WO2019106952A1 - Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément à cristaux liquides - Google Patents

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

Info

Publication number
WO2019106952A1
WO2019106952A1 PCT/JP2018/037081 JP2018037081W WO2019106952A1 WO 2019106952 A1 WO2019106952 A1 WO 2019106952A1 JP 2018037081 W JP2018037081 W JP 2018037081W WO 2019106952 A1 WO2019106952 A1 WO 2019106952A1
Authority
WO
WIPO (PCT)
Prior art keywords
liquid crystal
group
solvent
carbon atoms
aligning agent
Prior art date
Application number
PCT/JP2018/037081
Other languages
English (en)
Japanese (ja)
Inventor
哲 平野
幸志 樫下
Original Assignee
Jsr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 Jsr株式会社 filed Critical Jsr株式会社
Priority to JP2019557039A priority Critical patent/JP6897791B2/ja
Priority to CN201880062309.XA priority patent/CN111164501B/zh
Priority to KR1020207009464A priority patent/KR102341987B1/ko
Publication of WO2019106952A1 publication Critical patent/WO2019106952A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
    • C08G73/1032—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous characterised by the solvent(s) used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723—Polyimide, polyamide-imide

Definitions

  • the present disclosure relates to a liquid crystal aligning agent, a liquid crystal aligning film, and a liquid crystal element.
  • Liquid crystal elements are used in various applications including display devices such as televisions, personal computers, and smartphones. These liquid crystal elements have a liquid crystal alignment film having a function of aligning liquid crystal molecules in a predetermined direction.
  • the liquid crystal alignment film is generally formed on a substrate by applying a liquid crystal alignment agent in which a polymer component is dissolved in an organic solvent onto the substrate, and preferably by heating.
  • a liquid crystal alignment agent in which a polymer component is dissolved in an organic solvent onto the substrate, and preferably by heating.
  • polyamic acids and soluble polyimides are widely used because they are excellent in mechanical strength, liquid crystal alignment property, and affinity with liquid crystals.
  • a solvent having high solubility in a polymer such as polyamic acid or soluble polyimide for example, a good solvent such as N-methyl-2-pyrrolidone or ⁇ -butyrolactone
  • a mixed solvent with a solvent having high spreadability eg, poor solvent such as butyl cellosolve is generally used (see, for example, Patent Documents 1 and 2).
  • volatilization of the solvent from above the printing machine can be suppressed at the time of printing of the liquid crystal alignment agent on the substrate, and even when printing is performed continuously, it is heavy on the printing machine It is required that coalescence does not easily precipitate, that is, good continuous printability.
  • the present disclosure has been made in view of the above problems, and is a liquid crystal which has good coatability and continuous printability with respect to a fine concavo-convex structure, is less susceptible to temperature unevenness at the time of film formation, and has good afterimage characteristics. It aims at providing a liquid crystal aligning agent which can obtain a display element.
  • the present inventors have intensively studied to solve the above problems, and found that the above problems can be solved by using a specific lactone or lactam as a solvent component of a liquid crystal aligning agent. Specifically, the present disclosure adopts the following means in order to solve the problems.
  • a polymer component and a solvent component wherein the solvent component is at least one selected from the group consisting of 5-membered ring lactones, 6-membered ring lactones and 7-membered ring lactams, and having 2 carbon atoms
  • the liquid crystal aligning agent is at least one selected from the group consisting of carbon-carbon double bonds forming part of a ring [A ], The liquid crystal aligning agent.
  • the liquid crystal aligning agent of the present disclosure has good wettability and spreadability even when applied to a substrate surface having a fine uneven structure, and can form a liquid crystal alignment film uniformly on the substrate surface. Moreover, when printing is continuously performed in a manufacturing process, it can be made hard to precipitate a polymer on a printer. In addition, the liquid crystal aligning agent of the present disclosure is not susceptible to temperature unevenness at the time of film formation heating, and thus it is possible to obtain a liquid crystal alignment film in which characteristic variation due to temperature unevenness is suppressed. An excellent liquid crystal display element can be obtained.
  • FIG. 1 is a view showing a schematic configuration of an ITO electrode substrate for evaluation.
  • A is a top view
  • (b) is a sectional view which expanded a part.
  • the liquid crystal aligning agent is a liquid polymer composition which contains a polymer component and a solvent component, and the polymer component is dissolved in the solvent component.
  • the main skeleton of the polymer component contained in the liquid crystal aligning agent is not particularly limited.
  • polyamic acid, polyamic acid ester, polyimide, polyorganosiloxane, polyester, polyamide, polyamide imide, polybenzoxazole precursor, polybenzo Main skeletons such as oxazole, cellulose derivative, polyacetal, styrene-maleimide copolymer, poly (meth) acrylate and the like can be mentioned.
  • (meth) acrylate is meant to include acrylate and methacrylate.
  • polymer [P It is preferable to include] At least one polymer selected from the group consisting of polyamic acid, polyamic acid ester and polyimide among the above.
  • the polyamic acid can be obtained by reacting tetracarboxylic acid dianhydride with a diamine compound.
  • tetracarboxylic acid dianhydride examples include aliphatic tetracarboxylic acid dianhydrides, alicyclic tetracarboxylic acid dianhydrides, and aromatic tetracarboxylic acid dianhydrides. .
  • aliphatic tetracarboxylic acid dianhydride for example, 1,2,3,4-butanetetracarboxylic acid dianhydride etc .
  • alicyclic tetracarboxylic acid dianhydrides include 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 2,3,5-Tricarboxycyclopentylacetic acid dianhydride, 5- (2,5-dioxotetrahydrofuran-3-yl) -3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1 , 3-dione, 5- (2,5-dioxotetrahydrofuran-3-yl) -8-methyl-3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1,3-
  • Diamine compound As a diamine compound used for the synthesis
  • combination of a polyamic acid, an aliphatic diamine, an alicyclic diamine, aromatic diamine, a diamino organosiloxane etc. can be mentioned, for example.
  • these diamines include, as aliphatic diamines, for example, metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine and the like; as alicyclic diamines, for example, 1,4 -Diaminocyclohexane, 4,4'- methylenebis (cyclohexylamine) and the like;
  • an aromatic diamine for example, dodecanoxy-2,4-diaminobenzene, pentadecanoxy-2,4-diaminobenzene, hexadecanoxy-2,4-diaminobenzene, octadecanoxy-2,4-diaminobenzene, pentadecanoxy-2,5-diamino Benzene, octadecanoxy-2,5-diaminobenzene, cholestanyloxy-3,5-diamin
  • side chain type diamines such as diamines having a cinnamic acid structure in the side chain:
  • a polyamic acid can be obtained by reacting the above-described tetracarboxylic acid dianhydride and a diamine compound, as necessary, together with a molecular weight modifier.
  • the use ratio of the tetracarboxylic acid dianhydride and the diamine compound to be subjected to the synthesis reaction of the polyamic acid is such that the acid anhydride group of the tetracarboxylic acid dianhydride is 0.2 with respect to 1 equivalent of the amino group of the diamine compound. A ratio of ⁇ 2 equivalents is preferred.
  • the molecular weight modifier examples include acid monoanhydrides such as maleic anhydride, phthalic anhydride and itaconic anhydride, monoamine compounds such as aniline, cyclohexylamine and n-butylamine, and monoisocyanate compounds such as phenyl isocyanate and naphthyl isocyanate. It can be mentioned.
  • the use ratio of the molecular weight modifier is preferably 20 parts by mass or less with respect to 100 parts by mass in total of the tetracarboxylic acid dianhydride used and the diamine compound.
  • the synthesis reaction of polyamic acid is preferably carried out in an organic solvent.
  • the reaction temperature at this time is preferably -20 ° C to 150 ° C, and the reaction time is preferably 0.1 to 24 hours.
  • the organic solvent used for the reaction include aprotic polar solvents, phenolic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons and the like.
  • organic solvents are N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, ⁇ -butyrolactone, tetramethylurea, hexamethylphosphortriamide, m-cresol, xylenol And using one or more selected from the group consisting of and halogenated phenols as a solvent, or using a mixture of one or more of these and another organic solvent (eg, butyl cellosolve, diethylene glycol diethyl ether, etc.) preferable.
  • organic solvent eg, butyl cellosolve, diethylene glycol diethyl ether, etc.
  • the amount (a) of the organic solvent used is such that the total amount (b) of the tetracarboxylic acid dianhydride and the diamine is 0.1 to 50% by mass with respect to the total amount (a + b) of the reaction solution. Is preferred.
  • a reaction solution in which the polyamic acid is dissolved is obtained. This reaction solution may be used as it is for preparation of a liquid crystal aligning agent, or may be used for preparation of a liquid crystal aligning agent after the polyamic acid contained in the reaction solution is isolated.
  • the polyamic acid ester is, for example, [I] a method of reacting a polyamic acid obtained by the above synthesis reaction with an esterifying agent, [II] tetracarboxylic acid diester These compounds can be obtained by a method of reacting a diamine compound with a diamine compound, a method of reacting a [III] tetracarboxylic acid diester dihalide with a diamine compound, or the like.
  • the polyamic acid ester to be contained in the liquid crystal aligning agent may have only an amic acid ester structure, or may be a partially esterified product in which an amic acid structure and an amic acid ester structure coexist.
  • the reaction solution obtained by dissolving the polyamic acid ester may be used as it is for preparation of a liquid crystal aligning agent, or the polyamic acid ester contained in the reaction solution may be isolated and then provided for preparation of a liquid crystal aligning agent. Good.
  • the polyimide can be obtained, for example, by dehydration ring closure and imidization of the polyamic acid synthesized as described above.
  • the polyimide may be a completely imidized product obtained by dehydrating and ring closing all of the amic acid structure of the precursor polyamic acid, and only a part of the amic acid structure may be dehydrating and ring closing, and the amic acid structure and the imide. It may be a partial imidate coexisting with a ring structure.
  • the polyimide used for the reaction preferably has an imidation ratio of 20 to 99%, more preferably 30 to 96%.
  • the imidation ratio is a percentage representing the ratio of the number of imide ring structures to the total number of amic acid structures of polyimide and the number of imide ring structures.
  • part of the imide ring may be an isoimide ring.
  • the dehydration ring closure of the polyamic acid is preferably carried out by dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration ring closure catalyst to this solution, and heating as necessary.
  • a dehydrating agent for example, an acid anhydride such as acetic anhydride, propionic anhydride, trifluoroacetic anhydride and the like can be used.
  • the amount of the dehydrating agent used is preferably 0.01 to 20 moles relative to 1 mole of the polyamic acid's amic acid structure.
  • the dehydration ring closure catalyst for example, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used.
  • the amount of the dehydrating ring-closing catalyst used is preferably 0.01 to 10 moles relative to 1 mole of the dehydrating agent used.
  • an organic solvent used for a dehydration ring-closing reaction the organic solvent illustrated as what is used for the synthesis
  • the reaction temperature of the dehydration ring closure reaction is preferably 0 to 180 ° C.
  • the reaction time is preferably 1.0 to 120 hours.
  • a reaction solution containing a polyimide is obtained. This reaction solution may be used as it is for preparation of a liquid crystal aligning agent, or may be used for preparing a liquid crystal aligning agent after isolating the polyimide.
  • Polyimides can also be obtained by imidization of polyamic acid esters.
  • the polyamic acid, polyamic acid ester and polyimide obtained as described above preferably have a solution viscosity of 10 to 800 mPa ⁇ s when this is made into a solution with a concentration of 10% by mass, preferably 15 to 500 mPa. More preferably, it has a solution viscosity of s.
  • the solution viscosity (mPa ⁇ s) of the polyamic acid, polyamic acid ester and polyimide is 10% by mass of a solution prepared using a good solvent of these polymers (eg, ⁇ -butyrolactone, N-methyl-2-pyrrolidone, etc.)
  • the polymer solution of the above was a value measured at 25.degree. C. using an E-type rotational viscometer.
  • the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of polyamic acid, polyamic acid ester and polyimide is preferably 1,000 to 500,000, and more preferably 2,000 to 500 It is 300,000.
  • the molecular weight distribution (Mw / Mn) represented by the ratio of Mw to the polystyrene-equivalent number average molecular weight (Mn) measured by GPC is preferably 15 or less, more preferably 10 or less.
  • the content ratio of the polymer [P] (in the case of containing two or more, the total amount thereof) is the total amount of the polymer components contained in the liquid crystal aligning agent from the viewpoint of making the quality of the liquid crystal element obtained better.
  • the content is preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably 50% by mass or more.
  • the liquid crystal aligning agent of the present disclosure is at least one member selected from the group consisting of 5-membered ring lactones, 6-membered ring lactones and 7-membered ring lactams as at least a part of the solvent component, and an alkyl having 2 to 10 carbon atoms.
  • an alkoxy group having 2 to 10 carbon atoms an alkoxyalkyl group having 2 to 10 carbon atoms, an alkoxyalkoxyalkyl group having 2 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, a group “—COR 12 ” (wherein , R 12 is an alkyl group having 1 to 3 carbon atoms) and at least one partial structure selected from the group consisting of carbon-carbon double bonds forming part of a ring (hereinafter also referred to as “specific partial structure”) Containing a solvent [A].
  • the solvent [A] has a structure in which one hydrogen atom bonded to the ring of a specific cyclic ester ( ⁇ -butyrolactone, ⁇ -valerolactone or ⁇ -caprolactam) is substituted with a group consisting of a chain structure, or a specific It has a structure in which one ethylene group constituting the ring of the cyclic ester is substituted by a group having a carbon-carbon double bond.
  • the coatability (printability) of the liquid crystal aligning agent to the substrate surface which has an electrode structure of fine concavo-convex shape can be improved.
  • the boiling point of the solvent component of the liquid crystal aligning agent can be adjusted to an appropriate height, and the influence of temperature unevenness can be made less at the time of film formation.
  • the solvent [A] is preferably an alkyl group having 2 to 10 carbon atoms, an alkoxy group having 2 to 10 carbon atoms, or an alkoxyalkyl group having 2 to 10 carbon atoms in the ring part of ⁇ -butyrolactone or ⁇ -valerolactone.
  • R 13 -OR 14 alkoxyalkoxyalkyl group (-R 13 -OR 15 -OR 14 2 to 10 carbon atoms), a compound having an alkoxyalkoxy group having 2 to 10 carbon atoms (-OR 13 -OR 14) ( a-1) a compound (a-2) in which one ethylene group constituting the ring of substituted or unsubstituted ⁇ -butyrolactone is replaced with a carbon-carbon double bond, and a nitrogen in the ring of ⁇ -caprolactam It is a compound (a-3) in which "-COR 12 " is bonded to an atom.
  • R 13 represents an alkanediyl group
  • R 14 represents an alkyl group
  • R 15 represents an alkanediyl group
  • R 1 represents an alkyl group having 2 to 10 carbon atoms, an alkoxy group having 2 to 10 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, an alkoxyalkoxyalkyl group having 2 to 10 carbon atoms or It is a C2-C10 alkoxy alkoxy group, n is 1 or 2.
  • R 2 is a divalent group represented by the following formula (4-1) or formula (4-2).
  • R 4 to R 11 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • “* 1” represents an oxygen atom Indicates that it is a bond with
  • R 3 is an alkyl group having 1 to 3 carbon atoms.
  • R 1 may be linear or branched.
  • R 1 include, as an alkyl group, for example, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group, 3-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group etc.
  • each of the substituted alkyl groups is an oxygen atom or the like as an alkoxyalkyl group, for example, a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, a propoxymethyl group, a propoxyethyl group, a butoxyethyl group etc .;
  • an alkoxy alkoxy alkyl group of -10 for example, methoxy methoxymethyl group, ethoxy methoxy group
  • an alkoxy alkoxy group for example, a methoxy ethoxy group, an ethoxy ethoxy group, an ethoxy propoxy group, a propoxy propoxy group etc. can be mentioned as an alkoxy alkoxy group.
  • R 1 is preferably linear, more preferably a linear alkyl group having 3 or more carbon atoms, still more preferably a linear alkyl group having 3 to 8 carbon atoms, and having 5 to 8 carbon atoms Particularly preferred is a linear alkyl group of R 1 may be bonded to any position of the ⁇ -butyrolactone ring or the ⁇ -valerolactone ring, but is preferably bonded to the position ⁇ to the oxygen atom in the ring.
  • the alkyl group of R 4 to R 11 in the above formulas (4-1) and (4-2) may be linear or branched and, for example, a methyl group, an ethyl group, n And -propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl and the like.
  • R 8 to R 11 is preferably an alkyl group, and the alkyl group is bonded to the alpha position to the oxygen atom in the ring More preferable.
  • R 4 and R 8 be a methyl group or an ethyl group
  • R 5 to R 7 and R 9 to R 11 be a hydrogen atom.
  • Specific examples of the compound represented by the above formula (2) include ⁇ -angelica lactone, ⁇ -angelica lactone and the like.
  • the compound represented by the said Formula (2) can be used individually by 1 type or in combination of 2 or more types.
  • R 3 may be linear or branched, and examples thereof include a methyl group, an ethyl group, an n-propyl group and an isopropyl group.
  • R 3 is preferably a methyl group or an ethyl group, more preferably a methyl group.
  • Specific examples of the compound represented by the above formula (3) include, for example, N-acetyl- ⁇ -caprolactam, N-propionyl- ⁇ -caprolactam and the like. Preferably, it is N-acetyl- ⁇ -caprolactam.
  • the compound represented by the said Formula (3) can be used individually by 1 type or in combination of 2 or more types.
  • the solvent [A] preferably has a substituent at the ring portion of the cyclic ester in that the coating property on the substrate surface having a fine uneven electrode structure can be made better, More preferred is at least one selected from the group consisting of a compound represented by the formula (1) and a compound represented by the above formula (2).
  • the solvent component is at least one selected from the group consisting of alcohol solvents, chain ester solvents, ether solvents and ketone solvents together with the solvent [A] in that the wettability of the liquid crystal aligning agent can be further enhanced. It is preferable to further include a solvent which is different from the solvent [A] (hereinafter, also referred to as “solvent [B]”).
  • solvent [B] examples include alcohol solvents such as methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, diacetone alcohol, and the like.
  • chain ester solvents include ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxy propionate, diethyl oxalate, diethyl malonate, isoamyl propionate, Isoamyl isobutyrate etc;
  • ether solvents for example, diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol i-propyl ether, ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl Ether acetate, diethylene glycol dimethyl ether, di
  • the solvent [B] is preferably at least one selected from the group consisting of alcohol solvents, chain ester solvents and ether solvents, from the viewpoint of a higher effect of improving the coating properties, and ethylene, ethylene Glycol monobutyl ether (butyl cellosolve), diacetone alcohol, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and one selected from the group consisting of 3-methoxy-1-butanol It is more preferable that
  • 1 type can be used individually or in combination of 2 or more types.
  • solvent component secures the solubility of the polymer in the solvent component, and for the purpose of suppressing the reduction in product yield caused by the precipitation of the polymer in the coating step, together with the solvent [A], the boiling point at 1 atmospheric pressure is 200 ° C. or higher It is preferable to further include a solvent different from the solvent [A] (hereinafter, also referred to as “solvent [C]”).
  • the solvent [C] is preferably at least one selected from the group consisting of aprotic polar solvents and phenols, and is more preferably aprotic polar solvents.
  • aprotic polar solvents from N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, gamma butyrolactone, propylene carbonate and a compound represented by the following formula (5)
  • Particularly preferred is at least one selected from the group consisting of (In the formula (5), R 21 and R 22 are each independently a hydrogen atom, or a monovalent hydrocarbon group which has carbon atoms 1 be ⁇ 6 have an ether bond, R 21 and R 22 may combine with each other to form a ring, and R 23 is an alkyl group having 1 to 4 carbon atoms.
  • examples of the monovalent hydrocarbon group having 1 to 6 carbon atoms as R 21 and R 22 include, for example, a chain hydrocarbon group having 1 to 6 carbon atoms, and an alicyclic having 3 to 6 carbon atoms.
  • a hydrocarbon group, an aromatic hydrocarbon group having 5 or 6 carbon atoms and the like can be mentioned.
  • the monovalent group having an ether bond includes, for example, an alkoxyalkyl group having 2 to 6 carbon atoms.
  • the ring R 21, R 22 is bonded to R 21 and R 22 are formed together with the nitrogen atom bonded with each other, such as pyrrolidine ring, and a nitrogen-containing heterocyclic ring such as a piperidine ring.
  • a monovalent chain hydrocarbon group such as a methyl group may be bonded to these nitrogen-containing heterocycles.
  • R 21 and R 22 are preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, still more preferably a hydrogen atom or a methyl group .
  • the alkyl group having 1 to 4 carbon atoms of R 23 may be linear or branched.
  • R 23 is preferably a methyl group or an ethyl group.
  • the compound represented by the above formula (5) include, for example, 3-butoxy-N, N-dimethylpropanamide, 3-methoxy-N, N-dimethylpropanamide, 3-hexyloxy-N, N- Dimethylpropanamide, isopropoxy-N-isopropyl-propionamide, n-butoxy-N-isopropyl-propionamide and the like.
  • the compound represented by the said Formula (5) can be used individually by 1 type or in combination of 2 or more types.
  • the content rate of solvent [A] is 10 mass% or more with respect to the whole quantity of the solvent component contained in a liquid crystal aligning agent among solvent components.
  • the content ratio of the solvent [A] is more preferably 10 to 85% by mass, and still more preferably 15 to 15%, since the balance between the solubility of the polymer component and the wettability of the liquid crystal aligning agent can be improved. It is 75% by mass, particularly preferably 15 to 60% by mass.
  • the content ratio of the solvent [B] is preferably 10 to 80% by mass with respect to the total amount of the solvent component contained in the liquid crystal aligning agent, in that the wettability of the liquid crystal aligning agent can be further enhanced. It is more preferable to set it to 70% by mass, and it is further preferable to set it to 20 to 50% by mass.
  • the content ratio of the solvent [C] is preferably 70% by mass or less in order to lower the heating temperature at the time of film formation.
  • the content ratio of the solvent [C] is more preferably 1 to 70% by mass with respect to the total amount of the solvent component contained in the liquid crystal aligning agent It is more preferably 5 to 65% by mass, and particularly preferably 10 to 60% by mass.
  • the liquid crystal aligning agent may contain only the solvent [A] as a solvent component, but the solvent component consists of the solvent [A] and the solvent [B], or the solvent [A] and the solvent [B] and the solvent It is particularly preferable to consist of [C].
  • the solvent component consists of the solvent [A] and the solvent [B]” and “the solvent component is composed of the solvent [A], the solvent [B] and the solvent [C]” It is acceptable to contain solvents [B] and other solvents other than the solvent [C] to such an extent that they do not interfere with the effects of the present invention.
  • other solvents include halogenated hydrocarbon solvents, hydrocarbon solvents and the like.
  • halogenated hydrocarbon solvents such as dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene and the like; hydrocarbon solvents such as hexane, heptane and octane , Benzene, toluene, xylene and the like can be mentioned respectively.
  • the content ratio of the other solvent is preferably 1% by mass or less, more preferably 0.5% by mass or less, and more preferably 0.2% by mass or less based on the total amount of the solvent component in the liquid crystal aligning agent. It is further preferred that
  • the liquid crystal aligning agent contains a polymer component and a solvent component, but may contain other components as needed.
  • examples of such other components include epoxy group-containing compounds (for example, N, N, N ', N'- tetraglycidyl-m-xylene diamine, N, N, N', N'- tetraglycidyl-4, 4 Functional amino compounds (eg, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, etc.), antioxidants, metal chelate compounds, curing A catalyst, a hardening accelerator, surfactant, a filler, a dispersing agent, a photosensitizer, etc. are mentioned.
  • the blend ratio of the other components can be appropriately selected according to each compound as long as the effects of the present disclosure are not impaired.
  • the solid content concentration in the liquid crystal aligning agent (the ratio of the total mass of components other than the solvent of the liquid crystal aligning agent to the total mass of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, etc. It is in the range of 1 to 10% by mass.
  • the solid content concentration is less than 1% by mass, the film thickness of the coating film becomes too small, and it becomes difficult to obtain a good liquid crystal alignment film.
  • the solid content concentration exceeds 10% by mass, the film thickness of the coating film becomes too large to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent increases and the coatability decreases. There is a tendency.
  • the liquid crystal element of the present disclosure includes a liquid crystal alignment film formed using the liquid crystal alignment agent described above.
  • Liquid crystal elements can be effectively applied to various applications. For example, clocks, portable games, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, mobile phones, smartphones, various monitors, liquid crystal televisions It can be used as various display devices such as information display, light control film, retardation film and the like.
  • the operation mode of the liquid crystal is not particularly limited.
  • TN type For example, TN type, STN type, vertical alignment type (including VA-MVA type, VA-PVA type, etc.), IPS type, FFS type, OCB
  • IPS type For example, TN type, STN type, vertical alignment type (including VA-MVA type, VA-PVA type, etc.), IPS type, FFS type, OCB
  • OCB Optically Compensated Bend
  • a method of manufacturing a liquid crystal element will be described by taking a liquid crystal display element as an example.
  • the liquid crystal display element can be manufactured, for example, by a method including the following steps 1 to 3.
  • Step 1 differs in the substrate used according to the desired operation mode.
  • Steps 2 and 3 are common to each operation mode.
  • a liquid crystal aligning agent is applied on a substrate, and preferably a coated surface is formed to form a coating film on the substrate.
  • the substrate for example, glass such as float glass and soda glass; transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate and poly (alicyclic olefin) can be used.
  • a transparent conductive film provided on one side of the substrate an NESA film (registered trademark of PPG, USA) 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 TN type, STN type or VA type liquid crystal element two substrates provided with a patterned transparent conductive film are used.
  • a substrate provided with an electrode made of a transparent conductive film or a metal film patterned in a comb shape, and a counter substrate not provided with an electrode Use
  • a film made of a metal such as chromium can be used as the metal film.
  • the application of the liquid crystal aligning agent to the substrate is preferably performed by an offset printing method, a spin coating method, a roll coater method, a flexographic printing method, or an ink jet printing method on the electrode formation surface.
  • preheating is preferably performed for the purpose of preventing dripping of the applied liquid crystal alignment agent.
  • the prebake temperature is preferably 30 to 200 ° C., and the prebake time is preferably 0.25 to 10 minutes.
  • a baking (post-baking) step is carried out to completely remove the solvent and, if necessary, thermally imidize the amic acid structure present in the polymer.
  • the baking temperature (post-baking temperature) at this time is preferably 80 to 300 ° C., and the post-baking time is preferably 5 to 200 minutes.
  • the film thickness of the film thus formed is preferably 0.001 to 1 ⁇ m.
  • Step 2 orientation treatment
  • a treatment for imparting liquid crystal alignment ability to the coating film formed in the above step 1 is carried out.
  • the alignment ability of the liquid crystal molecules is imparted to the coating film to form a liquid crystal alignment film.
  • rubbing treatment is performed by rubbing the coating film in a fixed direction with a roll wound with a cloth made of fibers such as nylon, rayon and cotton, or light irradiation to the coating film formed on the substrate using a liquid crystal alignment agent.
  • the optical alignment processing etc. which carry out and provide liquid crystal aligning ability to a coating film are mentioned.
  • the coating film formed in the above step 1 can be used as it is as a liquid crystal alignment film, but the coating film may be subjected to alignment treatment.
  • the liquid crystal aligning agent suitable for a liquid crystal display element of a vertical alignment type can also be used suitably also for a liquid crystal display element of a PSA (Polymer sustained alignment) type.
  • Step 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 is disposed between two substrates disposed opposite to each other to manufacture a liquid crystal cell.
  • a liquid crystal cell for example, (1) two substrates are disposed opposite to each other with a spacer between them so that the liquid crystal alignment film faces each other, and peripheral portions of the two substrates are sealed using a sealing agent.
  • Liquid crystal is injected and filled into a cell gap separated by a substrate surface and a sealing agent, and then the injection hole is sealed, (2) a seal is made at a predetermined place on one substrate on which a liquid crystal alignment film is formed.
  • Liquid crystal is applied onto the surface of the liquid crystal alignment film, and then the other substrate is bonded so that the liquid crystal alignment film faces each other and the liquid crystal is spread over the entire surface of the substrate (ODF method Etc.).
  • the liquid crystal cell produced is preferably further heated to a temperature at which the liquid crystal used has an isotropic phase, and then gradually cooled to room temperature to remove the flow alignment at the time of liquid crystal filling.
  • an epoxy resin containing a hardening agent and aluminum oxide spheres as a spacer can be used as a spacer.
  • a photo spacer, a bead spacer, etc. can be used as a spacer.
  • liquid crystals include nematic liquid crystals and smectic liquid crystals, among which nematic liquid crystals are preferred.
  • cholesteric liquid crystals, chiral agents, ferroelectric liquid crystals, etc. may be added to nematic liquid crystals or smectic liquid crystals, for example.
  • a polarizing plate is attached to the outer surface of the liquid crystal cell as required.
  • the polarizing plate include a polarizing plate called a “H film” obtained by absorbing iodine while stretching and orienting polyvinyl alcohol, sandwiched by a cellulose acetate protective film, or a polarizing plate consisting of the H film itself.
  • a liquid crystal display element is obtained.
  • the weight average molecular weight Mw of the polymer, the imidation ratio of the polyimide in the polymer solution, the solution viscosity of the polymer solution, and the epoxy equivalent were measured by the following methods.
  • the necessary amounts of the raw material compounds and the polymers used in the following examples were secured by repeating the synthesis on the synthesis scale shown in the following synthesis examples as necessary.
  • the weight average molecular weight Mw is a polystyrene conversion value measured by GPC under the following conditions.
  • Imidation rate of polyimide The solution of the polyimide was poured into pure water, and the obtained precipitate was sufficiently dried under reduced pressure at room temperature, then dissolved in deuterated dimethyl sulfoxide, and 1 H-NMR was measured at room temperature using tetramethylsilane as a reference substance.
  • the imidation ratio [%] was determined from the obtained 1 H-NMR spectrum by the following formula (1).
  • Imidation ratio [%] (1 ⁇ (A 1 / (A 2 ⁇ ⁇ ))) ⁇ 100 (1)
  • a 1 is a proton-derived peak area of an NH group appearing in the vicinity of a chemical shift of 10 ppm
  • a 2 is a peak area derived from other protons
  • ⁇ is a precursor of a polymer (polyamic acid It is the number ratio of other protons to one proton of NH group in).
  • Solution viscosity of polymer solution The solution viscosity (mPa ⁇ s) of the polymer solution was measured at 25 ° C. using an E-type rotational viscometer. [Epoxy equivalent] The epoxy equivalent was measured by the hydrochloric acid-methyl ethyl ketone method described in JIS C 2105.
  • Synthesis of Polyimide (PI-1) 22.4 g (0.1 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride (TCA) as tetracarboxylic acid dianhydride, 8.6 g (0.08 mol) of p-phenylenediamine (PDA) as diamine ) And 10.5 g (0.02 mol) of cholestanyl 3,5-diaminobenzoate (HCDA) are dissolved in 166 g of N-methyl-2-pyrrolidone (NMP) and reacted at 60 ° C.
  • TCA 2,3,5-tricarboxycyclopentylacetic acid dianhydride
  • PDA p-phenylenediamine
  • HCDA cholestanyl 3,5-diaminobenzoate
  • the solvent in the system is solvent-substituted with fresh NMP (pyridine and acetic anhydride used for dehydration ring closure reaction are removed out of the system by this operation.
  • NMP pyridine and acetic anhydride used for dehydration ring closure reaction are removed out of the system by this operation.
  • the imidization rate is about 68.
  • a solution containing 26% by weight of polyimide (PI-1) was obtained. A small amount of the obtained polyimide solution was taken, NMP was added, and the solution viscosity measured as a solution having a polyimide concentration of 10% by mass was 45 mPa ⁇ s.
  • the reaction solution was then poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40 ° C. for 15 hours to obtain polyimide (PI-1).
  • Synthesis Example 2 Synthesis of Polyimide (PI-2) 110 g (0.50 mol) of TCA and 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) naphtho as tetracarboxylic acid dianhydride 160 g (0.50 mol) of [1,2-c] furan-1,3-dione, 91 g (0.85 mol) of PDA as a diamine, 25 g of 1,3-bis (3-aminopropyl) tetramethyldisiloxane 0.10 mol) and 25 g (0.040 mol) of 3,6-bis (4-aminobenzoyloxy) cholestane and 1.4 g (0.015 mol) of aniline as a monoamine are dissolved in 960 g of NMP at 60 ° C.
  • the reaction was carried out for 6 hours to obtain a solution containing polyamic acid.
  • a small amount of the obtained polyamic acid solution was fractionated, NMP was added, and the solution viscosity measured as a solution of 10 mass% of polyamic acid concentration was 60 mPa ⁇ s.
  • 2,700 g of NMP was added to the obtained polyamic acid solution, 390 g of pyridine and 410 g of acetic anhydride were added, and dehydration ring closure reaction was carried out at 110 ° C. for 4 hours.
  • Synthesis Example 3 Synthesis of Polyimide (PI-3) The above-mentioned Synthesis Example 1 and Example 2 were changed except that the diamine used was changed to 0.08 moles of 3,5-diaminobenzoic acid (3,5DAB) and 0.02 moles of cholestanyloxy-2,4-diaminobenzene (HCODA).
  • a polyamic acid solution was obtained by the same method. A small amount of the obtained polyamic acid solution was fractionated, NMP was added, and the solution viscosity measured as a solution of 10 mass% of polyamic acid concentration was 80 mPa ⁇ s.
  • Synthesis Example 4 Synthesis of Polyimide (PI-4) The above-mentioned Synthesis Example 1 was repeated except that the diamine used was changed to 0.06 mol of 4,4'-diaminodiphenylmethane, 0.02 mol of compound (DA-1) and 0.02 mol of compound (DA-2). A polyamic acid solution was obtained by the same method. A small amount of the obtained polyamic acid solution was fractionated, NMP was added, and the solution viscosity measured as a solution of 10 mass% of polyamic acid concentration was 60 mPa ⁇ s.
  • Synthesis Example 5 Synthesis of Polyimide (PI-5) While changing the tetracarboxylic acid dianhydride used to 0.08 moles of 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride and 0.02 moles of pyromellitic dianhydride, the diamine used is Other than 0.098 mol of 4-aminophenyl 4-aminobenzoate (compound represented by the above formula (DA-6)) and 0.002 mol of 3,6-bis (4-aminobenzoyloxy) cholestane A polyamic acid solution was obtained in the same manner as in Synthesis Example 1 above.
  • a small amount of the obtained polyamic acid solution was fractionated, NMP was added, and the solution viscosity measured as a solution of 10 mass% of polyamic acid concentration was 80 mPa ⁇ s.
  • imidization was performed by the same method as in Synthesis Example 1 to obtain a solution containing 26% by mass of polyimide (PI-5) having an imidization rate of about 75%.
  • a small amount of the obtained polyimide solution was taken, NMP was added, and the solution viscosity measured as a solution having a polyimide concentration of 10% by mass was 41 mPa ⁇ s.
  • the reaction solution was then poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried at 40 ° C. under reduced pressure for 15 hours to obtain polyimide (PI-5).
  • Synthesis Example 6 Synthesis of Polyamic Acid (PA-1) 200 g (1.0 mol) of 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride (CB) as tetracarboxylic acid dianhydride, 210 g of 2,2'-dimethyl-4,4'-diaminobiphenyl as diamine (1.0 mol) was dissolved in a mixed solvent of NMP 370 g and GBL 3, 300 g and reacted at 40 ° C. for 3 hours to obtain a polyamic acid solution having a solid concentration of 10 mass% and a solution viscosity of 160 mPa ⁇ s. The polyamic acid solution was then poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried at 40 ° C. under reduced pressure for 15 hours to obtain polyamic acid (PA-1).
  • PA-1 Polyamic Acid
  • Synthesis Example 7 Synthesis of Polyamic Acid (PA-2) 7.0 g (0.031 mol) of TCA as tetracarboxylic acid dianhydride, 13 g of a compound (DA-5) (corresponding to 1 mol per 1 mol of TCA) as a diamine are dissolved in 80 g of NMP and 4 at 60 ° C. By performing the reaction for time, a solution containing 20% by mass of polyamic acid (PA-3) was obtained. The solution viscosity of this polyamic acid solution was 2,000 mPa ⁇ s.
  • Compound (DA-5) was synthesized according to the description in JP-A-2011-100099. The polyamic acid solution was then poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried at 40 ° C. under reduced pressure for 15 hours to obtain polyamic acid (PA-2).
  • Synthesis Example 8 Synthesis of Polyamic Acid (PA-3) Polyamic acid solution in the same manner as in Synthesis Example 6 except that the diamine used was changed to 0.7 mol of 1,3-bis (4-aminophenethyl) urea and 0.3 mol of compound (DA-2) I got A small amount of the obtained polyamic acid solution was fractionated, NMP was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by mass was 70 mPa ⁇ s. The polyamic acid solution was then poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried at 40 ° C. under reduced pressure for 15 hours to obtain polyamic acid (PA-3).
  • PA-3 Polyamic acid
  • Synthesis Example 10 Synthesis of Polyamic Acid (PA-5) Except that the diamine used was changed to 0.2 mol of 2,4-diamino-N, N-diallylaniline, 0.2 mol of 4,4'-diaminodiphenylamine and 0.6 mol of 4,4'-diaminodiphenylmethane A polyamic acid solution was obtained in the same manner as in Synthesis Example 6 above. A small amount of the obtained polyamic acid solution was fractionated, NMP was added, and the solution viscosity measured as a solution of 10 mass% of polyamic acid concentration was 95 mPa ⁇ s. The polyamic acid solution was then poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40 ° C. for 15 hours to obtain polyamic acid (PA-5).
  • PA-5 Polyamic acid
  • the weight average molecular weight Mw of the obtained polyamic acid ester (PAE-1) was 34,000.
  • Synthesis Example 12 Synthesis of Polyorganosiloxane (APS-1) In a reaction vessel equipped with a stirrer, thermometer, dropping funnel and reflux condenser, 100.0 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (ECETS), 500 g of methyl isobutyl ketone and 10.0 g of triethylamine Charge and mix at room temperature. Next, 100 g of deionized water was added dropwise over 30 minutes from the dropping funnel, and then reaction was performed at 80 ° C. for 6 hours while stirring under reflux.
  • EETS 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane
  • EPS-1 reactive polyorganosiloxane
  • EPS-1 was obtained as a viscous transparent liquid.
  • the weight average molecular weight Mw of the obtained reactive polyorganosiloxane was 3,500, and the epoxy equivalent was 180 g / mol.
  • Example 1 Preparation of Liquid Crystal Alignment Agent
  • ⁇ HL ⁇ -heptanolactone
  • NMP N-methyl-2-pyrrolidone
  • BC butyl cellosolve
  • the solution was sufficiently stirred and then filtered through a filter with a pore size of 1 ⁇ m to prepare a liquid crystal aligning agent (S-1).
  • the liquid crystal aligning agent (S-1) is mainly for the production of a vertical alignment type liquid crystal display element.
  • the liquid crystal aligning agent (S-1) is dispensed (one-way) on the anilox roll at one-minute intervals, and each time, the operation (hereinafter referred to as idle operation) of bringing the anilox roll and printing plate into contact It did (it does not print on a glass substrate during this time).
  • This idle operation is an operation carried out to intentionally carry out the printing of the liquid crystal alignment agent under severe conditions.
  • main printing was subsequently performed using a glass substrate. In this printing, after idle operation, five substrates are loaded at intervals of 30 seconds, each substrate after printing is heated (prebaked) at 80 ° C. for 1 minute to remove the solvent, and then heated at 200 ° C.
  • the printability was evaluated by observing the coating film with a microscope with a magnification of 20 times. In the evaluation, continuous printability “good ( ⁇ )” is observed when precipitation of the polymer is not observed from the first printing after idling, while precipitation of the polymer is observed at the first printing after idling. Continuous printability is "Available ( ⁇ )” when precipitation of the polymer is not observed during 5 times of actual printing, and continuous precipitation is observed when precipitation of the polymer is observed even after repeating 5 times of actual printing. Printability was "bad (x)".
  • the liquid crystal aligning agent (S-1) prepared in the above was dropped to evaluate the easiness of the substrate to the uneven surface.
  • the coating property of the liquid crystal aligning agent on the fine uneven surface is better, the larger the wetting and spreading of the droplets (specifically, the larger the wetting spread area S (mm 2 / ⁇ L) of the droplets with respect to the liquid amount). You can say that.
  • the liquid crystal aligning agent (S-1) prepared in the above was treated with a liquid crystal alignment film printing machine (Nippon Photo Printing Co., Ltd.), a glass substrate with a transparent electrode having a fine slit ITO electrode structure, and a patterned ITO electrode structure. It apply
  • pre-baking on an 80 ° C. hot plate for 1 minute to remove the solvent
  • Each coated substrate was subjected to ultrasonic cleaning for 1 minute in ultrapure water and then dried in a clean oven at 100 ° C. for 10 minutes. Thus, a pair of substrates (two sheets) having a liquid crystal alignment film was obtained. Next, an aluminum oxide sphere-containing epoxy resin adhesive having a diameter of 5.5 ⁇ m is applied to the outer edge of the surface having the liquid crystal alignment film, and then a pair of substrates are superposed and pressure bonded so that the liquid crystal alignment film faces each other. The agent was allowed to cure.
  • nematic liquid crystal (MLC-6608, manufactured by Merck & Co., Ltd.) was filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photo-curing adhesive to manufacture a liquid crystal cell. Further, a liquid crystal cell was manufactured by the same method as described above except that the post-baking temperature was changed from 180 ° C. to 120 ° C. or 230 ° C., respectively. The obtained liquid crystal cell is as described in 6. below. Used in the evaluation of
  • the measurement of the pretilt angle is based on the method described in Non-patent document (T. J. Scheffer et. Al. J. Appl. Phys. Vo. 19, p. 2013 (1980)), He-Ne laser light
  • the value of the inclination angle of the liquid crystal molecules from the substrate surface measured by the crystal rotation method using the above was taken as the pretilt angle [°].
  • the evaluation is “good ( ⁇ )” when ⁇ is 0.2 ° or less, “good ( ⁇ )” when it is greater than 0.2 ° and less than 0.5 °, 0.5 °
  • the case where it is above was made into “defect (x).”
  • the post-baking margin was evaluated as “good” and when it was 120 ° C., it was evaluated as “good”.
  • the AC residual image characteristic is “good ( ⁇ )”, and when it is 2% or more and less than 3%, “good ( ⁇ )”, 3% or more It evaluated as “defect (x).” As a result, it was an evaluation of "good” in this example.
  • Examples 2 to 10 and Comparative Examples 1 to 8 Liquid crystal aligning agents (S-2 to S-10, SR-1 to SR-8) in the same manner as in Example 1 except that the type and blending amount of the polymer, and the solvent composition were as described in Table 1 below, respectively. Were prepared. Further, various evaluations were performed in the same manner as in Example 1 using the prepared liquid crystal aligning agent. The evaluation results are shown in Tables 2 and 3 below.
  • Example 11 Preparation of Liquid Crystal Alignment Agent A liquid crystal alignment agent (S-11) was prepared in the same manner as in Example 1 except that the polymer components and the solvent composition were changed as described in Table 1 below.
  • the liquid crystal aligning agent (S-11) is mainly for the production of a horizontal alignment type liquid crystal display element. 2. Evaluation of Liquid Crystal Alignment Agent The surface asperity, the continuous printability, and the coating property on the fine asperity surface were evaluated in the same manner as in Example 1 except that the liquid crystal alignment agent (S-11) was used. The results are shown in Table 2 below.
  • the coating film surface was rubbed at a roll rotational speed of 400 rpm, a stage moving speed of 3 cm / sec, and a hair-foot push-in length of 0.1 mm by a rubbing machine having a roll wound with rayon cloth. Then, ultrasonic cleaning was performed in ultrapure water for 1 minute, and then dried in a clean oven at 100 ° C. for 10 minutes to obtain a substrate having a liquid crystal alignment film. Next, a pair of substrates having a liquid crystal alignment film is screen-printed with an epoxy resin adhesive containing an aluminum oxide sphere having a diameter of 5.5 ⁇ m, leaving a liquid crystal injection port on the edge of the surface on which the liquid crystal alignment film is formed.
  • Example 12 and 13 Liquid crystal aligning agents (S-12) and (S-13) were respectively prepared in the same manner as in Example 1 except that the polymer component and the solvent composition were changed as described in Table 1 below. Moreover, while evaluating the surface asperity, continuous printability, and coating property on fine asperity surface in the same manner as in Example 1 except that the liquid crystal aligning agents (S-12) and (S-13) were used, respectively, In the same manner as in Example 11, a rubbing FFS type liquid crystal cell was manufactured and various evaluations were performed. The results are shown in Table 2 below.
  • Example 14 Preparation of Liquid Crystal Alignment Agent A liquid crystal alignment agent (S-14) was prepared in the same manner as in Example 1 except that the polymer components and the solvent composition were changed as described in Table 1 below.
  • the liquid crystal aligning agent (S-14) is mainly for the production of a PSA type liquid crystal display element. 2. Evaluation of Liquid Crystal Alignment Agent The surface asperity, the continuous printability, and the coating property on the fine asperity surface were evaluated in the same manner as in Example 1 except that the liquid crystal alignment agent (S-14) was used. The results are shown in Table 2 below.
  • liquid crystal compound represented by the following formula (L1-1) was represented by 5% by mass with respect to 10 g of nematic liquid crystal (MLC-6608 manufactured by Merck Ltd.), and by the following formula (L2-1)
  • the liquid crystal composition LC1 was obtained by adding 0.3 mass% of the photopolymerizable compounds and mixing them.
  • a liquid crystal alignment film printing machine (Nippon Photography printing (A) was carried out on each electrode surface of two glass substrates each having a conductive film consisting of an ITO electrode and the liquid crystal alignment agent (S-14) prepared above. (Pre-baking) on a hot plate at 80 ° C. for 2 minutes to remove the solvent, and then heating (post-baking) on a hot plate at 150 ° C. for 10 minutes to obtain an average film. A coating of 0.06 ⁇ m in thickness was formed. The coated films were subjected to ultrasonic cleaning in ultrapure water for 1 minute and then dried in a clean oven at 100 ° C. for 10 minutes to obtain a pair (two sheets) of substrates having a liquid crystal alignment film.
  • the pattern of the used electrode is the same pattern as the electrode pattern in the PSA mode.
  • an aluminum oxide sphere-containing epoxy resin adhesive having a diameter of 5.5 ⁇ m is applied to the outer edge of the surface of the one of the pair of substrates having the liquid crystal alignment film, and then the liquid crystal alignment film faces one another. It was pressure-bonded together and the adhesive was cured.
  • the liquid crystal composition LC1 prepared above was filled between a pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photo-curing adhesive to manufacture a liquid crystal cell.
  • Examples 15 to 17, 27, 28 Liquid crystal aligning agents were prepared in the same manner as in Example 1 except that the polymer component and the solvent composition were changed as described in Table 1 below. Moreover, while evaluating surface asperity, continuous printability, and coating property on fine asperity surface in the same manner as in Example 1 except that each liquid crystal aligning agent was used, in the same manner as in Example 14, a PSA type liquid crystal cell was obtained. It manufactured and performed various evaluations. The results are shown in Tables 2 and 3 below.
  • Example 18 Preparation of Liquid Crystal Alignment Agent A liquid crystal alignment agent (S-18) was prepared in the same manner as in Example 1 except that the polymer components and the solvent composition were changed as described in Table 1 below.
  • the liquid crystal aligning agent (S-18) is mainly for the production of a liquid crystal display element of the light vertical alignment type.
  • the surface asperity, the continuous printability, and the coating property on the fine asperity surface were evaluated in the same manner as in Example 1 except that the liquid crystal alignment agent (S-18) was used. The results are shown in Table 2 below.
  • the liquid crystal aligning agent (S-18) prepared above is applied on a transparent electrode surface of a glass substrate with a transparent electrode made of an ITO film using a spinner, and a hot plate at 80 ° C. Pre-baked for 1 minute. Thereafter, the inside of the chamber was heated at 230 ° C. for 1 hour in an oven purged with nitrogen to form a coating having a thickness of 0.1 ⁇ m.
  • this coated film surface is irradiated with polarized ultraviolet light of 1,000 J / m 2 containing an emission line of 313 nm from a direction inclined 40 ° from the substrate normal to obtain liquid crystal alignment ability. Granted. The same operation was repeated to form a pair (two sheets) of substrates having a liquid crystal alignment film.
  • An epoxy resin adhesive containing aluminum oxide spheres having a diameter of 3.5 ⁇ m is applied by screen printing to the outer periphery of the surface having a liquid crystal alignment film of one of the above substrates, and then the liquid crystal alignment film surfaces of a pair of substrates are made to face each other.
  • Example 19 and 20 Liquid crystal aligning agents were prepared in the same manner as in Example 1 except that the polymer component and the solvent composition were changed as described in Table 1 below. Moreover, while evaluating surface asperity, continuous printability, and coating property on fine asperity surface in the same manner as in Example 1 except that each liquid crystal aligning agent was used, optical vertical alignment liquid crystal as in Example 18 The cell was manufactured and various evaluations were performed. The results are shown in Table 2 below.
  • Example 21 Preparation of Liquid Crystal Alignment Agent A liquid crystal alignment agent (S-21) was prepared in the same manner as in Example 1 except that the polymer components and the solvent composition were changed as described in Table 1 below.
  • the liquid crystal aligning agent (S-21) is mainly for producing a light horizontal alignment type liquid crystal display element. 2. Evaluation of Liquid Crystal Alignment Agent The surface asperity, the continuous printability, and the coating property on the fine asperity surface were evaluated in the same manner as in Example 1 except that the liquid crystal alignment agent (S-21) was used. The results are shown in Table 2 below.
  • the coating film surface is irradiated with ultraviolet light of 1,000 J / m 2 including a linearly polarized light emission line of 254 nm from the normal direction of the substrate using an Hg-Xe lamp to perform photoalignment treatment, and liquid crystal alignment on the substrate A film was formed.
  • a pair of substrates having a liquid crystal alignment film is screen-printed with an epoxy resin adhesive containing an aluminum oxide sphere having a diameter of 5.5 ⁇ m, leaving a liquid crystal injection port at the edge of the surface on which the liquid crystal alignment film is formed.
  • the substrates were superposed and pressure-bonded so that the projection directions of the polarization axes on the substrate surface at this time were antiparallel, and the adhesive was thermally cured at 150 ° C. for 1 hour.
  • nematic liquid crystal manufactured by Merck, MLC-7028
  • nematic liquid crystal manufactured by Merck, MLC-7028
  • this was heated at 120 ° C. and then gradually cooled to room temperature to manufacture a liquid crystal cell.
  • the postbake margin, the AC afterimage characteristics and the DC afterimage characteristics were evaluated in the same manner as in Example 1 except that the light horizontal alignment type liquid crystal cell obtained in 1. above was used. The results are shown in Table 2 below.
  • Example 22 to 26 Liquid crystal aligning agents were prepared in the same manner as in Example 1 except that the polymer component and the solvent composition were changed as described in Table 1 below. Moreover, while evaluating surface asperity, continuous printability, and coating property on fine asperity surface in the same manner as in Example 1 except that each liquid crystal aligning agent was used, in the same manner as in Example 21, a light horizontal alignment type liquid crystal The cell was manufactured and various evaluations were performed. The results are shown in Table 2 below.
  • Example 29 Preparation of Liquid Crystal Alignment Agent A liquid crystal alignment agent (S-29) was prepared in the same manner as in Example 1 except that the polymer components and the solvent composition were changed as described in Table 1 below.
  • the liquid crystal aligning agent (S-29) is mainly for the production of a TN mode liquid crystal display element. 2. Evaluation of Liquid Crystal Alignment Agent The surface asperity, the continuous printability, and the coating property on the fine asperity surface were evaluated in the same manner as in Example 1 except that the liquid crystal alignment agent (S-29) was used. The results are shown in Table 3 below.
  • the liquid crystal aligning agent (S-29) prepared in the above was applied using a spinner, and prebaked for 1 minute on a hot plate at 80.degree. Thereafter, the inside of the chamber was heated at 230 ° C. for 1 hour in an oven purged with nitrogen to form a coating having a thickness of 0.1 ⁇ m.
  • the coating film was rubbed at a roll rotational speed of 400 rpm, a stage moving speed of 3 cm / sec, and a hair-foot push-in length of 0.1 mm by a rubbing machine having a roll wound with rayon cloth.
  • ultrasonic cleaning was performed in ultrapure water for 1 minute, and then dried in a clean oven at 100 ° C. for 10 minutes to obtain a substrate having a liquid crystal alignment film.
  • a pair (two sheets) of substrates having a liquid crystal alignment film was formed.
  • An epoxy resin adhesive containing aluminum oxide spheres with a diameter of 3.5 ⁇ m is applied by screen printing to the outer periphery of the surface of one of the above substrates having a liquid crystal alignment film, and then the liquid crystal alignment film surfaces are superimposed to face each other. It was pressure-bonded together and the adhesive was cured.
  • nematic liquid crystal manufactured by Merck, MLC-6221
  • MLC-62211 was filled between a pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photo-curing adhesive.
  • the postbake margin, the AC afterimage characteristics and the DC afterimage characteristics were evaluated in the same manner as in Example 1 except that the TN type liquid crystal cell obtained in 1. above was used. The results are shown in Table 3 below.
  • the numerical value of a polymer component shows the compounding ratio (mass part) of each polymer with respect to a total of 100 mass parts of the polymer component used for preparation of a liquid crystal aligning agent.
  • the numerical value of the solvent composition indicates the blending ratio (parts by mass) of each solvent to 100 parts by mass in total of the solvent components used for the preparation of the liquid crystal aligning agent.
  • Abbreviations of the compounds are as follows.

Landscapes

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

Abstract

L'agent d'alignement de cristaux liquides de l'invention comprend un composant polymère et un composant solvant. Le composant solvant consiste en au moins un élément choisi dans un groupe constitué d'une lactone cyclique à cinq membres, d'une lactone cyclique à six membres et d'un lactame cyclique à sept membres, et contient un solvant [A] qui possède au moins une sorte de sous-structure choisie dans un groupe constitué d'un groupe alkyle de 2 à 10 atomes de carbone, d'un groupe alcoxy de 2 à 10 atomes de carbone, d'un groupe alcoxyalkyle de 2 à 10 atomes de carbone, d'un groupe alcoxyalcoxyalkyle de 2 à 10 atomes de carbone, d'un groupe alcoxyalcoxy de 2 à 10 atomes de carbone, d'un groupe 「－ＣＯＲ１２」 (Ｒ１２ représente un groupe alkyle de 1 à 3 atomes de carbone.), et d'une double liaison carbone-carbone formant une partie d'un cycle.
PCT/JP2018/037081 2017-11-30 2018-10-03 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément à cristaux liquides WO2019106952A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2019557039A JP6897791B2 (ja) 2017-11-30 2018-10-03 液晶配向剤、液晶配向膜及び液晶素子
CN201880062309.XA CN111164501B (zh) 2017-11-30 2018-10-03 液晶取向剂、液晶元件的制造方法、液晶取向膜及液晶元件
KR1020207009464A KR102341987B1 (ko) 2017-11-30 2018-10-03 액정 배향제, 액정 배향막, 그리고 액정 소자 및 그의 제조 방법

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017229974 2017-11-30
JP2017-229974 2017-11-30

Publications (1)

Publication Number Publication Date
WO2019106952A1 true WO2019106952A1 (fr) 2019-06-06

Family

ID=66664914

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/037081 WO2019106952A1 (fr) 2017-11-30 2018-10-03 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément à cristaux liquides

Country Status (5)

Country Link
JP (1) JP6897791B2 (fr)
KR (1) KR102341987B1 (fr)
CN (1) CN111164501B (fr)
TW (1) TWI786195B (fr)
WO (1) WO2019106952A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022176713A1 (fr) * 2021-02-16 2022-08-25 日産化学株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément à cristaux liquides dispersés dans un polymère
WO2022211086A1 (fr) * 2021-04-02 2022-10-06 旭化成株式会社 Polyimide, composition de résine, film de polyimide et procédé de production associé

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5872924A (ja) * 1981-10-28 1983-05-02 Hitachi Ltd 液晶表示素子
JP2004245869A (ja) * 2003-02-10 2004-09-02 Hitachi Cable Ltd 液晶配向膜および液晶表示素子

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20030007186A (ko) * 2001-07-17 2003-01-23 미쯔이카가쿠 가부시기가이샤 광 양이온성 경화가능 수지 조성물 및 그 용도
KR20060017138A (ko) * 2004-08-20 2006-02-23 삼성전자주식회사 배향막의 형성방법 및 안정화 방법
JP6421412B2 (ja) * 2013-03-19 2018-11-14 Jsr株式会社 液晶配向剤、液晶配向膜及び液晶表示素子
JP6057075B2 (ja) * 2013-04-18 2017-01-11 Jsr株式会社 液晶配向剤
JP6672821B2 (ja) 2015-04-16 2020-03-25 Jsr株式会社 液晶配向剤及び液晶配向膜の製造方法
JP6870377B2 (ja) 2016-04-25 2021-05-12 Jsr株式会社 液晶配向剤、液晶配向膜及びその製造方法、並びに液晶素子

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5872924A (ja) * 1981-10-28 1983-05-02 Hitachi Ltd 液晶表示素子
JP2004245869A (ja) * 2003-02-10 2004-09-02 Hitachi Cable Ltd 液晶配向膜および液晶表示素子

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022176713A1 (fr) * 2021-02-16 2022-08-25 日産化学株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément à cristaux liquides dispersés dans un polymère
WO2022211086A1 (fr) * 2021-04-02 2022-10-06 旭化成株式会社 Polyimide, composition de résine, film de polyimide et procédé de production associé
JP7174199B1 (ja) * 2021-04-02 2022-11-17 旭化成株式会社 ポリイミド、樹脂組成物、ポリイミドフィルム、及び、その製造方法
JP2022190112A (ja) * 2021-04-02 2022-12-22 旭化成株式会社 ポリイミド、樹脂組成物、ポリイミドフィルム、及び、その製造方法
JP7436606B2 (ja) 2021-04-02 2024-02-21 旭化成株式会社 ポリイミド、樹脂組成物、ポリイミドフィルム、及び、その製造方法

Also Published As

Publication number Publication date
JP6897791B2 (ja) 2021-07-07
KR102341987B1 (ko) 2021-12-21
JPWO2019106952A1 (ja) 2020-07-30
CN111164501A (zh) 2020-05-15
TW201925183A (zh) 2019-07-01
CN111164501B (zh) 2022-10-04
KR20200046093A (ko) 2020-05-06
TWI786195B (zh) 2022-12-11

Similar Documents

Publication Publication Date Title
TWI608278B (zh) 液晶配向劑、液晶配向膜及液晶顯示元件
KR20130054126A (ko) 막 형성 재료의 제조 방법, 막 및 액정 표시 소자
KR101823949B1 (ko) 액정 배향제, 액정 배향막 및 액정 표시 소자
JP6477039B2 (ja) 液晶配向剤、液晶配向膜及び液晶表示素子
TWI582147B (zh) 液晶配向劑、液晶配向膜及液晶顯示元件
KR20140102117A (ko) 액정 표시 소자 및 그의 제조 방법
WO2019106952A1 (fr) Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément à cristaux liquides
JP7409325B2 (ja) 液晶配向剤及び液晶素子の製造方法
TWI510520B (zh) 液晶配向劑、液晶配向膜及液晶顯示元件
JP6962440B2 (ja) 液晶配向剤、液晶配向膜及び液晶素子
CN110383156B (zh) 液晶取向剂及其应用、液晶元件及聚合物
KR20210125901A (ko) 액정 배향제, 액정 배향막 및 그의 제조 방법, 그리고 액정 소자
JP6682795B2 (ja) 液晶配向膜の製造方法、液晶素子の製造方法及び光配向用重合体組成物
JP6962449B2 (ja) 液晶配向剤、液晶配向膜及び液晶素子
JP2022191063A (ja) 液晶配向剤、液晶配向膜、液晶素子、重合体及び化合物
JP2018155920A (ja) 液晶配向剤、液晶配向膜およびそれを用いた液晶表示素子

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: 18883851

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2019557039

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 20207009464

Country of ref document: KR

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: 18883851

Country of ref document: EP

Kind code of ref document: A1