 感光性ジアミン、液晶配向剤および液晶表示素子
JP6183674B2 (ja) 2013-07-12 2017-08-23 エルジー・ケム・リミテッド 液晶セル
KR20150118527A (ko) * 2014-04-14 2015-10-22 제이엔씨 주식회사 액정 배향제, 액정 배향막 및 액정 표시 소자
JP6421545B2 (ja) * 2014-10-21 2018-11-14 Jnc株式会社 ポリアミック酸またはその誘導体を含む液晶配向剤、液晶配向膜および液晶表示素子
JP2017021097A (ja) 2015-07-08 2017-01-26 大日本印刷株式会社 調光フィルム
KR102350408B1 (ko) * 2016-03-29 2022-01-11 닛산 가가쿠 가부시키가이샤 액정 배향제, 액정 배향막, 및 액정 표시 소자

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011237755A (ja) * 2009-09-18 2011-11-24 Jnc Corp 液晶配向剤、液晶配向膜、液晶配向膜の製造方法および液晶表示素子
CN106978195A (zh) * 2015-11-17 2017-07-25 奇美实业股份有限公司 液晶配向膜、液晶显示组件以及其制造方法
WO2017146216A1 (ja) * 2016-02-26 2017-08-31 日産化学工業株式会社 液晶表示素子

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024166693A1 (ja) * 2023-02-08 2024-08-15 日産化学株式会社 液晶配向剤、液晶配向膜、液晶表示素子、化合物、及び重合体

Also Published As

Publication number Publication date
TWI838370B (zh) 2024-04-11
JP7355007B2 (ja) 2023-10-03
JP7548390B2 (ja) 2024-09-10
JPWO2019208765A1 (ja) 2021-05-20
TW201945527A (zh) 2019-12-01
KR20210005015A (ko) 2021-01-13
JP2023166498A (ja) 2023-11-21
CN112041739B (zh) 2024-06-11
CN112041739A (zh) 2020-12-04

Similar Documents

Publication Publication Date Title
JP6460341B2 (ja) 液晶表示素子および液晶表示素子の製造方法
WO2014133042A1 (ja) 重合体、液晶配向処理剤、液晶配向膜および液晶表示素子
JP2011158835A (ja) 液晶配向剤
JP7548390B2 (ja) 液晶調光素子
WO2020162462A1 (ja) 液晶配向剤、液晶配向膜及びそれを用いた液晶表示素子
TW201827579A (zh) 液晶配向劑、液晶配向膜、液晶元件及聚合體
JP7298156B2 (ja) 液晶配向剤、液晶配向膜、及び液晶表示素子
JP7632576B2 (ja) 液晶配向剤、液晶配向膜、液晶表示素子及びジアミン
JP4666137B2 (ja) 液晶配向膜の形成方法、液晶表示素子および光学部材
WO2021005888A1 (ja) 液晶配向剤、液晶配向膜及び液晶素子
KR102548025B1 (ko) 액정 배향제, 액정 배향막, 및 액정 표시 소자
JP7052355B2 (ja) 液晶表示素子、液晶光学素子及び液晶構造体安定化膜用組成物
JP7001063B2 (ja) 液晶配向剤、液晶配向膜、及び液晶表示素子
TWI711671B (zh) 液晶配向劑、液晶配向膜、液晶元件、以及液晶配向膜及液晶元件的製造方法
WO2019176276A1 (ja) 液晶配向剤、液晶配向膜及び液晶素子
KR102534902B1 (ko) 액정 배향제, 액정 배향막, 및 액정 표시 소자
JP2024009757A (ja) 液晶配向剤及びその製造方法、液晶配向膜、並びに液晶素子
JP2024164805A (ja) 液晶配向剤、液晶配向膜及び液晶素子

Legal Events

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

Ref document number: 19792404

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2020515600

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19792404

Country of ref document: EP

Kind code of ref document: A1