WO2020138109A1 - Agent de traitement d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides - Google Patents

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

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WO2020138109A1
WO2020138109A1 PCT/JP2019/050687 JP2019050687W WO2020138109A1 WO 2020138109 A1 WO2020138109 A1 WO 2020138109A1 JP 2019050687 W JP2019050687 W JP 2019050687W WO 2020138109 A1 WO2020138109 A1 WO 2020138109A1
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Prior art keywords
liquid crystal
crystal alignment
group
treatment agent
alignment treatment
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PCT/JP2019/050687
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English (en)
Japanese (ja)
Inventor
加名子 鈴木
雅章 片山
真文 高橋
保坂　和義
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日産化学株式会社
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Priority to KR1020217019557A priority Critical patent/KR20210108962A/ko
Priority to CN201980086391.4A priority patent/CN113260910A/zh
Priority to JP2020563321A priority patent/JP7392663B2/ja
Publication of WO2020138109A1 publication Critical patent/WO2020138109A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/45—Heterocyclic compounds having sulfur in the ring
    • C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • 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

Definitions

  • the present invention relates to a liquid crystal alignment treatment agent used for manufacturing a liquid crystal display element, a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent, and a liquid crystal display element using the liquid crystal alignment film.
  • a film made of an organic material such as a polymer material is widely used as an interlayer insulating film, a protective film, etc. in electronic devices, because of its ease of formation and insulating performance.
  • an organic film made of polyimide is used as a liquid crystal alignment film.
  • the liquid crystal alignment film is used to control the alignment state of the liquid crystal.
  • it is required to reduce the contrast of the liquid crystal display elements and suppress display defects due to long-term use.
  • liquid crystal display devices have been used for mobile applications such as smartphones and mobile phones.
  • mobile applications such as smartphones and mobile phones.
  • the drawing position of the sealant is at a position in contact with the end of the liquid crystal alignment film, which has weak adhesion to the sealant, or at the upper part of the liquid crystal alignment film. Therefore, in recent years, the adhesion between the substrates of the liquid crystal display element has become weaker than in the past.
  • the present invention is excellent in storage stability of the liquid crystal alignment treatment agent, has high adhesiveness (also referred to as adhesiveness) between the substrates of the liquid crystal display element, and is further exposed to high temperature and high humidity for a long time. It is an object of the present invention to provide a liquid crystal alignment film capable of suppressing the generation of bubbles in the liquid crystal display element and the peeling of the element even under such an environment. In addition, another object is to provide a liquid crystal display device having the above liquid crystal alignment film and a liquid crystal alignment treatment agent capable of producing the above liquid crystal alignment film.
  • the present inventor has completed the present invention having the following points. That is, it is a liquid crystal alignment treatment agent containing a compound having a group represented by the following formula [1] (also referred to as a specific compound). (* represents a binding site with another structure.)
  • the liquid crystal alignment treatment agent of the present invention is excellent in storage stability, has high adhesiveness between substrates of a liquid crystal display element, and further, even in an environment exposed to high temperature and high humidity for a long time, bubbles in the liquid crystal display element It is possible to provide a liquid crystal alignment film capable of suppressing generation and peeling of elements.
  • a liquid crystal display device having the above liquid crystal alignment film and a liquid crystal alignment treatment agent capable of producing the above liquid crystal alignment film can be provided. Therefore, the liquid crystal display element of the present invention is used for a liquid crystal display element such as a smartphone or a mobile phone.
  • SS disulfide bond
  • the liquid crystal display device can suppress the generation of bubbles and the peeling of the device.
  • the specific compound is a compound having a group represented by the above formula [1].
  • a compound represented by the following formula [1a] can be mentioned.
  • X 1 is selected from the group consisting of the following formulas [1-a] to [1-k].
  • T A represents an alkyl group having 1 to 3 carbon atoms.
  • the formula [1-b], the formula [1-c] or the formula [1-d] is preferable.
  • X 2 represents a single bond or an organic group having 1 to 18 carbon atoms. Of these, a single bond or an organic group having 1 to 6 carbon atoms is preferable.
  • X 3 represents a group represented by the above formula [1].
  • Specific preferred examples of the specific compound include compounds represented by the following formula [1-1a], and it is preferable to use these.
  • the specific compound is used in an amount of 0.1 to 30 parts by mass based on 100 parts by mass of all the polymers contained in the liquid crystal alignment treatment agent.
  • the amount is preferably 0.5 part by mass, more preferably 0.5 to 20 parts by mass, and most preferably 1 to 15 parts by mass.
  • the specific compound may be used alone or in combination of two or more depending on each characteristic.
  • the polymer contained in the liquid crystal alignment treatment agent is preferably a polymer having a functional group capable of reacting with the specific compound.
  • the functional group capable of reacting is a concept that includes a functional group capable of forming a covalent bond at room temperature as well as a functional group capable of potentially forming a covalent bond. Examples of such a functional group include heating and/or electromagnetic waves.
  • the functional group capable of reacting include a carboxyl group, an amino group, a (meth)acrylic group, an acid anhydride group, a phenol group, a hydroxyl group, a silanol group, an imide group, an ester group, an amide group, and a urea group. ..
  • the polymer having a functional group capable of reacting with the specific compound is at least selected from the group consisting of acrylic polymer, methacrylic polymer, novolac resin, polyhydroxystyrene, polyimide precursor, polyimide, polyamide, polyester, cellulose, and polysiloxane.
  • One kind is preferable. More preferably, it is a polyimide precursor or polyimide.
  • a polyimide precursor or a polyimide (collectively referred to as a polyimide-based polymer) is used as the polymer, they are a polyimide precursor obtained by reacting a diamine component and a tetracarboxylic acid component or the polyimide.
  • a polyimide obtained by imidizing a precursor is preferable.
  • the polyimide precursor preferably has a structure represented by the following formula [A].
  • R 1 represents a tetravalent organic group.
  • R 2 represents a divalent organic group.
  • a 1 and A 2 each represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
  • a 3 and A 4 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an acetyl group.
  • n represents a positive integer.
  • the diamine component may be a diamine having two primary or secondary amino groups in the molecule.
  • the tetracarboxylic acid component include a tetracarboxylic acid compound, a tetracarboxylic acid dianhydride, a tetracarboxylic acid dihalide compound, a tetracarboxylic acid dialkyl ester compound, and a tetracarboxylic acid dialkyl ester dihalide compound.
  • a polyimide-based polymer can be obtained relatively easily by using a tetracarboxylic acid dianhydride of the following formula [B] and a diamine of the following formula [C] as a raw material, so that the following formula [D]
  • a polyamic acid having a structural formula of a repeating unit or a polyimide obtained by imidizing the polyamic acid is preferable.
  • the diamine component for producing the polyimide polymer is not particularly limited. Specifically, the diamine compounds of the formulas [3a-1] to [3a-5] described on pages 34 to 38 of WO 2016/076412 and pages 39 to 42 of the publication. Other examples include diamine compounds and the diamine compounds of the formulas [DA1] to [DA15] described on pages 42 to 44 of the publication. These diamine components may be used either individually or in combination of two or more, depending on the characteristics.
  • the tetracarboxylic acid component for producing the polyimide polymer is not particularly limited. Specifically, the tetracarboxylic dianhydride of the formula [4] described on pages 44 to 45 of International Publication WO2016/076412 and the other tetracarboxylic acid components described on pages 45 to 46 are Can be mentioned. These tetracarboxylic acid components may be used either individually or in combination of two or more, depending on the characteristics.
  • the method for synthesizing the polyimide polymer is not particularly limited. Usually, it is obtained by reacting a diamine component and a tetracarboxylic acid component. Specific examples thereof include the methods described on pages 46 to 50 of International Publication WO2016/076412.
  • the reaction between the diamine component and the tetracarboxylic acid component is usually performed in a solvent containing the diamine component and the tetracarboxylic acid component.
  • the solvent used at that time is not particularly limited as long as it can dissolve the generated polyimide precursor.
  • N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, ⁇ -butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide or 1,3-dimethyl-imidazolidinium Non is included.
  • the polyimide precursor has high solvent solubility, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone or a solvent represented by the following formula [D1] to [D3] is used. it can.
  • D 1 and D 2 represent an alkyl group having 1 to 3 carbon atoms.
  • D 3 represents an alkyl group having 1 to 4 carbon atoms.
  • these may be used alone or as a mixture. Further, even a solvent that does not dissolve the polyimide precursor may be used by mixing with the above-mentioned solvent as long as the generated polyimide precursor does not precipitate. Further, since water in the organic solvent inhibits the polymerization reaction and causes hydrolysis of the generated polyimide precursor, it is preferable to use dehydrated and dried organic solvent.
  • the total number of moles of the tetracarboxylic acid component is preferably 0.8 to 1.2 when the total number of moles of the diamine component is 1.0.
  • the polymer has an amino group structure at the terminal.
  • the polymer end When it is greater than 0, that is, when the total number of moles of the tetracarboxylic acid component is greater than the number of moles of the diamine component, the polymer end has a carboxylic acid anhydride or dicarboxylic acid structure.
  • the effect of the specific compound that is, the effect of enhancing the adhesiveness between the liquid crystal alignment film of the liquid crystal display element and the metal electrode becomes higher, so that the total number of moles of the tetracarboxylic acid component is more than 1.0.
  • the total number of moles of the tetracarboxylic acid component is larger than that of the diamine component.
  • the total number of moles of the diamine component is 1.0
  • the total number of moles of the tetracarboxylic acid component is preferably 1.05 to 1.20.
  • Polyimide is obtained by ring-closing a polyimide precursor.
  • the polyimide does not necessarily have a ring closure rate (also referred to as an imidization rate) of an amic acid group of 100%, and can be arbitrarily prepared according to the application or purpose. Among them, 30 to 80% is preferable from the viewpoint of the solubility of the polyimide polymer in the solvent. More preferably, it is 40 to 70%.
  • the molecular weight of the polyimide-based polymer is 5 in terms of weight average molecular weight measured by GPC (Gel Permeation Chromatography) method in consideration of the strength of the liquid crystal alignment film obtained therefrom, workability in forming the liquid crystal alignment film, and coating property. It is preferably from 1,000 to 1,000,000, and more preferably from 10,000 to 150,000.
  • the liquid crystal alignment treatment agent is a solution for forming a liquid crystal alignment film, and is a solution containing a specific compound, a polymer and a solvent. In that case, two or more types can be used for each of a specific compound and a polymer.
  • the content of the solvent in the liquid crystal alignment treatment agent can be appropriately selected from the viewpoint of applying the liquid crystal alignment treatment agent and obtaining a target film thickness. Among them, the content of the solvent in the liquid crystal alignment treatment agent is preferably 50 to 99.9 mass% from the viewpoint of forming a uniform liquid crystal alignment film by coating. Among them, 60 to 99 mass% is preferable. More preferably, it is 65 to 99% by mass.
  • the solvent used for the liquid crystal alignment treatment agent is not particularly limited as long as it is a solvent that dissolves the specific compound and the polymer.
  • the polymer is a polyimide precursor, polyimide, polyamide or polyester, or when the solubility of the acrylic polymer, methacrylic polymer, novolac resin, polyhydroxystyrene, cellulose or polysiloxane in the solvent is low, It is preferable to use a solvent (also referred to as a solvent A).
  • N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or ⁇ -butyrolactone is preferable. Moreover, these may be used individually or may be mixed and used.
  • the polymer is an acrylic polymer, a methacrylic polymer, a novolac resin, polyhydroxystyrene, cellulose or polysiloxane, further, the polymer is a polyimide precursor, polyimide, polyamide or polyester, the solvent of these polymers When the solubility is high, the following solvent (also referred to as solvent B) can be used.
  • solvent Bs include the solvent Bs described on pages 58 to 60 of International Publication WO2014/171493.
  • 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, cyclohexanone, cyclopentanone or the above formula [D1] To Formula [D3] are preferred.
  • N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or ⁇ -butyrolactone of the above-mentioned solvent A is used in combination for the purpose of improving the coating property of the liquid crystal alignment treatment agent. It is preferable to use. Since these solvents B can enhance the coating property and surface smoothness of the liquid crystal alignment film when applying the liquid crystal alignment treatment agent, when a polyimide precursor, polyimide, polyamide or polyester is used as the polymer, It is preferable to use it in combination with the above solvents A. At that time, the amount of the solvent B is preferably 1 to 99% by mass of the whole solvent contained in the liquid crystal alignment treatment agent. Among them, 10 to 99 mass% is preferable. More preferably, it is 20 to 95% by mass.
  • the liquid crystal alignment treatment agent includes a compound having an epoxy group, an isocyanate group, an oxetane group, a cyclocarbonate group, a hydroxy group, a hydroxyalkyl group or a lower alkoxyalkyl group (collectively, a crosslinker in order to enhance the film strength of the liquid crystal alignment film It is also preferable to introduce a compound). In that case, it is necessary to have two or more groups in the compound.
  • the liquid crystal alignment treatment agent is a group selected from an epoxy group, an isocyanate group, an oxetane group, a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group, an alkoxyalkyl group having 1 to 3 carbon atoms, or a polymerizable unsaturated bond group. It is preferable to include at least one crosslinkable compound composed of a compound having two or more.
  • crosslinkable compound having an epoxy group or an isocyanate group examples include the crosslinkable compounds having an epoxy group or an isocyanate group described on pages 63 to 64 of WO 2014/171493.
  • Specific examples of the crosslinkable compound having an oxetane group include crosslinkable compounds of the formulas [4a] to [4k] described on pages 58 to 59 of International Publication WO2011/132751.
  • crosslinkable compound having a cyclocarbonate group examples include crosslinkable compounds of the formulas [5-1] to [5-42] described on pages 76 to 82 of WO 2012/014898.
  • Specific examples of the crosslinkable compound having a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group include melamine derivatives or benzoguanamine derivatives described on pages 65 to 66 of WO2014/171349, and WO2011/132751.
  • the content of the crosslinkable compound in the liquid crystal alignment treatment agent is preferably 0.1 to 100 parts by mass with respect to 100 parts by mass of all polymer components contained in the liquid crystal alignment treatment agent. In order to allow the crosslinking reaction to proceed and to produce the desired effect, 0.1 to 50 parts by mass is more preferable, and 1 to 30 parts by mass is most preferable, relative to 100 parts by mass of all polymer components. ..
  • a compound that improves the film thickness uniformity and the surface smoothness of the liquid crystal alignment film when the liquid crystal alignment treatment agent is applied can be used. Further, a compound or the like that improves the adhesiveness between the liquid crystal alignment film and the electrode substrate can be used.
  • Compounds that improve the film thickness uniformity and surface smoothness of the liquid crystal alignment film include fluorine-based surfactants, silicone-based surfactants, and nonion-based surfactants. Specific examples thereof include the surfactants described on page 67 of International Publication WO2014/171493. Further, the use ratio thereof is preferably 0.01 to 2 parts by mass with respect to 100 parts by mass of all polymer components contained in the liquid crystal alignment treatment agent. More preferably, it is 0.01 to 1 part by mass.
  • the compound that improves the adhesiveness between the liquid crystal alignment film and the electrode substrate include the compounds described on pages 67 to 69 of International Publication WO2014/171493. Further, the use ratio thereof is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of all polymer components contained in the liquid crystal alignment treatment agent. More preferably, it is 1 to 20 parts by mass.
  • a liquid crystal alignment treatment agent may be added with a dielectric or a conductive substance for the purpose of changing the electrical properties such as the dielectric constant and conductivity of the liquid crystal alignment film.
  • the liquid crystal alignment treatment agent can be used as a liquid crystal alignment film by applying alignment treatment by rubbing treatment or light irradiation after coating and baking on the substrate. Further, in the case of vertical alignment applications, it can be used as a liquid crystal alignment film without alignment treatment.
  • the substrate used in this case is not particularly limited as long as it is a highly transparent substrate, and in addition to glass substrates, acrylic substrates, polycarbonate substrates, plastic substrates such as PET (polyethylene terephthalate) substrates, and further films thereof. Can be used. From the viewpoint of simplifying the process, a substrate on which an ITO electrode for driving a liquid crystal, a metal electrode such as an IZO (Indium Zinc Oxide) electrode and an IGZO (Indium Gallium Zinc Oxide) electrode, and an organic conductive film are formed. Is preferably used. Further, in the case of a reflective liquid crystal display element, if only one substrate is used, a substrate such as a silicon wafer or a metal such as aluminum or a substrate on which a dielectric multilayer film is formed can be used.
  • the method for applying the liquid crystal alignment treatment agent is not particularly limited, but industrially, a method such as screen printing, offset printing, flexographic printing or an inkjet method is generally used. Other coating methods include a dip method, a roll coater method, a slit coater method, a spinner method or a spray method, and these may be used depending on the purpose.
  • After applying the liquid crystal alignment treatment agent on the substrate it is preferably heated at 30 to 300° C., depending on the solvent used for the liquid crystal alignment treatment agent, by a heating means such as a hot plate, a heat circulation type oven or an IR (infrared) type oven. Can be used as a liquid crystal alignment film by evaporating the solvent at a temperature of 30 to 250° C.
  • the thickness of the liquid crystal alignment film after firing is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display device, and if it is too thin, the reliability of the liquid crystal display device may be deteriorated. Is 10 to 200 nm.
  • the liquid crystal alignment film after firing is treated by rubbing or irradiation with polarized ultraviolet light.
  • the liquid crystal used for the liquid crystal display element is not particularly limited, but for example, nematic liquid crystal, smectic liquid crystal or cholesteric liquid crystal can be used.
  • a liquid crystal having a positive or negative dielectric anisotropy can be selected according to the method of the liquid crystal display element.
  • a dichroic dye may be dissolved in the liquid crystal to form a guest-host type liquid crystal display device.
  • the method of injecting the liquid crystal is not particularly limited, but for example, the following method may be mentioned. That is, a pair of substrates on which a liquid crystal alignment film is formed is prepared, and a sealant is applied to all four of the substrates on one side except for a part thereof, and then the liquid crystal alignment film surface is placed inside and the other side is applied. An empty cell in which the above substrates are bonded together is produced. Then, a method of injecting liquid crystal under reduced pressure from a place where the sealant is not applied to obtain a liquid crystal injection cell can be mentioned. Furthermore, prepare a pair of substrates on which a liquid crystal alignment film is formed, drop the liquid crystal on one substrate by ODF (One Drop Filling) method or inkjet method, and then bond the other substrate. Another method is to obtain a liquid crystal injection cell.
  • ODF One Drop Filling
  • the method of controlling the gap of the liquid crystal display device is not particularly limited, for example, a method of introducing a spacer of a desired size in the liquid crystal, a method of coating on a substrate having a column spacer of the desired size, the purpose A method using a liquid crystal containing a column spacer having a size of
  • the size of the gap of the liquid crystal display element is preferably 1 to 100 ⁇ m, more preferably 1 to 50 ⁇ m, and particularly preferably 2 to 30 ⁇ m. If the gap is too small, the contrast of the liquid crystal display device will be lowered, and if it is too large, the driving voltage of the device will be high.
  • solvent NMP: N-methyl-2-pyrrolidone
  • NEP N-ethyl-2-pyrrolidone
  • BCS ethylene glycol monobutyl ether
  • PB propylene glycol monobutyl ether
  • the imidization ratio is determined by using a proton derived from a structure that does not change before and after imidization as a reference proton, and the peak integrated value of this proton and the proton peak derived from the NH group of amic acid that appears near 9.5 ppm to 10.0 ppm. It was calculated by the following formula using the integrated value.
  • Imidization rate (%) (1- ⁇ x/y) ⁇ 100 (X is a proton peak integrated value derived from NH group of amic acid, y is a peak integrated value of reference proton, ⁇ is a reference proton for one NH group proton of amic acid in the case of polyamic acid (imidization rate is 0%) Is the proportion of the number of.)
  • Table 1 shows the polyimide-based polymers obtained in the synthesis examples. *1: Polyamic acid. *2: Polyamic acid alkyl ester.
  • a 6 ⁇ m spacer is applied to the liquid crystal alignment film surface of one substrate, and a sealant (723K1, manufactured by Kyoritsu Chemical Industry Co., Ltd.) is applied to the liquid crystal alignment film surface of the other substrate.
  • the bonding was performed so that the liquid crystal alignment film surfaces of the substrates face each other.
  • the application amount of the sealing agent was adjusted so that the area of the sealing agent after the bonding was 5 ⁇ 50 mm (length ⁇ width).
  • the bonded substrates are irradiated with 3 J/cm 2 of ultraviolet rays at a wavelength of 365 nm by using a metal halide lamp with an illuminance of 20 mW/cm 2 , and then heated at 120° C.
  • the liquid crystal alignment treatment agents obtained in Examples and Comparative Examples were pressure-filtered with a membrane filter having a pore size of 1 ⁇ m, and washed with pure water and IPA.
  • a substrate with ITO electrodes (length 40 mm ⁇ width 30 mm, thickness) (0.7 mm) ITO surface is spin-coated, and heat-treated at 120° C. for 2 minutes on a hot plate and at 230° C. for 30 minutes in a heat circulation type clean oven to have a liquid crystal alignment film with a thickness of 100 nm.
  • the ITO substrate of was obtained.
  • liquid crystal alignment film surface of this substrate was rubbed with a rubbing device having a roll diameter of 120 mm under the conditions of a roll rotation speed of 500 rpm, a roll advancing speed of 30 mm/sec, and a pushing amount of 0.3 mm. Processed.
  • a spacer of 4 ⁇ m is applied to the liquid crystal alignment film surface of one substrate, and a sealant (XN- 1500T) (manufactured by Kyoritsu Kagaku Sangyo Co., Ltd.) was applied, and the substrates were laminated so that the liquid crystal alignment film surfaces of these substrates face each other. At that time, the substrates were laminated so that the rubbing directions of the substrates were opposite to each other.
  • heat treatment was performed at 120° C. for 90 minutes in a heat circulation type clean oven to prepare an empty cell. Liquid crystal was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain a liquid crystal cell.
  • Example 1 to 5 and 14 and Comparative Examples 1 and 2 a positive type liquid crystal (MLC-2003) (manufactured by Merck) was used as the liquid crystal, and in Examples 6 to 13 and Comparative Examples 3 and 4, the liquid crystal was used. Negative liquid crystal (MLC-6608, manufactured by Merck) was used.
  • MLC-2003 positive type liquid crystal
  • MLC-6608, manufactured by Merck negative liquid crystal
  • the liquid crystal cell was stored in a constant temperature and constant humidity chamber at a temperature of 80° C. and a humidity of 90% RH for 48 hours, and peeling of the liquid crystal cell and the presence or absence of bubbles were confirmed. Specifically, the liquid crystal cell is not peeled (a state where it is peeled between the liquid crystal alignment film and the sealant and between the liquid crystal alignment film and the ITO electrode), and bubbles are generated in the liquid crystal cell. Those which were not evaluated were considered to be excellent in this evaluation (good display in the table).
  • Example 1 A1 (0.20 g), NMP (23.8 g) and BCS (7.83 g) were added to the polyamic acid solution (1) (10.0 g) obtained in Synthesis Example 1, and the mixture was stirred at 25° C. for 15 hours. Thus, a liquid crystal alignment treatment agent (1) was obtained.
  • Example 3 A1 (0.20 g), K2 (0.13 g), NMP (23.8 g) and BCS (7.83 g) were added to the polyamic acid solution (2) (10.0 g) obtained in Synthesis Example 2, The mixture was stirred at 25°C for 15 hours to obtain a liquid crystal alignment treatment agent (3).
  • NEP (31.3 g) was added to the polyimide powder (4) (2.50 g) obtained in Synthesis Example 4, and the mixture was stirred at 60° C. for 24 hours to be dissolved.
  • A1 (0.13 g) and BCS (7.83 g) were added to this solution, and the mixture was stirred at 25° C. for 15 hours to obtain a liquid crystal alignment treatment agent (5).
  • A1 (0.18 g), NMP (16.0 g) and BCS (15.7 g) were added to the polyamic acid solution (5) (10.0 g) obtained in Synthesis Example 5, and the mixture was stirred at 25° C. for 15 hours.
  • a liquid crystal alignment treatment agent (6) was obtained.
  • Example 7 A1 (0.18 g), NMP (16.0 g) and BCS (15.7 g) were added to the polyamic acid solution (6) (10.0 g) obtained in Synthesis Example 6, and the mixture was stirred at 25° C. for 15 hours. Thus, a liquid crystal alignment treatment agent (7) was obtained.
  • NEP (23.5 g) was added to the polyimide powder (7) (2.50 g) obtained in Synthesis Example 7, and the mixture was stirred at 60° C. for 24 hours to be dissolved.
  • Example 11 A1 (0.25 g), NMP (16.0 g) and BCS (15.7 g) were added to the polyamic acid solution (9) (10.0 g) obtained in Synthesis Example 9, and the mixture was stirred at 25° C. for 15 hours. Thus, a liquid crystal alignment treatment agent (11) was obtained.
  • Example 12 To the polyamic acid solution (9) (10.0 g) obtained in Synthesis Example 9, A1 (0.25 g), K2 (0.08 g), NMP (16.0 g) and BCS (15.7 g) were added, The mixture was stirred at 25°C for 15 hours to obtain a liquid crystal alignment treatment agent (12).
  • Example 13 In the polyamic acid solution (10) (10.0 g) obtained in Synthesis Example 10, A1 (0.08 g), K1 (0.18 g), NMP (16.0 g), BCS (7.83 g) and PB( 7.83 g) was added and the mixture was stirred at 25° C. for 15 hours to obtain a liquid crystal alignment treatment agent (13).
  • NMP (31.3 g) was added to the polyamic acid alkyl ester powder (11) (2.50 g) obtained in Synthesis Example 11 and dissolved by stirring at 40° C. for 24 hours. A1 (0.13 g) and BCS (7.83 g) were added to this solution, and the mixture was stirred at 25° C. for 15 hours to obtain a liquid crystal alignment treatment agent (14).
  • *3 Indicates the content (parts by mass) of the specific compound with respect to 100 parts by mass of the polymer.
  • *4 Indicates the content (parts by mass) of the crosslinkable compound with respect to 100 parts by mass of the polymer.
  • *5 A very small amount of bubbles were found in the device.
  • *6 A small amount of bubbles were found in the element (more than *5).
  • *7 Bubbles were found in the element (more than *6).
  • the polymer terminal has a structure of a carboxylic acid anhydride or a dicarboxylic acid, that is, during the polymerization reaction of a diamine component and a tetracarboxylic acid component, a tetracarboxylic acid Those in which the total number of moles of the components is larger than the number of moles of the diamine component have a polymer terminal having a structure of an amino group (in the polymerization reaction, the total number of moles of the tetracarboxylic acid component is smaller than the number of moles of the diamine component.
  • the occurrence of bubbles in the liquid crystal cell in the emphasis test was suppressed as compared with that of No. Specifically, in comparison under the same conditions, there are comparison between Example 1 and Example 2 and comparison between Example 6 and Example 7.
  • the adhesiveness between the substrates of the liquid crystal display device is high, further, even in a harsh environment exposed to high temperature and high humidity for a long time,
  • the liquid crystal display device capable of suppressing the generation of bubbles in the liquid crystal display device and the peeling of the device is particularly obtained. Therefore, it can be suitably used for a liquid crystal display element for mobile devices such as smartphones and mobile phones.

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

Abstract

L'invention concerne : un agent de traitement d'alignement de cristaux liquides qui peut être utilisé pour produire un film d'alignement de cristaux liquides qui présente une excellente stabilité de conservation, fournit une adhésivité (adhérence) élevée entre des substrats d'un élément d'affichage à cristaux liquides, et peut supprimer des bulles d'air générant à l'intérieur de l'élément d'affichage à cristaux liquides ainsi que le détachement de l'élément même dans un environnement exposé à une température élevée et une humidité élevée pendant une longue période de temps ; un film d'alignement de cristaux liquides obtenu en utilisant ledit agent ; et un élément d'affichage à cristaux liquides. L'agent de traitement d'alignement de cristaux liquides contient un composé comprenant un groupe représenté par la formule [1]. (* représente le site de liaison à une autre structure.)
PCT/JP2019/050687 2018-12-27 2019-12-24 Agent de traitement d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides WO2020138109A1 (fr)

Priority Applications (3)

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KR1020217019557A KR20210108962A (ko) 2018-12-27 2019-12-24 액정 배향 처리제, 액정 배향막 및 액정 표시 소자
CN201980086391.4A CN113260910A (zh) 2018-12-27 2019-12-24 液晶取向处理剂、液晶取向膜以及液晶显示元件
JP2020563321A JP7392663B2 (ja) 2018-12-27 2019-12-24 液晶配向処理剤、液晶配向膜及び液晶表示素子

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6037524A (ja) * 1983-08-10 1985-02-26 Hitachi Ltd 液晶表示装置
JPH10148835A (ja) * 1996-11-19 1998-06-02 Hitachi Chem Co Ltd 液晶配向膜
JP2014527555A (ja) * 2011-08-02 2014-10-16 ロリク アーゲーＲｏｌｉｃ Ａｇ 光配向性材料
US20150291882A1 (en) * 2013-05-31 2015-10-15 Boe Techinology Group Co., Ltd. Alignment and flattening material compositions, display device comprising same and process for adjusting display color

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61171762A (ja) 1985-01-28 1986-08-02 Japan Synthetic Rubber Co Ltd 可溶性ポリイミド樹脂組成物
JP2980080B2 (ja) 1997-10-09 1999-11-22 ジェイエスアール株式会社 液晶配向剤

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6037524A (ja) * 1983-08-10 1985-02-26 Hitachi Ltd 液晶表示装置
JPH10148835A (ja) * 1996-11-19 1998-06-02 Hitachi Chem Co Ltd 液晶配向膜
JP2014527555A (ja) * 2011-08-02 2014-10-16 ロリク アーゲーＲｏｌｉｃ Ａｇ 光配向性材料
US20150291882A1 (en) * 2013-05-31 2015-10-15 Boe Techinology Group Co., Ltd. Alignment and flattening material compositions, display device comprising same and process for adjusting display color

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JP7392663B2 (ja) 2023-12-06
TW202035663A (zh) 2020-10-01
KR20210108962A (ko) 2021-09-03
CN113260910A (zh) 2021-08-13

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