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
  • G02F1/1334—Constructional arrangements; Manufacturing methods based on polymer dispersed liquid crystals, e.g. microencapsulated liquid crystals
• • 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
  • C08G73/1075—Partially aromatic polyimides
  • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
• • 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
  • 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
• • 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 transmission-scattering normal type liquid crystal display element that is in a scattering state when no voltage is applied and is in a transmission state when a voltage is applied.
• a TN (Twisted Nematic) mode As a liquid crystal display element, a TN (Twisted Nematic) mode has been put into practical use. In this mode, it is necessary to use a polarizing plate to switch the light by utilizing the optical rotation property of the liquid crystal. If a polarizing plate is used, the light utilization efficiency will be low.
• a liquid crystal display element that does not use a polarizing plate, there is an element that switches between a transparent state (also called a transparent state) and a scattering state of liquid crystal.
• a transparent state also called a transparent state
• a scattering state of liquid crystal In general, those using a high molecular dispersion liquid crystal (also referred to as PD LC (Polymer Dispersed Liquid Crystal)) or a polymer network liquid crystal (PN LC (Polymer Network Liquid Crystal) are known. ing.
• PD LC Polymer Dispersed Liquid Crystal
• PN LC Polymer Network Liquid Crystal
• liquid crystal display elements In these 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 to It forms a complex with a cured product of a polymerizable compound (for example, a polymer network). Then, in this liquid crystal display element, the scattering state and the transmitting state of the liquid crystal are controlled by applying a voltage.
• a polymerizable compound for example, a polymer network
• the liquid crystal In a liquid crystal display device using PD LC or PN LC, the liquid crystal is oriented in a random direction when no voltage is applied, resulting in a cloudy (scattering) state, and when voltage is applied, the liquid crystal is aligned in the electric field direction.
• a normal type liquid crystal display element that transmits light and becomes a transmissive state (also called a normal type element).
• the electrode and the liquid crystal layer are in direct contact with each other (Patent References 1 and 2).
• Patent Document 1 Japanese Patent No. 3 5 5 2 3 2 8
• Patent Document 2 Japanese Patent No. 4 6 3 0 9 5 4
• the polymerizable compound in the liquid crystal composition has a role of forming a polymer network to obtain desired optical characteristics and a role of enhancing the adhesion between the liquid crystal layer and the electrode.
• an inorganic electrode such as To O (Indium Tin Oxide) is used in this device, the compatibility with the organic polymerizable compound, that is, the adhesiveness tends to be low. If the adhesion is low, the element will peel off or bubbles will be generated due to the harsh environment such as long-term use, especially the environment exposed to high temperature and high humidity or light irradiation, and the optical characteristics of the scattering state and the transparent state. More likely to cause
• the present invention provides a normal type liquid crystal capable of suppressing peeling of elements, generation of bubbles, and deterioration of optical characteristics even in a harsh environment exposed to high temperature and high humidity and irradiation of light for a long time.
• An object is to provide a display element.
• a liquid crystal composition containing a liquid crystal and a polymerizable compound which is disposed between a pair of substrates provided with electrodes, has a liquid crystal layer that is hardened by applying at least one of active energy rays and heat, and
• a transmission-scattering normal type liquid crystal display device comprising a resin film on at least one of the substrates, which is in a scattering state when no voltage is applied, and is in a transparent state when a voltage is applied,
• a symbol represents a binding site with another structure.
• a liquid crystal display device is obtained.
• the liquid crystal display device using the resin composition containing the specific compound becomes the liquid crystal display device having the above characteristics. Therefore, the liquid crystal display device of the present invention can be used for a liquid crystal display for display, a dimming window for controlling light blocking and light transmission, an optical shutter device, and the like.
• the specific compound is the compound of the above formula [1].
• Ding 1 shows at least one structure selected from the following formula [ 1_8 ] to formula [1_1"1].
• D represents an alkyl group having 1 to 3 carbon atoms.
• the formula [1 _ 10], the formula [1 _ 0] or the formula [1 _ 0 1] is preferable.
• Ding 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.
• Ding 3 shows the structure of the above formula [1].
• the use ratio of the specific compound is from 0.1 to 30 with respect to 100 parts by mass of all the polymers contained in the resin composition. Parts by mass are preferred. More preferably, it is 0.5 to 20 parts by mass. Most preferred ⁇ 2020/175 560 5 ⁇ (:171? 2020 /007782
• the amount is 1 to 15 parts by mass. Further, the specific compound may be used alone or in combination of two or more depending on each characteristic.
• the resin composition containing a specific compound of the present invention preferably comprises a polymer having at least one structure (also referred to as a specific structure.) Selected from the following formulas [2 _ 3] to the formula [2 _ ⁇ ] ..
• the specific structure is contained in the repeating unit that constitutes the polymer.
• the repeating unit containing a specific structure is preferably contained in an amount of 10 to 70 mol %, more preferably 20 to 60 mol %, based on the entire repeating units constituting the polymer.
• polymers having a specific structure may be used alone or in combination of two or more, depending on each characteristic.
• X represents a hydrogen atom or a benzene ring.
• the formulas [2-8] to [formula] are preferable. More preferred are formula [2-3] to formula [2-6]. From the viewpoint of the adhesion between the liquid crystal layer and the resin film, the formula [2-3], the formula [2_10], the formula [2_01], or the formula [2_ ⁇ ] is particularly preferable.
• photoreaction with the reactive group of the polymerizable compound in the liquid crystal composition occurs in the process of irradiation with ultraviolet light or heating during the production of the liquid crystal display element, ⁇ 2020/175 560 6 ⁇ (:171? 2020 /007782
• the polymer is not particularly limited, but at least one polymer selected from acrylic polymers, methacrylic polymers, novolac resins, polyhydroxystyrenes, polyimide precursors, polyimides, polyamides, polyesters, celluloses and polysiloxanes. Coalescence is preferred. More preferred are polyimide precursors or polyimides.
• polyimido polymer When a polyimido precursor or polyimido (collectively referred to as polyimido polymer) is used as a polymer, they are a polyimido precursor or a polyimido precursor obtained by reacting a diamine component with a tetracarboxylic acid component. Polyimide is preferred.
• the polyimide precursor has, for example, a structure of the following formula [8].
• [0025] represents a tetravalent organic group. Indicates a divalent organic group. Each 1 and eight 2 is a hydrogen atom or a carbon atoms
• n is 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 acid compound, a tetracarboxylic dianhydride, or a tetracarboxylic acid.
• examples thereof include a dihalide compound, a tetracarboxylic acid dialkyl ester compound, and a tetracarboxylic acid dialkylester dihalide compound.
• Polyimide prepared by imidizing polyamic acid is preferable.
• the polymer of the formula [mouth] obtained above is added to the polymer of the formula [8] having 1 and 2 alkyl groups 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.
• a diamine having the specific structure As a method of introducing the specific structure into the polyimide-based polymer, it is preferable to use a diamine having the specific structure as a part of the raw material. In particular, it is preferable to use a diamine having a structure of the following formula [2] (also referred to as a specific diamine). [0033] [Chemical 9]
• X 1 is a single bond, _ ⁇ _ .. _ (0 1 to 1 3 ) _ , _ 0 1 to 1 2 ⁇ _ , _ ⁇ ⁇ 1, 100 (0 1 ⁇ 1 3 )--, 1 (0 1 ⁇ 1 3 ) 0 ⁇ 1, 1
• X 2 represents a single bond, an alkylene group having 1 to 18 carbon atoms, or an organic group having 6 to 24 carbon atoms, which has a cyclic group selected from a benzene ring, a cyclohexane ring and a heterocycle.
• An arbitrary hydrogen atom of is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. It may be replaced.
• a single bond, an alkylene group having 1 to 12 carbon atoms, a benzene ring or a cyclohexane ring is preferable. From the viewpoint of adhesiveness between the liquid crystal layer and the resin film, more preferred is a single bond or an alkylene group having 1 to 12 carbon atoms.
• X 4 represents at least one structure selected from the above formula [2-8] to formula [2__]. Among them, the formulas [2-8] to [formula] are preferable. Equations [2-8] to [2-6] are more preferable. From the viewpoint of adhesion between the liquid crystal layer and the resin film, particularly preferred are Formula [2-8], Formula [2-10], Formula [2- ⁇ 1], or Formula [2-6]. ..
• X n represents an integer of 1 to 4. Of these, 1 or 2 is preferable.
• X represents the structure of the above formula [2].
• the details of X 1 to X 4 and the formula in Formula [2], and preferable combinations are as in Formula [2]. ⁇ 02020/175560 9 ⁇ (: 17 2020/007782
• B is an integer from 1 to 4. Among them, 1 is preferable.
• More specific diamines include the following formulas [23-1] to [23-1
• [0040] 1 represents an integer of 2 to 12.
• Gate 2 represents an integer of 0 to 12.
• 113 represents an integer of 2 to 12.
• formula [23-1], the formula [23-2], the formula [23-5] to the formula [2 3 1 7], the formula [23-1 1] or the formula [23-1 2] Is preferred. More preferred are formula [2 3 _5] to formula [2 3 — 7], formula [2 3 _ 11] or formula [2 3 —
• the use ratio of the specific diamine is preferably 10 to 70 mol% with respect to the entire diamine component. More preferred is 20 to 60 mol %.
• the specific diamine may be used alone or in combination of two or more, depending on each characteristic.
• a diamine other than the specific diamine (also referred to as other diamine) can also be used as the diamine component for producing the polyimide polymer.
• tetracarboxylic acid component for producing a polyimide-based polymer examples include tetracarboxylic acid dianhydride represented by the following formula [3], tetracarboxylic acid which is a tetracarboxylic acid derivative thereof, tetracarboxylic acid dihalide, and tetracarboxylic acid. It is preferable to use a carboxylic acid dialkyl ester or a tetracarboxylic acid dialkyl ester dihalide (all collectively referred to as a specific tetracarboxylic acid component).
• [0046] represents at least one structure selected from the following formula [33] to formula [3 I].
• Each represents a hydrogen atom, a methyl group, a chlorine atom or a benzene ring. £ and represent a hydrogen atom or a methyl group, respectively.
• the ratio of the specific tetracarboxylic acid component used is preferably 1 mol% or more based on all tetracarboxylic acid components. More preferred is 5 mol% or more, and particularly preferred is 10 mol% or more. Most preferably, it is 10 to 90 mol% from the viewpoint of optical characteristics of the liquid crystal display device.
• tetracarboxylic acid components other than the specific tetracarboxylic acid component can be used for the polyimide-based polymer.
• examples of other tetracarboxylic acid components include the following tetracarboxylic acid compounds, tetracarboxylic acid dianhydrides, dicarboxylic acid dihalide compounds, dicarboxylic acid dialkyl ester compounds and dialkyl ester dihalide compounds.
• the specific tetracarboxylic acid component and the other tetracarboxylic acid component may be used alone or in combination of two or more, depending on each characteristic.
• 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 include the method described on pages 35 to 36 of International Publication No. 201 5/01 2368 (Published May 29, 201).
• 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.
• solvent solubility of the polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone or a solvent represented by the following formula [mouth 1] to formula [03] is used. Can be used.
• ⁇ 3 represents an alkyl group having 1 to 4 carbon atoms.
• 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.
• an organic solvent Since the water content of the water 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 when the total number of moles of the diamine component is 1.0 is preferably 0.8 to 1.2.
• the polymer has an amino group-terminated structure, 1 If it is larger than 0.0, that is, if the total number of moles of the tetracarboxylic acid component is larger than the number of moles of the diamine component, the polymer end has a carboxylic acid anhydride or dicarboxylic acid structure.
• the total number of moles of the tetracarboxylic acid component is greater than 1.0, that is, the total number of moles of the tetracarboxylic acid component is greater than the number of moles of the diamine component. Is also preferably large. Specifically, when 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 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 is not necessarily 100%. It is not necessary and 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 was measured by the GPC (Gel Permeation Chromatography) method in consideration of the strength of the resin film obtained therefrom and the workability and coating property during resin film formation.
• the Mw weight average molecular weight is preferably 5,000 to 1,000,000. More preferably, it is 10,000 to 150,000.
• the resin composition contains a specific compound, and preferably forms a resin film. ⁇ 0 2020/175 560 14 ⁇ (: 17 2020/007782
• the content of the polymer component in the resin composition of the present invention can be appropriately changed according to the setting of the thickness of the resin film to be formed, but a uniform and defect-free resin film is formed. It is preferably 1% by weight or more from the standpoint of making it possible, and is preferably 10% by weight or less from the viewpoint of storage stability of the solution. Above all, 2 to 8% by weight is preferable, and 3 to 7% by weight is particularly preferable.
• All the polymer components in the resin composition may be a polymer having a specific structure, or may be a mixture of polymers having no specific structure.
• the ratio of the polymer having no specific structure to be used is preferably 10 to 400 parts by mass relative to 100 parts by mass of the polymer having a specific structure. More preferred is 10 to 300 parts by mass. Particularly preferred is 10 to 200 parts by mass.
• the content of the solvent in the resin composition can be appropriately selected from the viewpoint of obtaining the coating method of the resin composition and the desired film thickness.
• the content of the solvent in the resin composition is preferably 50 to 99.9 mass% from the viewpoint of forming a uniform resin film by coating. More preferably, it is 60 to 99 mass %. Particularly preferred is 65 to 99% by mass.
• the solvent used in the resin composition is not particularly limited as long as it is a solvent that dissolves the polymer.
• the polymer is a polyimide precursor, polyimide, polyamide or polyester, or when the solubility of acrylic polymer, methacrylic polymer, novolac resin, polyhydroxystyrene, cellulose or polysiloxane in the solvent is low. It is preferable to use the following solvents (also referred to as solvents).
• methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy _ 4-methyl-2-pentanone and the like it is preferable to use 1 ⁇ 1_methyl-2-pyrrolidone, 1 ⁇ 1-ethyl-2-pyrrolidone or ⁇ -butyrolactone. Further, these may be used alone or in combination.
• 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, When the solubility of these polymers in a solvent is high, the following solvent (also referred to as solvent) 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
• 1 ⁇ 1_methyl-2-pyrrolidone, 1 ⁇ 1_ethyl-2-pyrrolidone of the above-mentioned solvents 8 or ⁇ _ Butyrolactone is preferably used in combination. It is more preferable to use arbutyrolactone together.
• the polymer can be used as a polymer precursor, a polyimide, a polyamide or a polyester.
• the amount of the solvent is preferably 1 to 99% by mass of the whole solvent contained in the resin composition. Among them, 10 to 99 mass% is preferable. More preferable is 20 to 95% by mass.
• the resin composition contains an epoxy group and an isocyanate. ⁇ 2020/175 560 16 ⁇ (:171? 2020 /007782
• a compound (collectively referred to as a specific crosslinkable compound) having at least one selected from a nate group, an oxetane group, a cyclocarbonate group, a hydroxy group, a hydroxyalkyl group and a lower alkoxyalkyl group. .. In that case, it is necessary for the compound to have two or more of these groups.
• Specific examples of the crosslinkable compound having an epoxy group or an isocyanate group include epoxy groups or isocyanates described on pages 63 to 64 of International Publication WO 201 4/1 7 1 493 (201 4.1 0.23 publication). Examples thereof include crosslinkable compounds having a group.
• crosslinkable compound having an oxetane group are described in International Publication WO ⁇ /O 201.
• 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 (published on Feb. 2, 2011). ⁇ Crosslinkable compounds of the formula [5-42] are mentioned.
• crosslinkable compound having a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group are described in International Publication No. WO 201 4/1 7 1 493 (2 01 4.1 0 23), pages 65 to 66.
• the crosslinkable compound of a formula [6_48] is mentioned.
• the ratio of the specific crosslinkable compound used in the resin composition is set to be all polymer components.
• 0.1 to 100 parts by mass is preferable with respect to 100 parts by mass. More preferred is 0.1 to 50 parts by mass, because the crosslinking reaction proceeds and the desired effect is exhibited. Particularly preferred is 1 to 30 parts by mass.
• At least one kind of generator also referred to as a specific generator selected from a photoradical generator, a photoacid generator and a photobase generator into the resin composition.
• the resin composition a compound that improves the film thickness uniformity and the surface smoothness of the resin film when the resin composition is applied can be used. Furthermore, a compound or the like that improves the adhesion between the resin film and the substrate can also be used.
• Examples of the compound that improves the uniformity of the film thickness and the surface smoothness of the resin film include a fluorine-based surfactant, a silicone-based surfactant, and a nonionic surfactant. Specific examples thereof include the surfactants described on page 67 of International Publication Gazette ⁇ / ⁇ 201 4/1 7 1 493 (published 20 1 4.1 0.23). Further, the use ratio is preferably 0.01 to 2 parts by mass with respect to 100 parts by mass of all polymer components. More preferred is 0.01 to 1 part by mass.
• the resin composition may be added with a dielectric or a conductive substance for the purpose of changing electrical properties such as the dielectric constant and conductivity of the resin film.
• the liquid crystal composition has a liquid crystal and a polymerizable compound.
• liquid crystal nematic liquid crystal, smectic liquid crystal, or cholesteric liquid crystal can be used. Above all, it is preferable to use a liquid crystal having a positive dielectric anisotropy for the liquid crystal display element of the present invention. At that time, from the viewpoints of low voltage driving and dispersion characteristics, those having a large anisotropy of dielectric constant and a large anisotropy of refractive index are preferable. Further, as the liquid crystal, two or more kinds of liquid crystal can be mixed and used according to the physical properties such as the phase transition temperature, the dielectric anisotropy and the refractive index anisotropy.
• liquid crystal display element As an active element such as a TFT (Thin Fiber Imistor), it is required that the liquid crystal has a high electric resistance and a high voltage holding ratio (also called VHR). Therefore, it is preferable to use a fluorine-based or chlorine-based liquid crystal as the liquid crystal, which has a high electric resistance and whose VHR does not decrease due to active energy rays such as ultraviolet rays.
• the liquid crystal display device can be made into a guest-host type device by dissolving a dichroic dye in the liquid crystal composition. At that time, an element that absorbs (scatters) when no voltage is applied and becomes transparent when a voltage is applied is obtained. Moreover, in this device, the direction of the director of the liquid crystal (orientation direction) changes by 90 degrees depending on the presence or absence of voltage application. Therefore, by utilizing the difference in the light absorption characteristics of the dichroic dye, this device can obtain higher contrast than the conventional guest-host type device that performs switching in random alignment and vertical alignment.
• the polymerizable compound in the liquid crystal composition is for forming a polymer network (also referred to as a curable resin) through a polymerization reaction due to active energy rays and heat during production of the liquid crystal display element.
• the polymerization reaction in the present invention is preferably one that proceeds by irradiation with ultraviolet rays.
• a polymer obtained by polymerizing the polymerizable compound may be introduced into the liquid crystal composition in advance.
• a liquid crystal composition containing a polymerizable compound it is preferable to use.
• the polymerizable compound is not particularly limited as long as it is dissolved in the liquid crystal, but it is necessary that a temperature at which a part or the whole of the liquid crystal composition exhibits a liquid crystal phase exists when the polymerizable compound is dissolved in the liquid crystal. .. Even when a part of the liquid crystal composition exhibits a liquid crystal phase, the liquid crystal display element can be visually inspected and the entire inside of the element has almost uniform transparency and scattering. ⁇ 2020/175 560 19 ⁇ (:171? 2020/007782
• the polymerizable compound may be a compound that is polymerized by ultraviolet rays or heat, and in that case, the polymerization may proceed in any reaction mode to form a curable resin.
• Specific reaction modes include radical polymerization, cationic polymerization, anionic polymerization and polyaddition reaction.
• the reaction mode of the polymerizable compound is preferably radical polymerization from the viewpoint of optical characteristics of the liquid crystal display device.
• the polymerizable compound the following radical-type polymerizable compound or an oligomer thereof can be used. Further, as described above, it is also possible to use a polymer obtained by polymerizing these polymerizable compounds.
• radical-type polymerizable compounds or oligomers thereof are described in International Publication
• the proportion of the radical-type polymerizable compound or its oligomer used is 70 to 150 parts by mass with respect to 100 parts by mass of the liquid crystal in the liquid crystal composition. preferable. More preferably, it is 80 to 110 parts by mass. Further, the radical-type polymerizable compound may be used alone or in combination of two or more, depending on each characteristic.
• a radical initiator also referred to as a polymerization initiator
• a radical initiator that generates a radical by ultraviolet rays
• the radical initiator is preferably used in an amount of 0.01 to 20 parts by mass relative to 100 parts by mass of the liquid crystal in the liquid crystal composition. More preferred is 0.05 to 10 parts by mass.
• the radical initiator may be used alone or in combination of two or more, depending on each characteristic. ⁇ 02020/175 560 20 (: 17 2020/007782
• [0078] 3 1 represents at least one structure selected from the following formulas [4-8] to the formula [4_ ".
• the formula [4-8], the formula [4_! ⁇ ], the formula [4_ ⁇ ], the formula [4_], the formula [4-6], or the formula [4_dry] is preferable. More preferred are formula [4-8], formula [4_! ⁇ ], formula [4_ ⁇ ] or formula [4-6]. Especially preferred is the formula [4-8] or the formula [4_ !0].
• [0080] 3 represents a hydrogen atom or a benzene ring.
• 3 2 is a single bond, _ ⁇ 1, (01 ⁇ 1 3 )--, _01 ⁇ 1 2 0 1, --0 0 NH--, 1 1 ⁇ 1-10 0 1, 1 0 0 (01 ⁇ 1 3 )--, 1 (01 ⁇ 1 3 ) 00-- , 1 ⁇ 3 001 and at least 1 selected from 100 _.
• a single bond, _ 0 1, 1 0 ⁇ 1 2 0 1, _0.001 or 100_ is preferred. More preferred are single bonds, 101, 100001 or 100001.
• 3 3 is a single bond or one (Rei_1 ⁇ 1 2) 3 - shows a (3 is an integer from 1 1 5). 20/175560 21 ⁇ (: 171? 2020 /007782
• 3 4 is a single bond, one hundred and one, one Rei_rei_1 ⁇ 1 2 -, represents at least one Bareru selected from ten thousand and one and ten thousand and one. Of these, a single bond, _001 or 100001 is preferred. More preferred is Is.
• a benzene ring a divalent organic group having 1 7-5 1 carbon atoms with a divalent cyclic group, or steroid skeleton selected from the cyclohexane ring and heterocyclic, any of the said cyclic group Hydrogen atom is an alkyl group having 1 to 3 carbon atoms, 1 to 3 carbon atoms
• a C 3 alkoxy group a C 1 to C 3 fluorine-containing alkyl group, a C 1 to C 3 fluorine containing alkoxy group, or a fluorine atom.
• a benzene ring or a cyclohexane ring, or a divalent organic group having a carbon number of 17 to 51 and having a steroid skeleton is preferable. More preferred is a divalent organic group having a carbon number of 17 to 51 and having a benzene ring or a skeleton skeleton.
• 3 6 is a single bond, _ ⁇ _, _ 0 ⁇ ⁇ ⁇ 2 _, _ _ 0 0 1 - 1 2, _ 0 1 - 1 2 ⁇ _, selected from the group consisting of _ hundred ⁇ first and ten thousand and one Indicates at least one Of these, a single bond, 101, 100111 or 100001 is preferable. More preferred is a single bond, Is.
• a benzene ring shows a cyclic group selected from the cyclohexane ring and heterocyclic, any of hydrogen atoms on these cyclic groups, an alkyl group of from 1 to 3 carbon atoms, an alkoxy group having a carbon number of 1 to 3 It may be substituted with a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom. Of these, a benzene ring or a cyclohexane ring is preferable.
• an alkyl group or an alkoxy group having 1 to 18 carbon atoms or an alkenyl group having 2 to 18 carbon atoms is preferable. More preferably, the carbon number is 1 to 1. ⁇ 0 2020/175 560 22 ⁇ (: 17 2020 /007782
• 2 is an alkyl group or an alkoxy group.
• 3 represents an integer from 0 to 4. Among them, 0 to 2 is preferable.
• Specific liquid additive compound has a portion of rigid structure such as a benzene ring or a cyclohexane ring, and a portion of the polymerization reaction by ultraviolet rays or heat represented by 3 1 of the formula [4 3]. Therefore, when the specific liquid crystal additive compound is included in the liquid crystal composition, the rigid structure portion of the specific liquid crystal additive compound enhances the vertical alignment of the liquid crystal and accelerates the driving of the liquid crystal due to the voltage application, and The drive voltage can be lowered. Further, by 3 1 site in the formula [4 3] are reacted with the polymerizable compound, it is possible to keep the polymer network dense state.
• More specific specific liquid crystal compound addition following formula [4 3 _ 1] to the formula - include compounds of [4 3 1 1], it is preferable to use them.
• 3 & indicates 1001 or 1001, respectively. Each 3 has 1 carbon
• ⁇ 12 shows an alkyl group. Each 1 represents an integer of 1 to 10. Each 2 represents an integer of 1 or 2.
• 3 6 respectively show a _ ⁇ one or ten thousand and one.
• Each of 3 ⁇ represents a divalent organic group having a steroid skeleton and having 17 to 51 carbon atoms.
• 3 9 show respectively a carbon number 1-1 2 alkyl or alkenyl group of carbon number 2-1 8. Five Each represents an integer of 1 to 10.
• the specific liquid crystal additive compound is preferably used in a proportion of 0.1 to 30 parts by mass relative to 100 parts by mass of the liquid crystal in the liquid crystal composition. More preferably, it is 0.5 to 20 parts by mass. Particularly preferred is 1 to 10 parts by mass.
• the specific liquid crystal additive compound may be used alone or in combination of two or more depending on each characteristic.
• the liquid crystal composition may be prepared by mixing the liquid crystal, the polymerizable compound, and the specific liquid crystal additive compound together, or by previously mixing the polymerizable compound and the specific liquid crystal additive compound with the liquid crystal. There is a method of doing.
• a method of mixing a mixture of the polymerizable compound and the specific liquid crystal additive compound in advance with the liquid crystal is preferable.
• heating can be performed depending on the solubility of the polymerizable compound and the specific liquid crystal additive compound.
• the temperature at that time is preferably less than 100 °C.
• the substrate used for the liquid crystal display element is not particularly limited as long as it is a highly transparent substrate, and in addition to a glass substrate, a plastic substrate such as an acrylic substrate, a polycarbonate substrate, a PET (polyethylene terephthalate) substrate, or the like. These films can be used. In particular, when used for a light control window or the like, a plastic substrate or film is preferable.
• the T0 electrode for driving the liquid crystal the Z0 (Ind i um Z i nc Ox i de) electrode,
• a substrate on which an I G Z 0 (Indium Ga U ium Zi nc Oxide) electrode, an organic conductive film, or the like is 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 liquid crystal display element has a resin film obtained from a resin composition containing a specific compound on at least one of the substrates.
• a resin film obtained from a resin composition containing a specific compound on at least one of the substrates.
• both substrates have a resin film.
• the method of applying the resin composition is not particularly limited, but industrially, screen printing, offset printing, flexo printing ! ⁇ , ink jet method, dip method, mouth coater method, slit coater method, spinner, spinner Method, spray method, etc., and can be appropriately selected according to the type of substrate and the desired film thickness of the resin film.
• a heating means such as a hot plate, a heat-circulation type oven, or an 8 (infrared) type oven is used depending on the type of the substrate and the solvent used for the resin composition.
• the solvent can be evaporated at a temperature of 30 to 300°C, preferably 30 to 250°C to form a resin film.
• a plastic substrate is used as the substrate, it is preferable to process at a temperature of 30 to 150 °
• the thickness of the resin film after firing 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 element may be deteriorated.
• Is. Particularly preferred is 10 to 250.
• the liquid crystal composition used for the liquid crystal display element is the liquid crystal composition as described above, and a spacer for controlling the electrode gap (also referred to as a gap) of the liquid crystal display element is included therein. It can also be introduced.
• the method of injecting the liquid crystal composition is not particularly limited, and examples thereof include the following methods. That is, when using a glass substrate as the substrate, prepare a pair of substrates having a resin film formed thereon, apply the sealant on four pieces of the substrate on one side except for a part, and then, the surface of the resin film is An empty cell is produced by sticking the substrates on the other side so that they are on the inside. Then, a method of injecting the liquid crystal composition under reduced pressure from a place where the sealant is not applied to obtain a liquid crystal composition injection cell can be mentioned.
• the substrate when using a plastic substrate or film as the substrate, prepare a pair of substrates with a resin film formed on it, and then use the ⁇ ( ⁇ 0" ⁇ ⁇ ⁇ ⁇ beating) method or ink jet on one of the substrates.
• the liquid crystal composition may be dropped by a method such as a method, and then the other substrate may be bonded to obtain a liquid crystal composition injection cell.
• the gap of the liquid crystal display element can be controlled by the spacer or the like. That way ⁇ 2020/175 560 26 ⁇ (: 171-1? 2020/007782
• Examples thereof include a method of introducing a spacer having a target size into the liquid crystal composition and a method of using a substrate having a column spacer of a target size as described above.
• the gap can be controlled without introducing a spacer.
• the size of the gap of the liquid crystal display element is preferably 1 to 100.
• the more preferable range is 1 to 5001. Particularly preferred is 2 to 3001. If the gap is too small, the contrast of the liquid crystal display device will decrease, and if it is too large, the drive voltage of the device will increase.
• the liquid crystal display device is obtained by curing the liquid crystal composition to form a liquid crystal layer in a state where part or all of the liquid crystal composition exhibits liquid crystallinity.
• the liquid crystal composition is cured by irradiating the liquid crystal composition injecting cell with ultraviolet rays or heating. In the present invention, as described above, irradiation with ultraviolet rays is preferable.
• Examples of the light source of the ultraviolet irradiation device used for irradiation of ultraviolet rays include a metal halide lamp and a high-pressure mercury lamp.
• the wavelength of ultraviolet rays is 2 Is preferred. Of these, 310 to 370 n is preferable. Further, heat treatment may be performed after irradiation with ultraviolet rays.
• the temperature at that time is preferably 40 to 120°. More preferred is 40 to 80°
• Examples of the apparatus used for heating include heating means used after applying the resin composition onto the substrate. Further, the temperature at that time is appropriately selected depending on the temperature at which the reaction of the polymerizable compound proceeds and the type of the substrate. Specifically, preferably 8 0 ° ⁇ _ ⁇ 2 0 0 ° ⁇ .
• Standard sample for making calibration curve Ding 3 ⁇ Standard polyethylene oxide (Molecular weight: about 900,000, 150,000, 100,000 and 30,000) (Tosoh Corporation) and Polyethylene glycol (Molecular weight; Approx. 1 2,000, 4,000 and 1,000) (manufactured by Polymer Laboratory).
• Polyimide powder (Nuclear magnetic resonance) Put in a sample tube (IV! Sampling tube standard, ⁇ 5 (made by Kusano Science Co., Ltd.)) and add deuterated dimethyl sulfoxide (mouth 1 ⁇ /13 ⁇ 1,6, ⁇ .05 mass% 1 1 ⁇ /13 (Tetramethylsilane) mixture) (0.53111 I) was added, and ultrasonic waves were applied to completely dissolve it.
• This solution 500 IV! 1 to 12 protons IV! were measured with a measuring machine (" ⁇ /_Mitsuhachi 500) (manufactured by JEOL DATAM).
• the imidation rate is determined by using the proton derived from the structure that does not change before and after imidization as the reference proton, and the peak integrated value of this proton and the 1 ⁇ 11% of the amide acid appearing around 9.5 0 to 1 0.0. It was calculated by the following formula using the integrated value of the proton peak derived from ⁇ 1 group.
• Imidization rate (%) X 100 20/175560 30 ⁇ (: 171? 2020 /007782
• ⁇ 1 (2.709, 1 3. 801010 ⁇ ), ⁇ 1 (1.09 9 ,1 0. ⁇ I) and Mimi 2 (1. 249, 4.33 ⁇ 1 ⁇ 1 ⁇ 1) are mixed in 1 ⁇ /1? (1 5. 1 9) and reacted at 25 ° ⁇ for 8 hours.
• a polyamic acid solution (1) having a concentration of 25 mass% was obtained.
• the number average molecular weight (also called IV!) of this polyamidic acid was 27,200, and the weight average molecular weight (also called 1 ⁇ /1) was 81,800.
• a polyamic acid solution (6) having a resin solid content concentration of 25 mass% was obtained.
• the IV! n of this polyamic acid was 19,500 and 1 ⁇ /1 ⁇ « was 63,200.
• Table 1 shows the polyimide-based polymers obtained in the synthesis examples.
• a composition (2) was obtained. No abnormality such as turbidity or precipitation was observed in this resin composition, and it was a uniform solution.
• the liquid crystal composition () to ( ⁇ ) was dropped by the method of ⁇ ⁇ ( ⁇ 0 " ⁇ ⁇ Don 1 1 9), and then the other The substrates were laminated so that the resin film surfaces of the substrates face each other to obtain a liquid crystal display element before treatment.
• the liquid crystal display element before this treatment was Using a damp, wavelengths below 350 n were cut, and UV irradiation was performed for an irradiation time of 60 seconds. As a result, a liquid crystal display element (glass substrate) was obtained.
• the resin compositions obtained by the methods of Examples and Comparative Examples were pressure-filtered with a membrane filter having a pore size of 1.
• the obtained solution was washed with pure water.
• 1 x 0 x 150 0 01 01 01 I Dixel Ming board with electrodes (vertical: 1 500 1 01, horizontal: , Thickness: 0. 01 01 01) Apply on the surface with a bar coater, and heat-treat for 2 minutes at 120° in a heat-circulation oven to obtain a film thickness of 10
• the liquid crystal composition () to ( ⁇ ) was dropped on the resin film surface of the substrate coated with the spacer by the ⁇ ((0 0 ” ⁇ ⁇ ⁇ ⁇ beating) method, and then the other substrate
• the liquid crystal display element before treatment was obtained by pasting so that the resin film surfaces of the liquid crystal surface of the liquid crystal composition faced each other.
• a glass substrate was used as a supporting substrate for the attachment plate, and then the supporting substrate was removed before irradiation with ultraviolet rays.
• liquid crystal display element glass substrate and plastic substrate
• voltage AC drive:
• Example 6 The measurement results of Example 6 are summarized in Tables 5 to 7.
• the liquid crystal display elements (glass substrate and plastic substrate) were stored for 24 hours in a thermo-hygrostat at a temperature of 80 ° and a humidity of 90% [3 ⁇ 4! It was performed by confirming the presence or absence of air bubbles (as a stability test of the liquid crystal display element under high temperature and high humidity environment). Specifically, the evaluation was conducted with the element not peeled (the state where the liquid crystal layer and the resin film, or the resin film and the electrode are peeled off) and the case where no air bubbles were generated in the element. To be excellent (good indication in the table). At that time, in Examples 14 to 18, in addition to the standard test, as an emphasizing test, a temperature of 80° ⁇ and a humidity of 90% [3 ⁇ 4! Stored for hours ⁇ 2020/175 560 41 ⁇ (:171? 2020 /007782
• a desktop type II V curing device (1 to 10 3 3 2 8 1 to 1 1 1 1
• any one of the resin compositions (1) to (16) obtained by the method of Examples and Comparative Examples and the liquid crystal compositions (8) to ( ⁇ ) were used to obtain a liquid crystal display element by the above method. Fabrication, evaluation of optical characteristics (scattering characteristics and transparency), and evaluation of adhesion between the liquid crystal layer and the resin film (resin film and electrode) were performed, with Examples 14 to 20 being Examples 26 to Example 28, Comparative Example 4 and Comparative Example 5 were produced and each evaluation of a liquid crystal display device using a glass substrate, Examples 21 to Example 25 and Comparative Example 6 are, A plastic substrate was used.
• the liquid crystal display element of the example using the resin composition containing the specific compound was compared with the comparative example not using it, after the storage in the constant temperature and humidity chamber, and after 1 to The change of 1 3 2 6 became smaller.
• neither peeling of the liquid crystal display element nor generation of bubbles was observed even after storage in a constant temperature and constant humidity tank and after irradiation with ultraviolet rays.
• the polymer terminal has a carboxylic acid or dicarboxylic acid structure, that is, when the diamine component and the tetracarboxylic acid component are polymerized, If the total number of moles of the components is greater than the number of moles of the diamine component, one having a structure with an amino group at the polymer end (the total number of moles of the tetracarboxylic acid component during the above-mentioned polymer reaction is The generation of bubbles in the liquid crystal display element during the stress test was suppressed compared to the smaller one). Specifically, in comparison under the same conditions, Example 14 and Example 15 are compared.
• Example 15 when a specific diamine having a specific structure was used as the polymer, generation of bubbles in the liquid crystal display element in the highlighting test was suppressed. Specifically, it is a comparison between Example 15 and Example 16 in the comparison under the same conditions.
• liquid crystal display element of the present invention can be suitably used for a normal type element that is in a scattering state when no voltage is applied and is in a transparent state when a voltage is applied. Furthermore, this device can be used in liquid crystal displays for display purposes, and in dimming windows and optical shutter devices that control the blocking and transmission of light. A plastic substrate can be used.

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