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WO2018043326A1 - Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides - Google Patents

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

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Publication number
WO2018043326A1
WO2018043326A1 PCT/JP2017/030520 JP2017030520W WO2018043326A1 WO 2018043326 A1 WO2018043326 A1 WO 2018043326A1 JP 2017030520 W JP2017030520 W JP 2017030520W WO 2018043326 A1 WO2018043326 A1 WO 2018043326A1
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Prior art keywords
liquid crystal
diamine
formula
group
aligning agent
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PCT/JP2017/030520
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English (en)
Japanese (ja)
Inventor
尚士 鉄谷
武重 林
静如 呉
啓文 志田
Original Assignee
日産化学工業株式会社
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Application filed by 日産化学工業株式会社 filed Critical 日産化学工業株式会社
Priority to CN201780066434.3A priority Critical patent/CN109891310B/zh
Priority to JP2018537223A priority patent/JP7081488B2/ja
Priority to KR1020197008958A priority patent/KR102469386B1/ko
Publication of WO2018043326A1 publication Critical patent/WO2018043326A1/fr

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    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on 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 C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—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 invention relates to a liquid crystal aligning agent, a liquid crystal alignment film using the same, and a liquid crystal display element.
  • the liquid crystal alignment film is a constituent member of a liquid crystal display element widely used as a display device, and plays a role of aligning liquid crystals in a certain direction.
  • the main liquid crystal alignment film used industrially is formed from a liquid crystal aligning agent made of a polyimide precursor polyamic acid (also referred to as polyamic acid) or a polyimide solution. Specifically, a liquid crystal aligning agent is applied to a substrate, heated and fired, and then subjected to a liquid crystal aligning treatment.
  • an alignment process using a photoreaction has been proposed as an alignment process method instead of the rubbing method.
  • a method of imparting liquid crystal alignment ability by forming a polymer film having a specific site causing a photoreaction such as polyvinyl cinnamate on the substrate surface and irradiating with polarized or non-polarized radiation ( The photo-alignment method) is known. According to this method, uniform liquid crystal alignment can be realized without generating static electricity or dust, and viewing angle can be improved by alignment division (see Patent Documents 1 and 2).
  • the liquid crystal alignment film needs to have a function of tilting and aligning liquid crystal molecules at a predetermined angle (pretilt angle) with respect to the substrate surface.
  • pretilt angle a liquid crystal alignment film using a polyamic acid having an alkyl side chain, a side chain of a steroid skeleton, a side chain having a ring structure, polyimide, or the like is known (Patent Documents 3 and 4). 5).
  • the pretilt angle is usually given by irradiation with radiation whose incident direction to the substrate surface is inclined with respect to the normal direction of the substrate (see Patent Document 1).
  • liquid crystal display elements have been used in mobile electronic devices such as smartphones and mobile phones.
  • a so-called narrow frame is required in which the width of a sealing agent used for bonding between substrates of a liquid crystal display element is as narrow as possible.
  • a sealant used for manufacturing a liquid crystal display element is applied at a position close to the end of the liquid crystal alignment film or on the liquid crystal alignment film.
  • the liquid crystal alignment film usually has no or few polar groups, there is a problem that a covalent bond is not formed between the sealant and the liquid crystal alignment film, and adhesion between the substrates is insufficient. .
  • the main object of the present invention is to provide a liquid crystal aligning agent that can improve the adhesion between the liquid crystal aligning film and the sealing agent or the substrate without deteriorating the liquid crystal aligning property and electrical characteristics.
  • the present invention relates to a diamine component containing a diamine having the structure of the following formula [1], a diamine having the structure of the following formula [2], and a diamine having the structure of the following formula [3], and a tetracarboxylic dianhydride component.
  • the gist of the present invention is a liquid crystal aligning agent characterized by containing at least one polymer selected from the group consisting of a polyamic acid obtained by the reaction with and a polyimide obtained by imidizing the polyamic acid.
  • A represents a heat-eliminable group that is replaced with a hydrogen atom by heating at a temperature of 150 to 300 ° C.
  • the hydrogen atom of the benzene ring may be substituted with an alkyl group having 1 to 5 carbon atoms, an alkoxy group, or a halogen group.
  • m is an integer of 1 to 18, and when m is 3 to 18, —O— may exist between any carbon-carbon bonds.
  • n is an integer of 2 to 18. When n is 3 to 18, —O— may exist between any carbon-carbon bonds. * Represents a bond.
  • the liquid crystal aligning agent of the present invention can improve the seal adhesion in a liquid crystal display element sealed with a sealing agent, and the obtained liquid crystal aligning film is not colored black brown and does not lose transparency. And characteristics such as pretilde angle are good.
  • the liquid crystal aligning agent of the present invention includes a diamine having a structure represented by the above formula [1] (hereinafter also referred to as a specific diamine 1) and a diamine having a structure represented by the above formula [2] (hereinafter referred to as a specific diamine 2).
  • the specific diamine 1 contained in the liquid crystal aligning agent of the present invention is a diamine having a structure represented by the following formula [1].
  • A is a heat-eliminable group that can be replaced with hydrogen by heating at a temperature of 150 to 300 ° C.
  • the thermally desorbable group is more preferably removed at 170 to 300 ° C, particularly preferably at 180 to 250 ° C. * Represents a bond.
  • thermal leaving group examples include carbamate organic compounds represented by benzyloxycarbonyl group, 9-fluorenylmethyloxycarbonyl group, allyloxycarbonyl group, tertiary butoxycarbonyl group (also referred to as Boc group), and the like.
  • a Boc group or a 9-fluorenylmethoxycarbonyl group is particularly preferred from the viewpoint that the elimination efficiency is high and the gas is harmless at the time of elimination at a relatively low temperature.
  • the amino group possessed by the specific diamine is preferably a primary amino group, but may be a secondary amino group.
  • an amino group is substituted with an alkyl group having a relatively small molecular weight such as a methyl group, an ethyl group, a propyl group, or a butyl group.
  • the hydrogen atom of the benzene ring in the formula [1] is optionally substituted with an alkyl group or alkoxy group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, or a halogen group such as a chlorine atom, a bromine atom or a fluorine atom. May be.
  • Preferable specific examples of the diamine represented by the formula [1] include the following diamines.
  • Boc represents a tert-butoxycarbonyl group.
  • the specific diamine 2 contained in the liquid crystal aligning agent of the present invention is a diamine having a structure represented by the following formula [2].
  • m is an integer of 1 to 18, and preferably an integer of 2 to 18.
  • —O— may exist between any carbon-carbon bonds. * Represents a bond with another atom.
  • the hydrogen atom of the benzene ring in the formula [2] is optionally substituted with an alkyl or alkoxy group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, or a halogen group such as a chlorine atom, bromine atom or fluorine atom. May be.
  • Preferable specific examples of the diamine having the structure represented by the formula [2] include, but are not limited to, the following diamines.
  • the specific diamine 3 contained in the liquid crystal aligning agent of the present invention is a diamine having a structure represented by the following formula [3].
  • n is an integer of 2 to 18, and when n is an integer of 3 to 18, —O— may exist between any carbon-carbon bonds.
  • a and its preferred range are the same as A in formula [1]. * Represents a bond.
  • the hydrogen atom of the benzene ring in the formula [3] is optionally substituted with an alkyl group or alkoxy group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, or a halogen group such as a chlorine atom, bromine atom or fluorine atom. May be.
  • Preferable specific examples of the diamine represented by the formula [3] include, but are not limited to, the following diamines.
  • a tetracarboxylic dianhydride (also referred to as a specific tetracarboxylic dianhydride) represented by the following formula [7] is used as a part of the tetracarboxylic dianhydride component. It is preferable to use it.
  • Z 1 is a tetravalent organic group having 4 to 13 carbon atoms, and contains an aromatic cyclic hydrocarbon group. Specifically, a group represented by any of the following formulas [7a] to [7k] is preferable.
  • a preferred group of Z 1 is a group represented by the formula [7a] or the formula [7g] from the viewpoint of polymerization reactivity and ease of synthesis.
  • the formula [7a] is most preferable.
  • the tetracarboxylic dianhydride having the structure of the formula [7a] it is preferably 20% by mass or more of the total tetracarboxylic dianhydride component, more preferably 30% by mass or more. is there. A desired effect can be obtained by using it for the production of a polyimide precursor. More preferably, it is 30 mass% or more. All of the tetracarboxylic acid components used for the polyimide synthesis may be tetracarboxylic dianhydrides having the structure of the formula [7a].
  • an aliphatic tetracarboxylic dianhydride other than the specific tetracarboxylic dianhydride and other tetracarboxylic acid components can be used.
  • examples of the aliphatic tetracarboxylic dianhydride include 1,2,3,4-butanetetracarboxylic dianhydride.
  • Examples of the alicyclic tetracarboxylic dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4- Cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexane Tetracarboxylic dianhydride, 1,2,3,4-cycloheptanetetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 3,4-dicarboxy-1-cycl Hexyl
  • tetracarboxylic acid components include tetracarboxylic acid, tetracarboxylic acid dihalide, tetracarboxylic dianhydride, esterified product obtained by dialkyl esterifying the carboxylic acid group of tetracarboxylic acid, and dialkyl carboxylic acid group of tetracarboxylic acid dihalide. Examples include esterified esterified products.
  • the above-mentioned other tetracarboxylic acid components can be used alone or in combination of two or more kinds in consideration of characteristics such as liquid crystal alignment properties, voltage holding characteristics and accumulated charges of the liquid crystal alignment film to be formed.
  • the liquid crystal aligning agent contains a polyamic acid and / or a polyimide obtained by imidizing the polyamic acid (hereinafter also collectively referred to as a polymer).
  • the polymer of the present invention is a polyamic acid obtained by reaction of a diamine component containing the specific diamines 1, 2 and 3 and a tetracarboxylic dianhydride component, and / or imidizing the polyamic acid. It means the polyimide obtained.
  • the polymer other than the present invention is a polyamic acid obtained by reaction of a diamine component containing a diamine which is not thermally desorbed and protected and a tetracarboxylic dianhydride component, and / or the polyamic acid.
  • a polyamic acid obtained by reaction of a diamine component containing a diamine which is not thermally desorbed and protected and a tetracarboxylic dianhydride component, and / or the polyamic acid.
  • a polyamic acid is obtained by reaction of a diamine component containing a diamine and a tetracarboxylic dianhydride component.
  • the content ratio of the specific diamine 1, 2 and 3 in the diamine component for obtaining the polyamic acid as the polymer of the present invention by reaction with the tetracarboxylic dianhydride component is preferably 5 to 95 mol% of the specific diamine 1. More preferably, it is 10 to 60 mol%.
  • the total content of the specific diamine 2 and the specific diamine 3 in the diamine component for obtaining the polyamic acid which is the polymer of the present invention is preferably 10 to 60 mol%, more preferably 20 to 40 mol%.
  • the content ratio (molar ratio) of the specific diamine 2 to the specific diamine 3 is preferably 10:90 to 90:10, and more preferably 10:40 to 40:10.
  • the diamine component for obtaining a polyamic acid better satisfies various properties required for a liquid crystal alignment film, for example, a property of increasing the pretilt angle of liquid crystal and a property of improving the vertical alignment property of liquid crystal. Therefore, other diamines can be used in combination.
  • the content of the other diamines is preferably 1 to 50 mol%, more preferably 5 to 30 mol% in the amine component.
  • Examples of the other diamines include alicyclic diamines, aromatic-aliphatic diamines, heterocyclic diamines, and aliphatic diamines (excluding diamines represented by the formulas [1] to [3]). It is done.
  • alicyclic diamines examples include 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4′-diaminodicyclohexylmethane, 4,4′-diamino-3,3′-dimethyldicyclohexylamine, isophorone diamine Etc.
  • aromatic diamines examples include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 3,5-diaminotoluene, 1,4-diamino -2-methoxybenzene, 2,5-diamino-p-xylene, 1,3-diamino-4-chlorobenzene, 3,5-diaminobenzoic acid, 1,4-diamino-2,5-dichlorobenzene, 4,4 '-Diamino-1,2-diphenylethane, 4,4'-diamino-2,2'-dimethylbibenzyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane 4,4′-diamin
  • aromatic-aliphatic diamines include 3-aminobenzylamine, 4-aminobenzylamine, 3-amino-N-methylbenzylamine, 4-amino-N-methylbenzylamine, 3-aminophenethylamine, 4-aminobenzylamine, Aminophenethylamine, 3-amino-N-methylphenethylamine, 4-amino-N-methylphenethylamine, 3- (3-aminopropyl) aniline, 4- (3-aminopropyl) aniline, 3- (3-methylaminopropyl) Aniline, 4- (3-methylaminopropyl) aniline, 3- (4-aminobutyl) aniline, 4- (4-aminobutyl) aniline, 3- (4-methylaminobutyl) aniline, 4- (4-methyl Aminobutyl) aniline, 3- (5-aminopentyl) aniline, 4- (5-aminopentyl) Aniline, 3- (5-methyl)
  • heterocyclic diamines examples include 2,6-diaminopyridine, 2,4-diaminopyridine, 2,4-diamino-1,3,5-triazine, 2,7-diaminodibenzofuran, 3,6-diaminocarbazole 2,4-diamino-6-isopropyl-1,3,5-triazine, 2,5-bis (4-aminophenyl) -1,3,4-oxadiazole and the like.
  • aliphatic diamines examples include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,3-diamino-2,2-dimethylpropane, 1,6-diamino-2,5-dimethylhexane, 1,7- Diamino-2,5-dimethylheptane, 1,7-diamino-4,4-dimethylheptane, 1,7-diamino-3-methylheptane, 1,9-diamino-5-methylheptane, 1,12-diaminododecane 1,18-diaminooctadecan
  • diamine compound which has an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, or the macrocyclic substituent which consists of them in a side chain.
  • diamines represented by the following formulas [DA1] to [DA26] are exemplified.
  • R 6 is an alkyl group or a fluorine-containing alkyl group having 1 to 22 carbon atoms.
  • R 6 represents 1 to 22 carbon atoms. It has an alkyl group or a fluorine-containing alkyl group.
  • R 7 represents an alkyl group or alkoxy group having 1 to 22 carbon atoms.
  • R 6 represents —O—, —OCH 2 —, —CH 2 O—, —COOCH 2 —, or —CH 2 OCO—
  • R 7 represents an alkyl group or alkoxy group having 1 to 22 carbon atoms.
  • R 8 represents an alkyl group, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group having 1 to 22 carbon atoms.
  • R 9 represents a fluorine group, a cyano group, a trifluoromethane group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group, or a hydroxyl group.
  • R 10 is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer.
  • a diamine of the general formula [1] in combination with the diamines of the above [DA-1] to [DA-26] because a more stable pretilt angle can be obtained.
  • More preferred diamines that can be used in combination are those represented by the formulas [DA-10] to [DA-26], more preferably diamines of [DA-10] to [DA-16].
  • the preferred content of these diamines is not particularly limited, but is preferably 5 to 50 mol% in the diamine component, and is preferably 5 to 30 mol% in terms of printability. Moreover, you may use the following diamine together.
  • diaminosiloxanes represented by the following formula [DA-35] can also be mentioned as other diamines.
  • M is an integer from 1 to 10.
  • Other diamines can be used singly or in combination of two or more depending on properties such as liquid crystal alignment properties, voltage holding properties, and accumulated charges when the liquid crystal alignment film is formed.
  • ⁇ Production of polyamic acid> As a method for obtaining the polyamic acid of the present invention by the reaction of the tetracarboxylic dianhydride component and the diamine component, a known method can be used. In general, the tetracarboxylic dianhydride component and the diamine component are reacted in an organic solvent. The reaction between the tetracarboxylic dianhydride component and the diamine is advantageous in that it proceeds relatively easily in an organic solvent and no by-products are generated.
  • the organic solvent used for the reaction between the tetracarboxylic dianhydride component and the diamine is not limited as long as the produced polyamic acid dissolves. Specific examples are given below. N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide , ⁇ -butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate,
  • a method of adding by dispersing or dissolving in a solvent a method of adding a diamine component to a solution in which a tetracarboxylic dianhydride component is dispersed or dissolved in an organic solvent, and a tetracarboxylic dianhydride component and a diamine component.
  • the method of adding alternately etc. is mentioned, You may use any of these methods.
  • the tetracarboxylic dianhydride component or the diamine component is composed of a plurality of types of compounds, they may be reacted in a premixed state, may be individually reacted sequentially, or may be further reacted individually.
  • the body may be mixed and reacted to form a high molecular weight body.
  • the temperature at which the tetracarboxylic dianhydride component reacts with the diamine component can be selected from -20 to 150 ° C, but is preferably in the range of -5 to 100 ° C.
  • the reaction can be carried out at any concentration, but if the concentration is too low, it is difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring is difficult. Therefore, the total concentration of the tetracarboxylic dianhydride component and the diamine component in the reaction solution is preferably 1 to 50% by mass, more preferably 5 to 30% by mass.
  • the initial stage of the reaction is carried out at a high concentration, and then an organic solvent can be added.
  • the ratio of the total number of moles of the tetracarboxylic dianhydride component to the total number of moles of the diamine component is preferably 0.8 to 1.2, preferably 0.9 to 1. 1 is more preferable. Similar to the normal polycondensation reaction, the molecular weight of the polyamic acid produced increases as the molar ratio approaches 1.0.
  • the polyimide of the present invention is a polyimide obtained by dehydrating and ring-closing the polyamic acid, and is useful as a polymer for obtaining a liquid crystal alignment film.
  • the dehydration cyclization rate (imidation rate) of the amic acid group is not necessarily 100%, and can be arbitrarily adjusted according to the application and purpose.
  • Examples of the method for imidizing a polyamic acid include a thermal imidization method in which a polyamic acid solution is heated as it is, and a catalyst imidation method in which a catalyst is added to the polyamic acid solution.
  • the temperature at which the polyamic acid is thermally imidized in the solution is 100 to 400 ° C., preferably 120 to 250 ° C., and is preferably carried out while removing water generated by the imidization reaction from the system.
  • the catalytic imidation of polyamic acid can be carried out by adding a basic catalyst and an acid anhydride to a polyamic acid solution and stirring at -20 to 250 ° C., preferably 0 to 180 ° C.
  • the amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times the amidic acid group
  • the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol times the amido group. 30 mole times.
  • the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Among them, pyridine is preferable because it has basicity suitable for proceeding with the reaction.
  • Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated.
  • the imidization rate by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, reaction time, and the like.
  • the molecular weight of the polymer contained in the liquid crystal aligning agent of the present invention is determined by GPC (Gel Permeation Chromatography) method in consideration of the strength of the obtained coating film, workability at the time of coating film formation, and uniformity of the coating film.
  • the measured weight average molecular weight is preferably 5,000 to 1,000,000, and more preferably 10,000 to 150,000.
  • the liquid crystal aligning agent of this invention is a coating liquid for forming a liquid crystal aligning film, and is a solution which the resin component for forming a resin film melt
  • the said resin component contains at least 1 type of polymer chosen from the polymer of above-described this invention.
  • the content of the resin component in the liquid crystal aligning agent is preferably 1 to 20% by mass, more preferably 3 to 15% by mass, and particularly preferably 3 to 10% by mass. All of the resin components may be the polymer of the present invention, or other polymers may be mixed. In that case, the content of the other polymer in the resin component is 0.5 to 15% by mass, preferably 1 to 10% by mass. Examples of such other polymer include polyamic acid or polyimide obtained by using a diamine compound other than the specific diamine compound as a diamine component to be reacted with the tetracarboxylic dianhydride component.
  • the organic solvent used for the liquid crystal aligning agent of this invention will not be specifically limited if it is an organic solvent in which a resin component is dissolved. Specific examples are given below. N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, Dimethylsulfone, hexamethylsulfoxide, ⁇ -butyrolactone, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, 1,3 -Dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl is
  • the liquid crystal aligning agent of this invention may contain components other than the above.
  • examples thereof include compounds that improve the adhesion between the liquid crystal alignment film and the substrate, such as a solvent-rich substance that improves film thickness uniformity and surface smoothness when a liquid crystal aligning agent is applied.
  • a solvent-rich substance that improves film thickness uniformity and surface smoothness when a liquid crystal aligning agent is applied.
  • the following are mentioned as a specific example of the solvent (poor solvent) which improves the uniformity of film thickness and surface smoothness.
  • Examples of compounds that improve film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. More specifically, for example, F-top EF301, EF303, EF352 (manufactured by Tochem Products), MegaFuck F171, F173, R-30 (manufactured by Dainippon Ink), Florard FC430, FC431 (manufactured by Sumitomo 3M) Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.).
  • the use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the resin component contained in the liquid crystal aligning agent.
  • the compound for improving the adhesion between the liquid crystal alignment film and the substrate include the following functional silane-containing compounds and epoxy group-containing compounds.
  • phenoplast type additives for the purpose of preventing electrical characteristics from being deteriorated by the backlight. Specific phenoplast type additives are shown below.
  • the amount used is preferably 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the resin component. is there. If the amount used is less than 0.1 parts by mass, the effect of improving the adhesion cannot be expected, and if it exceeds 30 parts by mass, the orientation of the liquid crystal may deteriorate.
  • the liquid crystal aligning agent of the present invention may be a dielectric or conductive material for the purpose of changing the electrical properties such as dielectric constant and conductivity of the liquid crystal aligning film as long as the effects of the present invention are not impaired.
  • a crosslinkable compound or the like for the purpose of increasing the hardness and density of the liquid crystal alignment film may be added.
  • the liquid crystal aligning agent of the present invention can be applied as a liquid crystal alignment film without applying an alignment treatment in a vertical alignment application or the like after being applied on a substrate and baked and then subjected to an alignment treatment by rubbing treatment or light irradiation.
  • the substrate to be used is not particularly limited as long as it is a highly transparent substrate, and a glass substrate, an acrylic substrate, a polycarbonate substrate such as a polycarbonate substrate, or the like can be used.
  • an opaque material such as a silicon wafer can be used as long as only one substrate is used.
  • a material that reflects light such as aluminum, can also be used.
  • the application method of the liquid crystal aligning agent is not particularly limited, but industrially, it is generally performed by a method such as screen printing, offset printing, flexographic printing, or inkjet. Other coating methods include dip, roll coater, slit coater, spinner and the like, and these may be used depending on the purpose.
  • Firing after applying the liquid crystal aligning agent on the substrate can be carried out by a heating means such as a hot plate at 50 to 300 ° C., preferably 80 to 250 ° C., and the solvent can be evaporated to form a coating film. If the thickness of the coating film formed after baking is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered. The thickness is preferably 10 to 100 nm. When the liquid crystal is horizontally or tilted, the fired coating film is treated by rubbing or irradiation with polarized ultraviolet rays.
  • the liquid crystal display element of the present invention is a liquid crystal display element obtained by obtaining a substrate with a liquid crystal alignment film from the liquid crystal aligning agent of the present invention by the method described above, and then preparing a liquid crystal cell by a known method.
  • liquid crystal cell production prepare a pair of substrates on which a liquid crystal alignment film is formed, spread spacers on the liquid crystal alignment film of one substrate, so that the liquid crystal alignment film surface is on the inside, Examples include a method of bonding the other substrate and injecting liquid crystal under reduced pressure, or a method of bonding a substrate after sealing the liquid crystal on the liquid crystal alignment film surface on which spacers are dispersed, and sealing.
  • the thickness of the spacer is preferably 1 to 30 ⁇ m, more preferably 2 to 10 ⁇ m.
  • ⁇ Viscosity measurement> The viscosity of the solution was measured using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.) with a sample amount of 1.1 mL and a cone rotor TE-1 (1 ° 34 ′, R24) at a temperature of 25 ° C. .
  • a substrate with electrodes was prepared.
  • the substrate is a glass substrate having a rectangular shape of 30 mm length ⁇ 35 mm width and a thickness of 0.7 mm.
  • an IZO electrode having a solid pattern constituting a counter electrode as a first layer is formed on the substrate.
  • a silicon nitride (SiN) film formed by the CVD method is formed as a second layer on the counter electrode of the first layer.
  • the second layer SiN film has a thickness of 500 nm and functions as an interlayer insulating film.
  • a comb-like pixel electrode formed by patterning an IZO film as the third layer is arranged to form two pixels, a first pixel and a second pixel. ing.
  • the size of each pixel is 10 mm long and about 5 mm wide.
  • the first-layer counter electrode and the third-layer pixel electrode are electrically insulated by the action of the second-layer SiN film.
  • the pixel electrode of the third layer has a comb-like shape configured by arranging a plurality of “bow” -shaped electrode elements having a bent central portion.
  • the width in the short direction of each electrode element is 3 ⁇ m, and the distance between the electrode elements is 6 ⁇ m. Since the pixel electrode forming each pixel is formed by arranging a plurality of bent-shaped electrode elements in the central portion, the shape of each pixel is not rectangular, but in the central portion like the electrode elements. It has a shape that bends and resembles a bold “Koji”.
  • Each pixel is divided vertically with a central bent portion as a boundary, and has a first region on the upper side of the bent portion and a second region on the lower side.
  • the formation directions of the electrode elements of the pixel electrodes constituting them are different. That is, when the rubbing direction of the liquid crystal alignment film described later is used as a reference, the electrode element of the pixel electrode is formed to form an angle of + 10 ° (clockwise) in the first region of the pixel, and the pixel in the second region of the pixel. The electrode elements of the electrode are formed so as to form an angle of ⁇ 10 ° (clockwise).
  • the direction of the rotation operation (in-plane switching) of the liquid crystal induced by the voltage application between the pixel electrode and the counter electrode is in the substrate plane. It is comprised so that it may become a mutually reverse direction.
  • an ITO film is formed on the back surface as the prepared substrate with electrodes and a counter substrate, and glass having columnar spacers with a height of 4 ⁇ m.
  • Each of the substrates was spin coated.
  • the polyimide film with a film thickness of 60 nm was obtained on each board
  • the polyimide film is rubbed with a rayon cloth in a predetermined rubbing direction (roll diameter 120 mm, rotation speed 500 rpm, moving speed 30 mm / sec, pushing amount 0.3 mm), and then irradiated with ultrasonic waves in pure water for 1 minute. And dried at 80 ° C. for 10 minutes to obtain a liquid crystal alignment film.
  • the rubbing directions are combined so that they are antiparallel, the periphery is sealed leaving the liquid crystal injection port, and an empty cell with a cell gap of 3.5 ⁇ m is formed.
  • a liquid crystal (MLC-3019, manufactured by Merck & Co., Inc.) was vacuum-injected into the empty cell at room temperature, and the injection port was sealed to obtain an anti-parallel alignment liquid crystal cell.
  • the obtained liquid crystal cell constitutes an FFS mode liquid crystal display element. Thereafter, the obtained liquid crystal cell was heated at 120 ° C. for 1 hour and allowed to stand overnight before being used for each evaluation.
  • the rotation angle when the liquid crystal cell was rotated from the angle at which the second region of the first pixel became darkest to the angle at which the first region became darkest was calculated as an angle ⁇ .
  • the second area was compared with the first area, and a similar angle ⁇ was calculated.
  • the average value of the angle ⁇ values of the first pixel and the second pixel was calculated as the angle ⁇ of the liquid crystal cell. The smaller the angle ⁇ of the liquid crystal cell, the higher the liquid crystal alignment.
  • pretilt angle of the liquid crystal cell produced above was measured. Further, the liquid crystal cell was heated in a heat circulation oven at 110 ° C. for 1 hour, and then the pretilt angle was measured. The pretilt angle was measured using a minute tilt angle measuring device (OPTI-PRO manufactured by Shintech Co., Ltd.).
  • the liquid crystal aligning agent was filtered through a filter having a pore diameter of 1.0 ⁇ m, spin-coated on a glass substrate with a transparent electrode, dried on an 80 ° C. hot plate for 2 minutes, and then baked at 230 ° C. for 20 minutes to have a film thickness of 70 nm. A coating film was obtained. Two substrates thus obtained were prepared, and after spraying a 4 ⁇ m diameter bead spacer (manufactured by JGC Catalysts & Chemicals Co., Ltd., true ball, SW-D1) on the liquid crystal alignment film surface of one substrate, UV ( UV) curable adhesive was added dropwise.
  • Example 1 to 11 4.36 g of each of the polyamic acid solutions (PAA-1) to (PAA-12) obtained in Synthesis Examples 1 to 11 were collected. To this, 11.3 g of the polyamic acid solution (PAA-12) obtained in Synthesis Example 12 was added, and while stirring, an NMP solution containing 13.9 g of NMP, 8.00 g of BCS, and 1% by weight of LS-4668 was added, and the mixture was further stirred at room temperature for 2 hours to obtain liquid crystal alignment agents (AL-1) to (AL-11), respectively.
  • NMP solution containing 13.9 g of NMP, 8.00 g of BCS, and 1% by weight of LS-4668 was added, and the mixture was further stirred at room temperature for 2 hours to obtain liquid crystal alignment agents (AL-1) to (AL-11), respectively.
  • the liquid crystal aligning agent of the present invention is used in a wide range of fields such as a narrow frame type, a liquid crystal display device for mobile use such as a smart phone and a mobile phone, and a large liquid crystal display device that requires high definition and low cost. Is done. It should be noted that the entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2016-168471 filed on August 30, 2016 are cited herein as disclosure of the specification of the present invention. Incorporate.

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Abstract

L'invention fournit un agent d'alignement de cristaux liquides qui permet d'améliorer les propriétés de scellement et adhésion dans un élément d'affichage à cristaux liquides scellé à l'aide d'un agent de scellement, qui ne présente pas de coloration marron foncé d'un film d'alignement de cristaux liquides obtenu, ni de détérioration de sa transparence, et dont les caractéristiques d'alignement de cristaux liquides, d'angle de protrusion, ou similaire, sont satisfaisantes. Cet agent d'alignement de cristaux liquides comprend au moins un polymère choisi dans un groupe constitué d'une diamine possédant une structure de formule ［１］, d'une diamine possédant une structure de formule ［2］, d'un acide polyamique obtenu par réaction d'un composant diamine comprenant une diamine possédant une structure de formule ［3］ et d'un composant dianhydride d'acide tétracarboxylique, et d'un polyimide obtenu par imidation de cet acide polyamique. (Les symboles mentionnés dans les formules, sont définis dans la description.)
PCT/JP2017/030520 2016-08-30 2017-08-25 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides WO2018043326A1 (fr)

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JP2018537223A JP7081488B2 (ja) 2016-08-30 2017-08-25 液晶配向剤、液晶配向膜及び液晶表示素子
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CN111936923A (zh) * 2018-03-30 2020-11-13 日产化学株式会社 新型的液晶取向剂、液晶取向膜和液晶表示元件
WO2022168722A1 (fr) * 2021-02-04 2022-08-11 日産化学株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, procédé de production d'un élément d'affichage à cristaux liquides et élément d'affichage à cristaux liquides

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WO2022168722A1 (fr) * 2021-02-04 2022-08-11 日産化学株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, procédé de production d'un élément d'affichage à cristaux liquides et élément d'affichage à cristaux liquides

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