Classifications

• • 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
• • 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
• • 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
• • 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
  • G02F1/137—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 characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering
  • G02F1/139—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 characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering based on orientation effects in which the liquid crystal remains transparent

Definitions

• the present invention relates to a transmission/scattering type liquid crystal display element that controls a transparent state and a scattering state by applying a voltage and a method for manufacturing the same.
• a TN (Twisted Nematic) mode liquid crystal display device has been put into practical use. In this mode, it is necessary to use a polarizing plate in order to switch the light by utilizing the optical rotatory property of the liquid crystal, but the use efficiency of the light becomes low when the polarizing plate is used.
• As an element there is an element that switches between a transparent state (also called a transparent state) and a scattering state of liquid crystal.
• PD LC Polymer Dispersed Liquid Crystal
• PN LC Polymer Network Liquid Crystal
• liquid crystal display elements a liquid crystal composition containing a polymerizable compound that is polymerized by ultraviolet rays is placed between a pair of substrates equipped with electrodes, and the liquid crystal composition is cured by irradiation with ultraviolet rays. And a cured product of a polymerizable compound (for example, a polymer network) are formed.
• a polymerizable compound for example, a polymer network
• Patent Document 1 Japanese Patent No. 3552328.
• Patent Document 2 Japanese Patent No. 4630954.
• the polymerizable compound in the liquid crystal composition is cured, so an ultraviolet irradiation step is required.
• an object of the present invention is to provide a transmission/scattering type liquid crystal display element and a method for producing the same, which does not use a polymerizable compound in a liquid crystal composition and does not require an ultraviolet irradiation step.
• the present inventor has found an invention having the following gist.
• liquid crystal layer containing liquid crystal between a pair of substrates equipped with electrodes, and having a liquid crystal alignment film exhibiting liquid crystallinity on at least one of the substrates, transparent state and scattering state by voltage application Liquid crystal display element of transmission/scattering type for controlling light.
• a transmission-scattering type liquid crystal display element that does not use a polymerizable compound in a liquid crystal composition and does not require an ultraviolet ray irradiation step.
• the liquid crystal display device of the present invention can provide a liquid crystal display intended for display, a dimming window or an optical shutter device for controlling blocking and transmission of light.
• FIG. 1 is a polarizing microscope image (the film shows liquid crystallinity) of the film of the glass substrate with the liquid crystal alignment film obtained in Example 1.
• the present application provides a liquid crystal display element, particularly a transmission/scattering type liquid crystal display element that controls a transparent state and a scattering state by applying a voltage.
• a method for manufacturing the liquid crystal display device is provided.
• the present application has a liquid crystal layer containing liquid crystal between a pair of substrates provided with electrodes, and a liquid crystal alignment film exhibiting liquid crystallinity on at least one of the substrates.
• a scattering transmission type liquid crystal display device for controlling
• the liquid crystal display element of the present invention has a pair of substrates provided with electrodes.
• the substrate is not particularly limited as long as it can have an electrode, but a substrate having high transparency is preferably used.
• a substrate having high transparency is preferably used as the substrate.
• a plastic substrate such as a polyamide substrate, a polyimide substrate, a polyethylene sulfone substrate, an acrylic substrate, a polycarbonate substrate, a PET (polyethylene terephthalate) substrate, and the like.
• Those films can be used, but are not limited to these.
• a plastic substrate or film is preferable.
• the electrode is not particularly limited, but from the viewpoint of process simplification, a liquid crystal driving ⁇ T electrode, ⁇ Z 0 (Indium Zinc Oxide) electrode, ⁇ GZ ⁇ (Indiumum Gallium Zinc Oxide) It is preferable to use a substrate on which electrodes, organic conductive films, etc. are formed.
• 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 pair of substrates are arranged in parallel at a predetermined distance, and a liquid crystal layer containing liquid crystal is arranged between the pair of substrates.
• the electrode gap (also referred to as a gap) of the liquid crystal display element is preferably 2.0 to 50 Mm. It is more preferably 2.0 to 30 Mm, and particularly preferably 2.0 to 20 m.
• At least one of the pair of substrates is a liquid crystal layer of the substrate.
• a liquid crystal alignment film that exhibits liquid crystallinity is arranged on the side where is arranged.
• liquid crystal contained in the liquid crystal layer nematic liquid crystal, smectic liquid crystal or cholesteric liquid crystal can be used.
• those having a positive dielectric anisotropy are preferable in the present invention.
• a liquid crystal having a positive dielectric anisotropy an element that absorbs (scatters) when no voltage is applied and becomes transparent when a voltage is applied can be obtained.
• the liquid crystal display device is used for windows of automobiles, it is preferable that the clearing point (also referred to as T n i) is high.
• the liquid crystal preferably has a large An, preferably an An of 0.20 or more, more preferably 0.22 or more, and particularly preferably 0.26 or more.
• liquid crystal two or more kinds of liquid crystals can be mixed and used according to the physical property values of As and ⁇ n T n i.
• liquid crystal display element As an active element such as a TFT (Thin Film Transistor), it is required that the liquid crystal has a high electric resistance and a high voltage holding ratio (also referred to as VHR). Therefore, as the liquid crystal, it is preferable to use a fluorine-based or chlorine-based liquid crystal which has a high electric resistance and whose V H R does not decrease due to active energy rays such as ultraviolet rays.
• liquid crystal display element can be made into a guest-host type element by dissolving a dichroic dye in the liquid crystal layer.
• the liquid crystal alignment film exhibiting liquid crystallinity is arranged on at least one of the pair of substrates, particularly on the side of the substrate where the liquid crystal layer is arranged.
• the liquid crystal alignment film has a liquid crystallinity in the range of 80 to 350 ° C, preferably 100 to 300°C, more preferably 120 to 250°C. ⁇ 2020/175518 ⁇ (:171?2020/007619
• the liquid crystal alignment film preferably contains a liquid crystalline polymer.
• the liquid crystalline polymer is not particularly limited, but is not limited to acrylic polymer, methacrylic polymer, novolac resin, epoxy resin, polyhydroxystyrene, polyimide precursor, polyimide, polyamide, polyester, polyether, polyurethane, poly(ester). At least one polymer selected from the group consisting of amide), poly(ester-imide), poly(ester-anhydride), poly(ester-carbonate), cellulose and polysiloxane. More preferred is a polyimido precursor or polyimido (collectively referred to as polyimido-based polymer).
• the polyimide precursor has a structure of the following formula [8].
• 2 represents a divalent organic group.
• Each eight 1 and 2 is a hydrogen atom or an alkyl group having a carbon number of 1-8.
• 8 and 3 each represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an acetyl group.
• the door indicates a positive integer.
• the diamine component is a diamine having two primary or secondary amino groups in the molecule
• the tetracarboxylic acid component is a tetracarboxylic oxide compound or a tetracarboxylic dianhydride.
• a tetracarboxylic acid dihalide compound, a tetracarboxylic acid dialkyl ester compound or a tetracarboxylic acid dialkyl ester dihalide compound is a tetracarboxylic oxide compound or a tetracarboxylic dianhydride.
• a polyamic acid having a structural formula of a repeating unit of the formula [or] or a polyimide obtained by imidizing the polyamic acid is preferable. ⁇ 2020/175518 6 ⁇ (: 171-1? 2020/007619
• the polymer of the formula [mouth] obtained above is added to the polymer of the formula [8], which is 1 or 2 having 1 to 8 carbon atoms, and 3 and eight 4 alkyl group or an acetyl group with carbon number from 1 to 5 can also be introduced.
• the liquid crystalline polymer preferably has at least one partial structure (also referred to as a specific partial structure ()) selected from the following formulas [8 1] to [8 4], and preferably the formula [8] 4] is preferable.
• the liquid crystalline polymer is at least one selected from the following formulas [Mis 1] to [Mis 7]. ⁇ 2020/175518 7 ⁇ (: 171-1? 2020/007619
• Also has one kind of partial structure also referred to as a specific partial structure (Mi)
• a specific partial structure Mi
• ⁇ each independently represents an alkyl group having 1 to 3 carbon atoms, preferably 1 to 2 carbon atoms.
• n 1 to n 4 each independently represent an integer of 0 to 2, preferably 0 or 1. Hydrogen on the aromatic ring, _ ⁇ _1 to 1 3, ten 3, over one Rei_1 ⁇ 1, one thousand 1 to 1, one 1 ⁇ 1_Rei 2, one-! - snake hundred, Or — (600) 2 may be substituted (where ___ is ⁇ “1:-butoxycarbonyl group”).
• the liquid crystalline polymer is selected from at least one partial structure selected from the following formulas [8 1] to [8 4] and the following formulas [M 1] to [M 7] It is preferably a polyimide-based polymer having at least one kind of partial structure.
• a diamine having a specific partial structure (8) (also referred to as a specific diamine (8).) ⁇ 2020/175 518 8 ⁇ (:171? 2020 /007619
• a tetracarboxylic acid having a specific partial structure (Minami) (also referred to as a specific tetracarboxylic acid (B)), a diamine of the following formula [18] and a tetracarboxylic acid of the formula [2] are used, respectively. It is preferable.
• X 1 and X 3 are each independently a single bond, 101, -001, 100001, 10001, 1CNH- , 1 ⁇ 1 1 ⁇ 1 x 0 1 or 1 !-indicates at least one selected from. Among them, a single bond, 101, 1001, 100001 or 100001 is preferable.
• X 2 represents at least one selected from the above formula [8 1] to formula [8 4]. Above all, the formula [1] or the formula [4] is preferable from the viewpoint of the optical characteristics of the liquid crystal display device. Also, formula [8 1] to formula [8 4]
• each of 1 and 5 independently represents at least one selected from an aromatic ring, an alicyclic group and a heterocyclic group. Of these, an aromatic ring or an alicyclic group is preferable.
• 2 and 4 are each independently a single bond, 101, 1001, -0000 -, 1001, ⁇ one or one Indicates at least one selected from Of these, a single bond, 101, 1001, 100001 or —0.000— is preferable.
• Reference numeral 3 represents at least one selected from the above formulas [Mis 1] to [Mis 7]. Among them, from the viewpoint of the optical characteristics of the liquid crystal display device, the formula [Min 1], the formula [Min 4] or the formula [Min 7] is preferable. Further, the details and preferred values of 3 to 30 and n 1 to 114 in the formulas [Mis 1] to [Mis 7] are as described above.
• n 5 and n 6 each independently represent an integer of 0 or 1.
• n 5 and n 6 are integers of 0, the structures of the formulas [Mis 1] to [Mis 7] are assumed to be directly bonded to the bond of the tetracarboxylic acid.
• the use ratios of the specific diamine (8) and the specific tetracarboxylic acid (Mitsumi) are preferably as follows. Specifically, the use ratio of the specific diamine (8) is preferably 30 to 100 mol%, and preferably 50 to 100 mol% with respect to the entire diamine component from the viewpoint of the optical characteristics of the liquid crystal display element. More preferable. From the viewpoint of the optical characteristics of the liquid crystal display element, the use ratio of the specific tetracarboxylic acid (Mitsumi) is preferably 30 to 100 mol %, and preferably 50 to 100 mol% based on the whole tetracarboxylic acid component. % Is more preferable. Further, the specific diamine (8) and the specific tetracarbonic acid (Mitsumi) can be used either individually or in combination of two or more, depending on their respective characteristics.
• X 4 represents at least one selected from the formulas [1] to [7].
• the formula [Mis 1], the formula [Mis 4] or the formula [Mis 7] is preferable.
• 3 to 3° and 1 to in expression [Mis 1] to [Mis 7] The details and preferences of 4 are as described above.
• each of 6 and 1 independently represents at least one selected from an aromatic ring, an alicyclic group and a heterocyclic group. Of these, an aromatic ring or an alicyclic group is preferable.
• 7 and 9 are each independently a single bond, 101, 1001, -0000-, 10011, ⁇ one or one Few to choose from ⁇ 2020/175 518 10 ⁇ (:171? 2020 /007619
• Reference numeral 8 represents at least one selected from the formula [8 1] to the formula [8 4]. Among them, the formula [84] is preferable from the viewpoint of the optical characteristics of the liquid crystal display device. Also,
• Each of 7 and n 8 independently represents an integer of 0 or 1.
• the use ratio of each of the specific diamine (Mitsumi) and the specific tetracarboxylic acid (8) is preferably as follows. Specifically, from the viewpoint of the optical characteristics of the liquid crystal display element, the usage ratio of the specific diamine (Mitsumi) is preferably 30 to 100 mol% with respect to the entire diamine component, and 50 to 100 mol% is preferable. More preferable. From the viewpoint of the optical characteristics of the liquid crystal display element, the use ratio of the specific tetratracarboxylic acid () is preferably 30 to 100 mol %, and preferably 50 to 100 mol% with respect to the whole tetracarboxylic acid component. Is more preferable. Further, the specific diamine (Mitsumi) and the specific tetracarbonic acid () can be used either individually or in combination of two or more, depending on their respective characteristics.
• a diamine other than the specific diamine (8) and the specific diamine (Mitsumi) can be used as long as the effects of the present invention are not impaired.
• the formula described on pages 34 to 38 of International Publication Gazette ⁇ / ⁇ 2 0 1 6/0 7 6 4 1 2 (2 0 16.5.19 publication) [3 3-1] to diamine compounds of the formula [3 3-5] other diamine compounds described on pages 39 to 42 of the publication, and on pages 42 to 44 of the publication. Examples include diamine compounds represented by the formulas [0 8 1] to [0 8 15].
• Other Jami ⁇ 2020/175518 11 ⁇ (: 171-1? 2020/007619
• the specific tetracarboxylic acid () and the specific tetracarboxylic acid (Mi) are the tetracarboxylic dianhydrides of the above formulas [2 8] and [2] and their tetracarboxylic acid derivatives.
• a tetracarboxylic acid dihalide compound, a tetracarboxylic acid dialkyl ester compound or a tetracarboxylic acid dialkyl ester dihalide compound can be used.
• tetracarboxylic acid component other tetracarboxylic acid other than the specific tetracarboxylic acid () and the specific tetracarboxylic acid (Mitsumi) can be used.
• examples of other tetracarboxylic acids include the following tetracarboxylic acid compounds, tetracarboxylic acid dianhydrides, dicarboxylic acid dihalide compounds, dicarboxylic acid dialkyl ester compounds and dialkyl ester dihalide compounds.
• 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. Specifically, the method described on pages 46 to 50 of WO 201 6/0764 1 2 (Published on May 6, 2010) can be mentioned.
• 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 formed polyimide precursor. Specifically, 1 ⁇ !-methyl-2-pyrrolidone, 1 ⁇ 1-ethyl-2-pyrrolidone, arbutyrolactone, 1 ⁇ 1, 1 ⁇ 1_dimethylformamide, 1 ⁇ 1, 1 ⁇ 1_dimethyl Acetamide, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone and the like can be mentioned.
• methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy _4-methyl-2-pentanone or one of the following formulas [mouth 1] to formula [mouth 3] A solvent can be used.
• Port 2 represents an alkyl group having 1 to 3 carbon atoms.
• Port 3 represents an alkyl group having 1 to 4 carbon atoms.
• these may be used alone or in combination.
• a solvent that does not dissolve the polyimide precursor may be used as a mixture with the above-mentioned solvent as long as the formed polyimide precursor does not precipitate.
• water in the organic solvent inhibits the polymerization reaction and causes hydrolysis of the formed polyimide precursor, it is preferable to use dehydrated and dried organic solvent.
• the total number of moles of the tetracarboxylic acid component is 0.8 to 1.2 when the total number of moles of the diamine component is 1.0. ..
• Polyimide is a polyimide obtained by ring closure of a polyimide precursor, and in this polyimide, the ring closure rate (also referred to as imidation rate) of amide acid groups does not necessarily have to be 100%. , It can be adjusted arbitrarily according to the application and purpose. Among them, 30 to 80% is preferable from the viewpoint of the solubility of the polyimide polymer in the solvent. More preferred is 40 to 70%.
• the molecular weight of the polyimido polymer is determined by GPC (Gel Permeati on Chromatography)
• the measured weight average molecular weight is preferably from 5,000 to 1,000, 000, more preferably from 10,000 to 150,000.
• the liquid crystal display element of the present invention can be manufactured, for example, by the following manufacturing method. ⁇ 2020/175 518 13 ⁇ (: 171-1? 2020/007619
• the first substrate and the second substrate obtained in the step (IV) are arranged such that the liquid crystal alignment film faces the second substrate, and the first substrate and the second substrate described above are arranged. Arranging so as to be spaced apart from the second substrate;
• V I I A step of filling a liquid crystal into the separated space to form a liquid crystal layer
• the step () is a step of preparing the first substrate.
• the first substrate has the same definition as the above-mentioned substrate, and for example, a glass substrate or a plastic substrate can be used if it is a transparent substrate.
• the step ( ⁇ ) is a step of preparing a liquid crystal alignment treatment agent having a liquid crystalline polymer.
• the liquid crystalline polymer has the same definition as above.
• the liquid crystal alignment treatment agent is a solution for forming a liquid crystal alignment film, and contains the liquid crystalline high molecule and a predetermined solvent.
• the liquid crystal polymer one kind or two or more kinds can be used.
• the content of the solvent in the liquid crystal alignment treatment agent can be appropriately selected from the viewpoint of a method of applying the liquid crystal alignment treatment agent and obtaining a target film thickness.
• 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.
• 60 to 99 mass% is preferable. More preferably, it is 65 to 99% by mass. ⁇ 2020/175 518 14 (:171? 2020/007619
• the solvent used for the liquid crystal alignment treatment agent is not particularly limited as long as it is a solvent that dissolves the liquid crystalline polymer.
• the liquid crystalline polymer is a polyimide precursor, a polyimide, a polyamide, a polyester, a polyether, a polyurethane, a poly(esteramide), a poly(ester-imide), a poly(ester-anhydride) or a poly(ester-anhydride).
• solvent solvent It is also referred to as Eight kinds.
• 1 ⁇ 1_methyl-2-pyrrolidone, 1 ⁇ 1-ethyl-2-pyrrolidone or ⁇ -butyrolactone is preferable. These may be used alone or in combination.
• the liquid crystalline polymer is an acrylic polymer, a methacrylic polymer, a novolac resin, an epoxy resin, polyhydroxystyrene, cellulose or polysiloxane
• the liquid crystalline polymer is a polyimido precursor, a polyimid , Poly(amide), polyester, polyether, polyurethane, poly(ester amide), poly(ester-imide), poly(ester-anhydride) or poly(ester-carbonate), and their solubility in these solvents is When it is high, the following solvents (also called solvent solvents) can be used.
• solvent solvents are described on pages 58 to 60 of International Publication No. ⁇ 2 0 1 4/1 7 1 4 9 3 (2 0 1 4 1 .0.2 3 publication). Solvents such as Among them, 1-hexanol, cyclohexanol, 1,2-ethanedine
• the liquid crystal polymer can be used as a polyimide precursor, a polyimide, a polyamide, or a polyester.
• Polyether, polyurethane, poly(ester amide), poly(ester-imide), poly(ester-anhydride) or poly(ester-carbonate) should be used together with the above solvents.
• the amount of the solvent 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.
• 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 is introduced into the liquid crystal alignment treatment agent. You can also do it. In that case, it is necessary for the compound to have two or more of these groups.
• crosslinkable compound having an epoxy group or an isocyanate group are described in International Publication WO 201 4/1 7 1 493 (published 201 4.10.23), pages 63 to 64.
• examples thereof include crosslinkable compounds having a group or an isocyanate group.
• crosslinkable compound having an oxetane group are represented by the formulas shown on pages 58 to 59 of International Publication WO ⁇ /0201 1/1 3275 1 (201 1.1.0.27 publication). ⁇ Crosslinkable compounds of the formula [4 ! ⁇ ] are mentioned.
• crosslinkable compound having a cyclocarbonate group examples include compounds represented by the formula [5-1] disclosed on pages 76 to 82 of International Publication No. 0201 2/01 4898 (201 2.2.2 publication). ⁇ Crosslinkable compounds of the formula [5-42] are mentioned. Hydroxyl group, hydroxyalkyl group and lower alkoxyalkyl group ⁇ 2020/175 518 16 ⁇ (: 171-1? 2020/007619
• crosslinkable compound examples have the melamine derivative or the benzoguanamine derivative described on pages 65 to 66 of International Publication No. 201 4/1 7 1 493 (published on 2 01 4.1 0.23), and International There are cross-linkable compounds represented by the formulas [6-1] to [6_48], which are described on pages 62 to 66 of Published Publication No. 201 1/1 3275 1 (published on January 1.1 0.27).
• the content of the crosslinkable compound in the liquid crystal alignment treatment agent is not limited to all polymer components 1
• 0.1 to 100 parts by mass is preferable with respect to 00 parts by mass.
• 0.1 to 50 parts by mass is more preferable, and most preferably 1 to 30 parts by mass, relative to 100 parts by mass of all polymer components. It is a department.
• liquid crystal alignment treatment agent 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 as long as the effect of the present invention is not impaired. .. Furthermore, a compound or the like that improves the adhesion between the liquid crystal alignment film and the electrode substrate can be used.
• Examples of the compound that improves the film thickness uniformity and surface smoothness of the liquid crystal alignment film include a fluorine-based surfactant, a silicone-based surfactant, and a nonionic surfactant. Specifically, International Publication ⁇ 201 4/1 7 1 493 (
• 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 preferred is 0.01 to 1 part by mass.
• 30 parts by mass is preferred. More preferably, it is 1 to 20 parts by mass.
• the liquid crystal alignment treatment agent may be added with a dielectric or conductive substance for the purpose of changing the electrical properties of the liquid crystal alignment film, such as the dielectric constant and conductivity.
• the step ( ⁇ ) is a step of applying the liquid crystal alignment treatment agent to one surface of the first substrate.
• the method of applying the liquid crystal alignment treatment agent is not particularly limited, but industrially, screen printing, offset printing, flexo printing ! ⁇ , ink jet method, dip method, mouth coater method, slit coater method, spinner method.
• a spray method, etc. which can be appropriately selected according to the type of substrate and the film thickness of the target film.
• Step (V) is a step of heating the obtained coated surface to form a liquid crystal alignment film on the first substrate.
• the heating that is, the heat treatment, depends on the type of substrate used, the liquid crystal alignment treatment agent used, particularly the solvent used for the liquid crystal alignment treatment agent, and the temperature range where the liquid crystallinity of the liquid crystal alignment film develops.
• the temperature is preferably 80 to 350°, preferably 100 to 300°, more preferably 120 to 250°.
• the thickness of the liquid crystal alignment film after calcination,. 5 to 5 0 0 n m, preferably 1 0-3 0 0 11_Rei_1, more preferably 1 ⁇ _ ⁇ 2 5 0 ⁇ ! A is the good.
• Step (V) is a step of preparing the second substrate.
• the second substrate is not particularly limited as long as it has electrodes, and may be the same as or different from the first substrate.
• the second substrate preferably has a liquid crystal alignment film, as in the first substrate.
• the first substrate and the second substrate obtained in the step (IV) are arranged so that the liquid crystal alignment film faces the second substrate, and the first substrate and the second substrate are arranged.
• the liquid crystal alignment film is preferably arranged so as to face the first substrate.
• a spacer may be introduced in order to control the gap (also referred to as a gap) between the substrates.
• the gap depends on the type of substrate used, the liquid crystal alignment treatment agent used, etc., but is preferably 2.0 to 50, preferably 2 to 25, and more preferably 2 to 20.
• the step (V I I) is a step of filling a separated space with liquid crystal to form a liquid crystal layer.
• liquid crystal and the liquid crystal layer have the same definition as described above.
• the method of injecting liquid crystal is not particularly limited, but the following method may be mentioned, for example. That is, when using a glass substrate as a substrate, prepare a pair of substrates having a liquid crystal alignment film formed thereon, apply a sealant except for a part of four pieces of the substrate on one side, and then, Fabricate an empty cell with the other side of the substrate attached so that the surface is on the inside. Then, a method of obtaining a liquid crystal injection cell by injecting liquid crystal under reduced pressure from a position where the sealant is not applied can be mentioned.
• the liquid crystal injection cell can be obtained by dropping the liquid crystal by the ink jet method or the ink jet method and then bonding the other substrate.
• the gap of the liquid crystal display element can be controlled by the above spacer or the like.
• a method of introducing a spacer of a desired size into the liquid crystal a method of using a substrate having a column spacer of a desired size, and the like can be mentioned.
• the gap can be controlled without introducing spacers.
• the liquid crystal display element in which liquid crystal is injected is added for the purpose of stabilizing the alignment of the liquid crystal. ⁇ 2020/175518 19 ⁇ (: 171-1? 2020/007619
• the temperature at that time is preferably 40 to 150 ° . More preferably, it is 60 to 120 ° .
• the method for manufacturing a liquid crystal display element of the present invention may include steps other than the above steps () to (VI). For example, as described above, heat treatment may be performed after the step (V I I) for the purpose of stabilizing the alignment of the liquid crystal.
• the liquid crystal display device of the present invention can be applied to, for example, a liquid crystal display for display purposes, and further to a dimming window or an optical shutter device that controls blocking and transmission of light. Not limited to.
• Liquid crystal with physical properties of !_ 3 ( Ding: 102 ° 0, 8 ⁇ :a. 4, 8: ⁇ .236)
• Liquid crystal with physical properties of !_4 (Cho: 90°, eight ⁇ : a. 4, eight: ⁇ .299)
• Haze meter 1 to 12- 3 (manufactured by Suga Test Instruments Co., Ltd.)
• the medicine (7) was obtained. No abnormalities such as turbidity or precipitation were observed in this liquid crystal alignment treatment agent, and it was a uniform solution.
• Table 1 shows the liquid crystal alignment treatment agents obtained in the synthesis examples.
• the liquid crystal alignment treatment agent obtained by the method of Synthesis Example was pressure-filtered with a membrane filter having a pore size of 1.
• the obtained solution was spin-coated on a glass substrate (vertical: 300111111, lateral: 400!, thickness: 0.0) washed with pure water and isopropyl alcohol. At 80 ° ⁇ at 120 seconds, I
• a glass substrate with a liquid crystal alignment film having a film thickness of 100 mm was obtained by performing heat treatment at 150 ° C. for 30 minutes in an 8 (infrared) type heat circulation type clean oven.
• the liquid crystallinity of the obtained glass substrate with a liquid crystal alignment film was confirmed using the above-mentioned polarizing microscope with a cooling and heating stage for a microscope. Specifically, by observation with a polarizing microscope, those with an optical texture derived from the liquid crystal phase as shown in Fig. 1 were regarded as having liquid crystallinity, and those not observed were regarded as having no liquid crystallinity.
• a liquid crystal alignment film was sampled from the glass substrate with the liquid crystal alignment film obtained above, and the endothermic peak (liquid crystal phase/liquid crystal phase transition was measured using the differential scanning calorimeter (0 30). ) (Also referred to as Ding 1) and an endothermic peak (indicating a liquid crystal phase/isotropic phase transition) (also referred to as Ding 2) at which the rate of temperature rise/fall is 10 D/min and Ding 1 and Ding 2 were obtained from the second skiyan.
• Ding 1 and Ding 2 an endothermic peak at which the rate of temperature rise/fall is 10 D/min and Ding 1 and Ding 2 were obtained from the second skiyan.
• the liquid crystal alignment treatment agent obtained by the method of Synthesis Example was pressure-filtered with a membrane filter having a pore size of 1.
• the obtained solution was washed with pure water and ⁇ (isopropyl alcohol) ⁇ ⁇
• Glass substrate with electrodes (vertical: 40, horizontal: 3 0 01 111, thickness: 0.7 0 111 1 1) Spin coat on the surface and place it on the hot plate at 80 ° for 90 seconds.
• a glass substrate with a liquid crystal alignment film of was obtained.
• the heating treatment in the type I heat-circulation type clean oven was performed at 180° ⁇ for 30 minutes, and in Example 8 at 200° ⁇ for 30 minutes.
• Example 9 Example 10 and Comparative Examples 5 to 8 were performed at 230 ° for 30 minutes.
• a liquid crystal cell was obtained by leaving it at 23 ° for 15 hours.
• the obtained liquid crystal cell was subjected to no voltage application ( ⁇ V) and voltage application (AC drive: 20 V). (Haze) was measured.
• the measurement is based on I 3 ⁇ 7 1 3 6, and the higher the value of 1 to 1 3 2 6 when no voltage is applied, the better the scattering characteristics, and the lower the value of !! 3 2 6 when a voltage is applied, the more transparent it is. It is said that it has excellent properties.
• the Examples using the liquid crystal alignment treatment agent containing the specific polyimide polymer using the specific diamine and the specific tetracarboxylic acid do not contain them, or either Compared to the comparative example of the liquid crystal alignment treatment agent containing only one, the liquid crystal alignment film exhibited liquid crystallinity and had good optical characteristics, that is, Haze in the state without voltage application was high, and Haze in voltage application state was high. Became lower.
• the expression of liquid crystallinity is a comparison between Examples 1 to 3 and Comparative Examples 1 to 4, and the optical characteristics are a comparison between Examples 4 to 10 and Comparative Examples 5 to 8.
• the present liquid crystal display element can be used for a liquid crystal display intended for display, and also for a dimming window or an optical shutter element for controlling the blocking and transmission of light.
• a plastic substrate be able to.
• the device can also be used as a light guide plate of a display device such as an LC D (Liquid Crystal Display) or an LED (Organic Light-emitting Diode) display, or a back plate of a transparent display using these displays.

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