WO2022138418A1 - 高分子分散型液晶組成物、液晶素子及び調光素子 - Google Patents

高分子分散型液晶組成物、液晶素子及び調光素子 Download PDF

Info

Publication number
WO2022138418A1
WO2022138418A1 PCT/JP2021/046420 JP2021046420W WO2022138418A1 WO 2022138418 A1 WO2022138418 A1 WO 2022138418A1 JP 2021046420 W JP2021046420 W JP 2021046420W WO 2022138418 A1 WO2022138418 A1 WO 2022138418A1
Authority
WO
WIPO (PCT)
Prior art keywords
liquid crystal
group
polymer
crystal composition
polymerizable
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2021/046420
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
秀俊 中田
正直 高島
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DIC Corp
Original Assignee
DIC Corp
Dainippon Ink and Chemicals Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by DIC Corp, Dainippon Ink and Chemicals Co Ltd filed Critical DIC Corp
Priority to KR1020237016421A priority Critical patent/KR20230122577A/ko
Priority to CN202180074950.7A priority patent/CN116390961A/zh
Priority to JP2022544337A priority patent/JP7276619B2/ja
Publication of WO2022138418A1 publication Critical patent/WO2022138418A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/14—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/14—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain
    • C09K19/16—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain the chain containing carbon-to-carbon double bonds, e.g. stilbenes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/14—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain
    • C09K19/18—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain the chain containing carbon-to-carbon triple bonds, e.g. tolans
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • 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
    • G02F1/1334—Constructional arrangements; Manufacturing methods based on polymer dispersed liquid crystals, e.g. microencapsulated liquid crystals

Definitions

  • the present invention relates to a polymer-dispersed liquid crystal composition, a liquid crystal element obtained by using the polymer-dispersed liquid crystal composition, and a dimming element using the liquid crystal element.
  • the dimming element is a dimming element used for smart windows, window glass of buildings such as houses and buildings, doors, partitions, private glass, etc .; glass windows used for transportation media such as automobiles, airplanes, ships, trains, etc. Dimming elements used for mirrors, roofs, etc .; Used for optical shutters used for dimming digital cameras, smartphones, etc., light scattering plates for display light sources, light guide plates, reflective plates for reflective displays and transparent displays, etc. Includes a dimming element.
  • Polymer-dispersed (PNM) liquid crystal elements in which the liquid crystal material is dispersed in the polymer matrix and polymer-dispersed liquid crystal elements in which the liquid crystal material is interposed in the polymer network are different from general liquid crystal elements.
  • the degree of transmission / scattering of the liquid crystal can be adjusted. From the above characteristics, it is expected to be applied to high value-added displays such as reflective displays, transparent displays, local dimming light diffusing elements, and variable reflective elements.
  • high value-added displays such as reflective displays, transparent displays, local dimming light diffusing elements, and variable reflective elements.
  • window glass for building materials and transportation utilizing the dimming function of transmission / scattering, interior, exterior, private glass (SG), variable projector screen, smart glass such as digital signage, smart window (SW), etc.
  • Patent Document 1 shows an example in which a low voltage drive is realized by using a specific monomer compound, but there is a problem that the adhesion is insufficient.
  • Patent Document 2 uses a specific liquid crystal compound in order to improve the light resistance, and although a certain effect is observed in the light resistance, there is a problem that the light scattering property is insufficient. ..
  • Patent Document 3 a specific polymerizable compound is used to improve the adhesion, and although a certain effect is observed in the adhesion, there is a problem that the driving voltage is high. As described above, there has been a demand for a method for improving the scattering property, the driving voltage, and the adhesion in a well-balanced manner.
  • Japanese Unexamined Patent Publication No. 6-208107 Japanese Unexamined Patent Publication No. 2007-91850 Japanese Unexamined Patent Publication No. 2011-026526
  • the transparent base material, or the transparent electrode layer and the liquid crystal element layer may be used in various steps when producing using the flexible base material as described above. Good adhesion that does not come off is required. In addition, adhesion is also required when consideration is given to use and workability. Furthermore, it is necessary to have characteristics such as reliability and heat resistance that can withstand practical use as a dimming element, particularly transmittance after heating, and transparency when a voltage is turned on. Therefore, the problems to be solved by the present invention are excellent in drive voltage and adhesion, high reliability, good heat resistance, particularly little decrease in transmittance after heating, and transparency when the voltage is turned on. The purpose is to obtain a highly polymer-dispersed liquid crystal composition, a liquid crystal element, and a dimming element.
  • the polymerizable compound (MA) is As the first component, one or more cyclic monofunctional polymerizable compounds represented by the following general formula (ii) are contained.
  • Piii1 represents a polymerizable functional group and represents Z iii1 represents a single bond or an alkylene group having 1 to 7 carbon atoms, and one or two or more non-adjacent-CH 2 -in the alkylene group are independent so that oxygen atoms are not directly adjacent to each other. It may be substituted with -O-, -CO-, -COO- or -OCO-, and may be substituted.
  • a iii1 represents the general formulas (iii-1) to (ii-20).
  • one or more -CH 2- are independently replaced with -O-, -S-, -COO-, -OCO-, -NH-, -NCH 3- , or -CO-.
  • these are -O-O- and -O-.
  • the hydrogen atom in the general formulas (ii-1) to (ii-20) may be substituted with an alkyl group having 1 to 8 carbon atoms, and one or more of the alkyl groups are not adjacent to each other.
  • CH 2- may be independently substituted with -O-, -CO-, -COO- or -OCO- so that oxygen atoms are not directly adjacent to each other.
  • the black dots in the formula are for Ziii1 . Represents a bond.))
  • the non-polymerizable liquid crystal compound (LB) is Provided is a polymer-dispersed liquid crystal composition containing one or more trans-compounds represented by the following general formula (iii) as the second component.
  • R 11 is an n-alkyl having 1 to 7 carbon atoms, n-alkoxy, an alkenyl, an alkenyloxy or an alkoxyalkyl having 2 to 7 carbon atoms independently of each other.
  • R 12 represents a fluorine atom, a chlorine atom, a cyano group, a CF 3 group, an OCF 3 group, an OCHF 2 group, an NCS group, or an alkyl group having 1 to 10 carbon atoms, and is a non-adjacent 1 in the alkyl group.
  • CH-, trans-CF CF-, -COO-, -CH 2 -CH 2- , -CF 2 -CF 2- or single bond, where n is 0 or 1.
  • a polymer-dispersed liquid crystal display having excellent drive voltage and adhesion, high reliability, good heat resistance, little decrease in transmittance after heating, and high transparency when the voltage is turned on.
  • a composition, a liquid crystal element, and a dimming element can be obtained.
  • the polymer-dispersed liquid crystal composition of the present invention contains a polymerizable compound (MA) and a non-polymerizable liquid crystal compound (LB).
  • the polymerizable compound (MA) contains one or more cyclic monofunctional polymerizable compounds represented by the following general formula (ii) as the first component, and the non-polymerizable liquid crystal compound (LB). Contains one or more of the trans-polymers represented by the following general formula (iii) as the second component.
  • the weight ratio (LB / MA) of the non-polymerizable liquid crystal compound (LB) to the polymerizable compound (MA) is in the range of 30/70 to 70/30. It is preferably 40/60 to 60/40, more preferably 45/55 to 60/40, and particularly preferably 50/50.
  • each component constituting the polymerizable compound (MA) and each component constituting the non-polymerizable liquid crystal compound (LB) will be specifically described.
  • the first component is a cyclic monofunctional polymerizable compound represented by the following general formula (ii).
  • Piii1 represents a polymerizable functional group and represents Z iii1 represents a single bond or an alkylene group having 1 to 7 carbon atoms, and one or two or more non-adjacent-CH 2 -in the alkylene group are independent so that oxygen atoms are not directly adjacent to each other. It may be substituted with -O-, -CO-, -COO- or -OCO-, and may be substituted.
  • a iii1 represents the general formulas (iii-1) to (ii-20).
  • one or more -CH 2- are independently replaced with -O-, -S-, -COO-, -OCO-, -NH-, -NCH 3- , or -CO-.
  • these are -O-O- and -O-.
  • the hydrogen atom in the general formulas (ii-1) to (ii-20) may be substituted with an alkyl group having 1 to 8 carbon atoms, and the alkyl group may be a straight chain or a branched chain. It is also good that one or more non-adjacent -CH 2- in the alkyl group are independently -O-, -CO-, -COO- or -OCO- so that oxygen atoms are not directly adjacent to each other. It may be substituted. Further, the black dots in the equation represent the bond to Ziii1 .))))
  • the compound represented by the general formula (ii) of the first component is a material having excellent flexibility, and when this compound is used, cloudiness can be maintained even in a bent state. In addition, the adhesion can be enhanced and the compatibility of each component in the polymerizable composition can be enhanced.
  • the compound represented by the general formula (ii) is a non-liquid crystal compound.
  • Piii1 in the formula represents a polymerizable functional group, but preferably independently of each other, any one of the following formulas (P-1) to (P-21) can be used. More preferred. Further, in the following formulas (P-1) to (P-21), * indicates a bond with a carbon atom or another atom.
  • the formula (P-1), the formula (P-2), and the formula (P) are used from the viewpoint of enhancing the polymerizable property and the storage stability.
  • -7), formula (P-12), formula (P-13) or formula (P-21) is preferable, and formula (P-1), formula (P-2), formula (P-7), formula (P-7).
  • P-21) is more preferable, and the formula (P-1), the formula (P-2), and the formula (P-21) are particularly preferable.
  • Ziii1 in the formula represents a single bond or an alkylene group having 1 to 7 carbon atoms, and one or more -CH2- in the alkylene group is Each oxygen atom may be independently substituted with -O-, -CO-, -COO- or -OCO- so as not to be directly adjacent to each other, and one or more hydrogens present in the alkylene group. Each atom may be independently substituted with a fluorine atom.
  • Ziii1 is preferably a single bond or an alkylene group having 1 to 6 carbon atoms, more preferably a single bond or an alkylene group having 1 to 3 carbon atoms, and is a single bond or -CH 2- .
  • Aiii1 in the formula has a heterocyclic structure having a nitrogen atom, an oxygen atom, and a sulfur atom in Aiii1 from the viewpoint of further improving the adhesion. More specifically, the following general formulas (ii-a1) to (ii-a11) are preferable.
  • one or more -CH 2- may be independently substituted with -CO-, and the hydrogen atom in the general formulas (ii-a1) to (ii-a11) is a carbon atom. It may be substituted with an alkyl group of the number 1 to 8, and one or more non-adjacent -CH 2- in the alkyl group are independently -O-, so that oxygen atoms are not directly adjacent to each other. It may be substituted with -CO-, -COO- or -OCO-, and the hydrogen atom in the general formulas (ii-a1) to (ii-a11) is substituted with an alkyl group having 1 to 8 carbon atoms.
  • the alkyl group may be linear or branched, and one or more non-adjacent —CH2- in the alkyl group should be such that oxygen atoms are not directly adjacent. May be independently substituted with -O-, -CO-, -COO- or -OCO-, and the black dots in the formula represent the bond to Ziii1 .)
  • the adhesiveness of the cyclic structure can be further improved due to the presence of the nitrogen atom.
  • (X 5 in the formula represents a hydrogen atom or a methyl group.)
  • structural formulas (II-34) to (II-51), (II-34), (II-36), (II-38),. (II-39), (II-40), (II-43), (II-45), and (II-47) are more preferable.
  • the content of the compound represented by the general formula (ii), which is the first component, is in close contact with the total amount of the polymerizable compound (MA) contained in the polymer-dispersed liquid crystal composition of the present invention, which is 100% by mass.
  • the content is preferably 10% by mass or more, more preferably 20% by mass or more, and more preferably 30% by mass or more. Is particularly preferable.
  • it is preferably 80% by mass or less, more preferably 70% by mass or less, and particularly preferably 60% by mass or less.
  • the polymerizable compound (MA) may further contain a third component.
  • the third component is a polyfunctional (meth) acrylate oligomer having a weight average molecular weight of 2000 or more.
  • the third component, the polyfunctional (meth) acrylate oligomer is a compound required to introduce a crosslinked structure into the network structure of the polymer and to obtain good adhesion.
  • the polyfunctional (meth) acrylate oligomers bifunctional acrylate oligomers are preferable.
  • a urethane-based or polyester-based acrylate oligomer is preferable, and a urethane acrylate oligomer is even more preferable.
  • the urethane acrylate oligomer includes polyester type and polyether type, but the polyether type is preferable.
  • the weight average molecular weight is 2000 or more, preferably 2000 to 60,000, more preferably 2500 to 40,000, still more preferably 2800 to 35,000, and even more preferably 3000 to 30,000. This is because if the molecular weight is too small, the degree of curing shrinkage increases due to the increase in the crosslink density caused by the increase in the (meth) acrylic group contained in one molecule, and the adhesion deteriorates. On the contrary, the molecular weight is too small.
  • the polyfunctional urethane (meth) acrylate oligomer is obtained by reacting a hydroxyl group-containing acrylate with a polyol or polyisocyanate.
  • the polyol include polyether polyols, polyester polyols, polycarbonate polyols, polycaprolactone polyols, polybutadiene polyols, and examples of the polyether polyols include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.
  • polyisocyanate examples include 2,4- and 2,6-tolylene diisocyanate (TDI), orthotoluidine diisocyanate (TODI), naphthylene diisocyanate (NDI), xylylene diisocyanate (XDI), 4,4'-diphenylmethane diisocyanate ( MDI), methylenebis (4-cyclohexylisocyanate), xylylene diisocyanate, hydrogenated xylylene diisocyanate, hexamethylene diisocyanate, transcyclohexane 1,4-diisocyanate, 1,6,11-undecantry isocyanate, 1,8-diisocyanate-4 -Isocyanate methyl octane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, trimethylhexamethylene diisocyanate, dicyclopentadiene diisocyanate, norbornen
  • hydroxyl group-containing (meth) acrylate examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and polypropylene glycol mono (meth).
  • aliphatic urethane (meth) acrylates, aromatic urethane (meth) acrylates, and polyurethane diacrylate oligomers are preferable, and as the polyols to be used, polyether polyols, polyester polyols, and polycaprolactone polyols are preferable, and polyether polyols, A polyester polyol is particularly preferable, and as the polyisocyanate to be used, a polyisocyanate having a cyclic structure is preferable, and a polyisocyanate having an alicyclic structure is particularly preferable.
  • orthotoluidine diisocyanate TODI
  • methylenebis (4-cyclohexylisocyanate) methylenebis (4-cyclohexylisocyanate)
  • xylylene diisocyanate hydrogenated xylylene diisocyanate
  • transcyclohexane 1,4-diisocyanate 1,6,11-undecantry isocyanate
  • bicyclo Heptane triisocyanate dicyclopentadiene diisocyanate
  • norbornene diisocyanate norbornene diisocyanate
  • isophorone diisocyanate carbodiimide modified MDI
  • xylylene diisocyanate hydrogenated xylylene diisocyanate
  • transcyclohexane 1,4-diisocyanate 1,6.
  • 11-Undecantriisocyanate bicycloheptanetriisocyanate, dicyclopentadienediisocyanate, norbornendiisocyanate, isophoronediisocyanate are particularly preferable.
  • hydroxyl group-containing (meth) acrylate As the hydroxyl group-containing (meth) acrylate used, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,4- Cyclohexanedimethanol monoacrylate and mono (meth) acrylate modified with ⁇ -caprolactone are preferred, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-. Hydroxybutyl (meth) acrylates are particularly preferred.
  • X i1 independently represents a hydrogen atom or a methyl group
  • B 1 independently represents an alkyl group having 1 to 4 carbon atoms, and one or more of the alkyl groups.
  • -CH 2- may be substituted with an oxygen atom, -CO-, -COO-, -OCO-, b represents 1 to 20, and B 2 is the following (i-2) to (i-6). ), which may be used alone or in combination.
  • B 3 is a group selected from the following general formulas (i-7), (i-8) or (i-9), and may be used alone or in combination. )
  • X i2 represents a hydrogen atom or a methyl group
  • X i2 represents an alkyl group having 1 to 9 carbon atoms
  • Y5 represents an alkylene group having 1 to 15 carbon atoms, a divalent aromatic group, and a divalent alicyclic hydrocarbon group.
  • Y3 and Y4 represent a hydrogen atom or a methyl group.
  • t, t1 and t2 each independently represent an integer of 0 to 300, and t + t1 + t2 represent an integer of 20 to 300.
  • aliphatic urethane acrylates and polyurethane diacrylate oligomers are particularly preferable.
  • the content of the polymerizable compound selected from the polyfunctional (meth) acrylate oligomer having a weight average molecular weight of 2000 or more, which is the third component, is the polymerizable compound (MB) contained in the polymer-dispersed liquid crystal composition of the present invention.
  • MB polymerizable compound contained in the polymer-dispersed liquid crystal composition of the present invention.
  • the polymerizable compound (MA) may further contain a fourth component.
  • the fourth component is one or more selected from the group consisting of polyfunctional polymerizable oligomers having a weight average molecular weight of less than 2000 and polyfunctional polymerizable monomers represented by the following general formula (iv). Is preferable.
  • the molecular weight of the polyfunctional polymerizable oligomer and / or the polyfunctional polymerizable monomer is preferably 2000 or less, and more preferably 1000 or less.
  • Y 31 represents a hydrogen atom or a methyl group.
  • X 31 represents an alkylene group having 130 or less carbon atoms, and the alkylene group may have a cyclic hydrocarbon group or a branched chain, and the alkylene group or one or more of the cyclic hydrocarbon groups.
  • n 31 represents an integer from 2 to 6)
  • polyfunctional polymerizable oligomer having a weight molecular weight of less than 2000 or the polyfunctional polymerizable monomer represented by the general formula (iv) it is preferable to use a polymerizable compound represented by the general formula (iv-1). ..
  • Y 1 and Y 2 represent a hydrogen atom or a methyl group.
  • X 1 is a linear or branched alkylene in the range of 2 to 70 carbon atoms, but the carbon atom number is preferably in the range of 6 to 70. Above all, it is preferably in the range of 8 to 60, and particularly preferably in the range of 9 to 50 from the viewpoint of lowering the drive voltage.
  • Examples of the polymerizable compound represented by the above general formula (iv-1) include those having the following structure.
  • n + m is 1 to 10
  • n 2 is 1 to 18, n 3 and m 2 are n 3 + m 2 is 1 to 18, n 4 is 1 to 23, and n 5 is 1.
  • n 6 represent 4 to 30, n 7 represents 2 to 10, n 8 and n 9 represent 2 to 10, respectively).
  • the content of the polymerizable compound represented by the general formula (iv), which is the fourth component, is 100% by mass based on the total amount of the polymerizable compound (MA) contained in the polymer-dispersed liquid crystal composition of the present invention. From the viewpoint of improving heat resistance, it is preferably 2% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, and 50% by mass from the viewpoint of maintaining adhesion. % Or less, 40% by mass or less, 30% by mass or less, and 25% by mass or less are particularly preferable.
  • the polymerizable compound (MA) may further contain a fifth component.
  • the fifth component is preferably a chain monofunctional polymerizable compound represented by the following general formula (v).
  • Pia1 represents a polymerizable group and represents Ria2 represents a linear or branched alkyl group having 1 to 22 carbon atoms, and one or more -CH2- in the alkyl group are independent so that oxygen atoms are not directly adjacent to each other. It may be substituted with -O-, -CO-, -COO- or -OCO-, and one or more hydrogen atoms present in the alkyl group are independently fluorine atoms or It may be replaced with ⁇ OH.
  • Pia1 in the formula represents a polymerizable functional group, but is preferably the same as the polymerizable group represented by Piii1 in the general formula (ii).
  • Ria2 in the formula preferably represents a linear or branched alkyl group having 3 to 20 carbon atoms, and more preferably a linear or branched alkyl group having 6 to 18 carbon atoms. It is particularly preferable to represent an alkyl group from the viewpoint of suppressing crystallinity, further preferably to represent a branched alkyl group, and even more preferably to represent a branched alkyl group having 9 to 24 carbon atoms.
  • examples of the compound represented by the general formula (v) include ethyl (meth) acrylate, 2-hydroxyethyl acrylate, propyl (meth) acrylate, and butyl (meth) acrylate.
  • Mono (meth) acrylate having is preferable.
  • an acrylate in which Ria1 in the general formula (v) has a linear ether chain structure is preferable.
  • the acrylate having the ether chain structure a compound represented by the following structure is preferable.
  • q represents an integer of 1 to 12, preferably 1 to 5, and more preferably 1 to 3).
  • mono (meth) having a linear alkyl chain is particularly effective in reducing the driving voltage while maintaining good transparency when no voltage is applied. It is preferable to use acrylate.
  • the compound represented by the general formula (v) is preferably a mono (meth) acrylate having a branched alkyl chain represented by the following structure.
  • isobutyl (meth) acrylate isononyl (meth) acrylate, isodecyl (meth) acrylate, isomyristyl (meth) acrylate, and isostearyl (meth) acrylate are preferable.
  • an acrylate in which Ria1 in the general formula (v) has a linear ether chain structure is preferable.
  • a compound represented by the following structure is preferable.
  • (Q in the formula represents an integer of 1 to 10, preferably 1 to 5, and more preferably 1 to 3).
  • a mono (meth) acrylate having a branched alkyl chain from the viewpoint that the effect of reducing the driving voltage becomes remarkable while maintaining good transparency when no voltage is applied.
  • the content of the chain monofunctional polymerizable compound represented by the general formula (v), which is the fifth component, is 100, which is the total amount of the polymerizable compound (MA) contained in the polymer-dispersed liquid crystal composition of the present invention.
  • it is preferably 5% by mass or more, and more preferably 10% by mass or more. It is preferably 15% by mass or more, and particularly preferably 15% by mass or more.
  • it is preferably 60% by mass or less, more preferably 50% by mass or less, and particularly preferably 40% by mass or less.
  • the polymerizable compound (MA) may or may not contain, as other polymerizable compounds, a polymerizable compound having a mesogenic skeleton.
  • a polymerizable compound having a mesogenic skeleton examples include compounds represented by the following general formulas (2) to (8).
  • P11 to P74 represent polymerizable groups, and preferably independently of each other, any one of the following formulas (P- 1 ) to (P-20) is used. preferable. Further, in the following formulas (P-1) to (P-20), * indicates a bond with a carbon atom or another atom.
  • the formulas (P-1) and (P-2) are preferable from the viewpoint of enhancing the polymerizable property and the storage stability.
  • each P- (SX) -bond does not include -O-O-), especially single bonds, -O-,-.
  • Groups selected from S-, -CO-, -COO-, and -OCO- are preferred.
  • Each of M 11 , M 21 , M 31 , M 51 , and M 71 is a mesogen group represented by the following general formula (9-a) independently.
  • a 91 , A 92 , and A 93 are divalent groups each independently having at least one ring structure, and the divalent group is 1,2-cyclopropylene.
  • a 91 and / or A 92 may appear the same or different from each other.
  • Z 91 and Z 92 are independently -O-, -S-, -OCH 2- , -CH 2 O-, -CH 2 CH 2- , -CO-, -COO-, -OCO-, -CO.
  • j 91 and j 92 each independently represent 0 to 4
  • j 91 + j 92 represent an integer of 1 to 4
  • L 1 represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and a pentafluorosulfura.
  • Nyl group nitro group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, diethylamino group, diisopropylamino group, trimethylsilyl group, dimethylsilyl group, thioisocyano group, or one -CH 2 -or two or more non-adjacent -CH 2 -s are independently -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO.
  • the alkyl group may be linear or branched, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom, and the alkyl group may be substituted with a fluorine atom.
  • One -CH 2- or two or more non-adjacent -CH 2 -s are independently -O-, -S-, -CO-, -COO-, -OCO-, -CO-S- , -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO- or -C ⁇ C-).
  • M 41 is a trivalent organic group having a ring structure exemplified as A 91 , A 92 and A 93
  • M 61 has a ring structure exemplified as A 91 , A 92 and A 93 4 It is an organic group of valence.
  • R 11 and R 31 are hydrogen atoms, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, cyano groups, or alkyl groups having 1 to 20 carbon atoms, respectively.
  • the alkyl group may be linear or branched, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom, and one of the alkyl groups may be substituted.
  • -CH 2 -or two or more non-adjacent -CH 2 -s are independently -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S.
  • S 11 to S 72 each independently represent a spacer group or a single bond, and the spacer groups represented by the above S 11 to S 72 are carbon atoms.
  • the two CHs present in this group or two or more non-adjacent CHs are independent of each other and the oxygen atoms are not directly bonded to each other.
  • -O-, -S-, -NH-, -N (CH 3 )-, -CO-, -CH (OH)-, CH (COOH), -COO-, -OCO-, -OCOO-, -SCO -, -COS- or -C ⁇ C- may be substituted.
  • spacer groups from the viewpoint of orientation, a linear alkylene group having 2 to 8 carbon atoms and a fluorine atom are substituted.
  • An alkylene group having 2 to 6 carbon atoms and an alkylene group having 5 to 14 carbon atoms in which a part of the alkylene group is replaced with —O— are preferable.
  • S 11 to S 72 are present, they are the same. However, they may be different.
  • m1 to m7, n2 to n7, l4 to l6, and k6 independently represent integers from 0 to 5, and m1 to m7, n2 to n7, and l4 to each. It is preferable that l6 and k6 are independently 0 or 1, respectively.
  • the total content of the other polymerizable compounds other than the first component, the third component, the fourth component and the fifth component is the same as that of the polymerizable compound (MA) contained in the polymer-dispersed liquid crystal composition of the present invention.
  • the total amount is preferably 2% by mass or more, more preferably 5% by mass or more, and particularly preferably 10% by mass or more.
  • it is preferably 80% by mass or less, more preferably 70% by mass or less, and particularly preferably 60% by mass or less.
  • the polymerizable compound (MA) is the above-mentioned first component, third component, fourth component, fifth component, and the above-mentioned first component, third component, and fifth component.
  • an additive represented by the following general formula (X) is preferable to further contain an additive represented by the following general formula (X).
  • Y 31 represents a hydrogen atom or a methyl group.
  • X 31 represents an alkylene group having 130 or less carbon atoms, and the alkylene group may have a cyclic hydrocarbon group or a branched chain, and the alkylene group or one or more of the cyclic hydrocarbon groups.
  • n 31 represents an integer from 1 to 6 and represents It is preferable that X 31 has a group represented by the following formula (X-1).
  • X 6 , X 7 and X 8 each independently represent a hydrogen atom or a methyl group, and q, r, and s represent 1 to 4).
  • the amount of the compound having a group represented by the general formula (X-1) is preferably 0.005% by mass or more and 2% by mass or less of the total amount of the polymer-dispersed liquid crystal composition. , 0.01% by mass or more and 0.5% by mass or less, and further preferably 0.01% by mass or more and 0.2% by mass or less.
  • the second component is one or more trans-compounds represented by the following general formula (iii).
  • R 11 is an n-alkyl having 1 to 7 carbon atoms, n-alkoxy, an alkenyl, an alkenyloxy or an alkoxyalkyl having 2 to 7 carbon atoms independently of each other.
  • R 12 represents a fluorine atom, a chlorine atom, a cyano group, a CF 3 group, an OCF 3 group, an OCHF 2 group, an NCS group, or an alkyl group having 1 to 10 carbon atoms, and is a non-adjacent 1 in the alkyl group.
  • CH-, trans-CF CF-, -COO-, -CH 2 -CH 2- , -CF 2 -CF 2- or single bond, where n is 0 or 1.
  • the adhesion and the light scattering property are good, and low voltage drive at room temperature and low temperature can be realized. Also, preferably
  • the compound represented by the above general formula (iii) is used as a compound.
  • the compound represented by the above formula (iii) may preferably be a compound represented by the following dependent formulas (iii-1) to (iii-7).
  • R 11 and R 12 have the meanings shown under the above formula (iii), and Y 11 and Y 12 are H or F independently of each other.
  • the compound represented by the general formula (iii) is more preferably a compound represented by the dependent general formulas (iii-6) to (iii-7).
  • the compound represented by the above general formula (iii) may be a compound represented by the following dependent general formula (iii-8).
  • the compound represented by the above general formula (iii) as the third component is preferably 10% by mass or more and 80% by mass or less, preferably 25% by mass, based on 100% by mass of the total amount of the non-polymerizable liquid crystal compound (LB). More than 70% by mass is more preferable, and 35% by mass or more and 60% by mass or less is further preferable.
  • the non-polymerizable liquid crystal compound (LB) further preferably contains one or more compounds represented by the following general formula (vi-0) as the sixth component (however, the second component). except for).
  • R 11 represents an alkyl group having 1 to 10 carbon atoms, and one or two non-adjacent CH 2 groups in the alkyl group are replaced with oxygen atoms, -COO- and -OCO-. It may be, and one or more methylene groups may be replaced by -CH ⁇ CH-, and R12 has a fluorine atom, a chlorine atom, a cyano group, 3 CFs, 3 OCFs, and 2 OCHFs. , NCS group, cyano group, or alkyl group having 1 to 10 carbon atoms, and one or two non-adjacent CH 2 groups in the alkyl group are replaced with oxygen atom, -COO-, -OCO-.
  • a 11 , A 12 , and A 13 independently have a 1,4-phenylene group, a 1,4-cyclohexylene group, a 1,4-cyclohexenyl group, a tetrahydropyran-2,5-diyl group, and 1 , 3-Dioxane-2,5-diyl group, decahydronaphthalene-2,6-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, Representing a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group and a 2,6-naphthylene group, the 1,4-phenylene group, 1,2,3,4-tetrahydronaphthalene-2,6- The diyl group and 2,6-naphthylene group are unsubstituted or may have one or more fluorine atom
  • R 11 in the general formula (vi-0) is an alkyl group having 1 to 5 carbon atoms (one or two non-adjacent CH 2 in the alkyl group).
  • the group may be replaced with an oxygen atom), where R12 is a fluorine atom, a cyano group, or an alkyl group having 1-5 carbon atoms (one of the non-adjacent ones in the alkyl group or one of them).
  • CH 2- , -CF 2 O-, or -OCF 2- (when a plurality of Z 11s are present, they may be the same or different), and are preferably single-bonded, -COO-,. -CF 2 O- is more preferable, and A 11 , A 12 and A 13 are independently 1,4-phenylene group, 1,4-cyclohexylene group and 1,3-dioxane-2, respectively.
  • A13s may be the same or different), preferably 1,4-phenylene group, 1,4-cyclohexylene group, pyrimidin-2, 5-Diyl group, 2,6-naphthylene group (the 1,4-phenylene group, 2,6-naphthylene group is unsubstituted or has one or more fluorine atoms as substituents, or CH 3 groups.
  • n 1 is preferably 0 or 1.
  • the sixth component is one or more liquid crystal compounds represented by the following general formula (vi).
  • the 1,4-phenylene group is unsubstituted or can have one or more fluorine atoms, chlorine atoms, CF 3 , OCF 3 , or methyl groups as substituents.
  • Ring A 7 represents a 1,4-phenylene group or a 1,4-cyclohexylene group, and the 1,4-phenylene group is unsubstituted or has one or more fluorine atoms as a substituent.
  • Ring A 8 represents a 1,4-phenylene group, the 1,4-phenylene group being unsubstituted or as a substituent one or more fluorine atoms, a chlorine atom, CF 3 , OCF 3 , Or can have a methyl group
  • C ⁇ C- n represents 0 or 1. However, the second component is excluded.
  • R 3 is an alkyl group having 1 to 10 carbon atoms or an alkoxy group.
  • Ring A6 is a 1,4 phenylene group, a 1,4 cyclohexylene group (the 1,4 phenylene group is unsubstituted or can have one or more fluorine atoms as a substituent). It is more preferable to have. It is even more preferred that one selected from the group consisting of Y 4 , Y 5 , Y 8 and Y 9 represents a fluorine atom and the remaining three all represent hydrogen atoms.
  • Z 6 and Z 7 are each independently, more preferably single-bonded, -COO-, -OCO-, -CH 2 -CH 2- , and even more preferably single-bonded or -COO-.
  • R 3 represents an alkyl group having 1 to 10 carbon atoms, preferably 2 to 7, and more preferably 2 to 5.
  • Ring A6 has a 1,4 - phenylene group, a 1,4-cyclohexylene group, and the 1,4-phenylene group is unsubstituted or can have one fluorine atom as a substituent.
  • n represents 0.
  • ring A 7 and ring A 8 represent a 1,4-phenylene group, and any one of the 1,4-phenylene groups has at least one fluorine atom as a substituent.
  • Z 6 , Z 7 and Z 8 represent a single bond or -COO-
  • ring A 6 represents a 1,4-phenylene group or a 1,4 cyclohexylene group and n is represented by 0 or 1. It is preferable to use the compound to be used from the viewpoint of lowering the voltage.
  • R 51 represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms
  • Y 11 to Y 62 independently represent a hydrogen atom or a fluorine atom, respectively.
  • 11 to Y 62 may all represent hydrogen atoms, and one or more of them may represent fluorine atoms.
  • R 511 represents an alkyl group having 2 to 7 carbon atoms or an alkoxy group having 2 to 7 carbon atoms, preferably an alkyl group having 2 to 5 carbon atoms or an alkoxy group having 2 to 5 carbon atoms.
  • the compound represented by the above general formula (vi-0) as the sixth component is preferably 20% by mass or more and 90% by mass or less, preferably 30% by mass or less, based on 100% by mass of the total amount of the non-polymerizable liquid crystal compound (LB). It is more preferably mass% or more and 75% by mass or less, and further preferably 40% by mass or more and 65% mass% or less.
  • the total content of the liquid crystal compound represented by the general formula (vi) as the sixth component is 2% by mass or more and 70% by mass with respect to the total amount of the non-polymerizable liquid crystal compound (LB) of 100% by mass.
  • the following is preferable, 5% by mass or more and 50% by mass or less is more preferable, and 10% by mass or more and 30% by mass or less is further preferable.
  • the total content of the liquid crystal compounds represented by the general formulas (vi-1) to (vi-10) as the sixth component is 100% by mass of the total amount of the non-polymerizable liquid crystal compound (LB).
  • the total content of the liquid crystal compounds represented by the general formulas (vi-A) to (vi-F) as the sixth component is 100 mass by mass of the total amount of the non-polymerizable liquid crystal compound (LB). %, 2% by mass or more and 70% by mass or less is preferable, 5% by mass or more and 50% by mass or less is more preferable, and 10% by mass or more and 30% by mass or less is further preferable.
  • the refractive index anisotropy ( ⁇ n) of the non-polymerizable liquid crystal composition used for the polymer-dispersed liquid crystal element is generally preferably high, ⁇ n is preferably 0.16 or more, more preferably 0.18 or more, and 0.20. The above is even more preferable, and 0.22 or more is most preferable.
  • the normal light refractive index (no) of these non-polymerizable liquid crystal compositions having ⁇ n is usually about 1.50 to 1.54.
  • the refractive index of the actual polymer is higher than that of the pure polymer because it is cured in the form of embracing a part of the non-polymerizable liquid crystal composition. Therefore, the refractive index of the monomer and the oligomer is preferably lower than 1.5, more preferably 1.48 or less, and even more preferably 1.47 or less.
  • the polymer-dispersed liquid crystal composition of the present invention can contain a polymerization initiator.
  • the polymerization initiator used in the present invention is used for polymerizing the liquid crystal composition of the present invention.
  • the photopolymerization initiator used when the polymerization is carried out by light irradiation is not particularly limited, but has the above-mentioned one polymerizable group, a polymerizable compound satisfying the formula (I), and a mesogenic skeleton.
  • Known and commonly used compounds can be used to the extent that the orientation of the polymerizable compound is not impaired.
  • Examples of the photoacid generator include a diazodisulfone-based compound, a triphenylsulfonium-based compound, a phenylsulfone-based compound, a sulfonylpyridine-based compound, a triazine-based compound, and a diphenyliodonium-based compound.
  • the content of the photopolymerization initiator is preferably 0.1% by mass or more and 10% by mass or less, preferably 0% by mass, based on 100% by mass of the total amount of the polymerizable compound (MA) used in the polymer-dispersed liquid crystal composition of the present invention. .2% by mass or more and 6% by mass or less is more preferable. These can be used alone or in combination of two or more.
  • thermal polymerization initiator used in the thermal polymerization known and commonly used ones can be used, for example, methylacetate acetate peroxide, cumenhydroperoxide, benzoyl peroxide, bis (4-t-butylcyclohexyl).
  • the content of the thermal polymerization initiator is 0.1% by mass or more and 10% by mass or less with respect to 100% by mass of the total amount of the polymerizable compound (MA) used in the polymerizable composition of the polymer-dispersed liquid crystal composition of the present invention. Is preferable, and 1% by mass or more and 6% by mass or less is more preferable. These can be used alone or in combination of two or more.
  • the polymer-dispersed liquid crystal composition of the present invention is a polymerization inhibitor, an antioxidant, and a light stabilizer as long as it does not impair practical electro-optical properties and adhesion when made into a polymer-dispersed liquid crystal element.
  • Chain transfer agents, dyes, pigments, particles with a particle size of less than 1 ⁇ m, chiral compounds, or alignment materials can be added.
  • the polymer-dispersed liquid crystal composition is one or more selected from the group consisting of a polymerization inhibitor, an antioxidant, a light stabilizer, particles having a particle size of less than 1 ⁇ m, a dye, and a pigment. It is preferable to contain it.
  • the polymerization inhibitor used in the present invention is for controlling the electro-optical properties by controlling the polymerization reaction of the polymer-dispersed liquid crystal composition of the present invention, or is a polymerizable compound having a polarity which is a third component. It can be used to assist the efficacy of.
  • a known and commonly used compound can be used. For example, p-methoxyphenol, cresol, t-butylcatechol, 3.5-di-t-butyl-4-hydroxytoluene, 2.2'-methylenebis (4-methyl-6-t-butylphenol), 2.2.
  • 2-Hydroxy-1,4-naphthoquinone, 1,4-naphthoquinone, 2,3-dichloro-1,4-naphthoquinone, anthraquinone, diphenoquinone, and other quinone compounds are preferred, p-methoxyphenol, 4-methoxy- 1-naphthol, tert-butylhydroquinone and 2-hydroxy-1,4-naphthoquinone are particularly preferred.
  • the content of the polymerization inhibitor is 0 or more and 2.0% by mass or less with respect to 100% by mass of the total amount of the polymerizable compound (MA) used in the polymerizable composition of the polymer-dispersed liquid crystal composition of the present invention. It is preferable, and it is more preferable that it is 0 or more and 0.5% by mass or less.
  • the antioxidant used in the present invention can be used to impart practical durability to the polymer-dispersed liquid crystal element of the present invention.
  • a hydroquinone derivative, a nitrosamine-based polymerization inhibitor, a hindered phenol-based antioxidant and the like can be used.
  • tert-butylhydroquinone Wako Pure Chemical Industries, Ltd.
  • RH1 is an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms.
  • one or more hydrogen atoms present in the group may be independently substituted with a fluorine atom or a chlorine atom, respectively.
  • it may be an alkyl group having 2 to 7 carbon atoms, an alkoxyl group having 2 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyloxy group having 2 to 7 carbon atoms. It is more preferable that it is an alkyl group having 3 to 7 carbon atoms or an alkenyl group having 2 to 7 carbon atoms.
  • the compounds represented by the general formulas (H-2) to (H-3) are particularly preferable.
  • the content of the antioxidant is preferably 0 or more and 2.0% by mass or less, preferably 0 or more, with respect to 100% by mass of the total amount of the polymerizable compound (MA) used in the polymer-dispersed liquid crystal composition of the present invention. It is more preferably 0.5% by mass or less.
  • the light stabilizer used in the present invention can be used to impart practical durability of the polymer-dispersed liquid crystal element of the present invention.
  • Examples of such compounds include "TINUVIN 111FDL”, “TINUVIN 123”, “TINUVIN 144”, “TINUVIN 152”, “TINUVIN 292”, “TINUVIN 622”, “TINUVIN 770”, “TINUVIN 765", "TINUVIN”.
  • the amount of the ultraviolet absorber added is preferably 0.0 or more and 2.0% by mass or less, preferably 0 or more, with respect to the total amount of the polymerizable compound (MA) used in the polymer-dispersed liquid crystal composition of the present invention. It is more preferably 0.0 or more and 1.0% by mass or less.
  • the chain transfer agent used in the present invention can be used to further improve the adhesion between the polymer-dispersed liquid crystal composition and the substrate.
  • the chain transfer agent are mercaptan compounds such as octyl mercaptan, n-butyl mercaptan, n-pentyl mercaptan, n-hexadecyl mercaptan, n-tetradecylmel, n-dodecyl mercaptan, t-tetradecyl mercaptan, and t-dodecyl mercaptan.
  • R95 represents an alkyl group having 2 to 18 carbon atoms, and the alkyl group may be a straight chain or a branched chain, and one or more methylene groups in the alkyl group are oxygen atoms.
  • the content of the chain transfer agent is 0.0 or more and 10% by mass or less with respect to 100% by mass of the total amount of the polymerizable compound (MA) used in the polymerizable composition of the polymer-dispersed liquid crystal composition of the present invention. It is preferable, and it is more preferable that it is 0.0 or more and 5.0% by mass or less.
  • the dye used in the present invention can be used to impart color to or control the color of the polymer-dispersed liquid crystal element of the present invention.
  • the dye is not particularly limited, and known and commonly used dyes can be used as long as they are soluble in liquid crystal or dispersed in a polymer network.
  • Examples of the dye include a dichroic dye, a fluorescent dye and the like.
  • Examples of such pigments include polyazo pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, quinophthalone pigments, cyanine pigments, phthalocyanine pigments, perylene pigments, perinone pigments, squarylium pigments, and the like.
  • the dye is preferably a dye exhibiting liquidity.
  • the content of the dye is preferably 0 or more and 8% by mass or less, preferably 0 or more and 4% by mass, based on 100% by mass of the total amount of the non-polymerizable liquid crystal compound (LB) used in the polymer-dispersed liquid crystal composition of the present invention. It is more preferably mass% or less.
  • the pigment used in the present invention can be used to impart color to or control the color of the polymerizable liquid crystal element of the present invention.
  • the dye is not particularly limited, and a liquid crystal display or a known and commonly used dye can be used as long as it is dispersed in the network polymer.
  • examples of such pigments include azo pigments, diketopyrrolopyrrole pigments, quinacridone pigments, dioxazine pigments, perylene pigments, phthalocyanine pigments, carbon black pigments, and the like.
  • the pigment is preferably a pigment having good dispersibility in a network polymer.
  • the content of the pigment is preferably 0 or more and 8% by mass or less, preferably 0 or more and 4% by mass, based on 100% by mass of the total amount of the non-polymerizable liquid crystal compound (LB) used in the polymer-dispersed liquid crystal composition of the present invention. It is more preferably mass% or less.
  • particles with a particle size of less than 1 ⁇ m can be used to impart various functions to the polymer-dispersed liquid crystal element of the present invention.
  • Such particles are not particularly limited, but can be used as long as the electro-optical characteristics and adhesion of the liquid crystal element are not impaired.
  • Such particles include inorganic fillers such as alumina, titanium white, titanium black, aluminum hydroxide, talc, clay, mica, barium titanate, zinc oxide, glass fiber, metal powder such as silver powder and copper powder, and nitrided metal.
  • magnesia aluminum oxide
  • silica crystalline silica
  • silicon oxide fused silica
  • graphite carbon fiber including carbon nanofibers, etc.
  • Examples thereof include conductive fillers, silver nanoparticles, QD illuminant particles, perovskite type illuminant particles and the like.
  • the particles are preferably particles having good dispersibility in the network polymer.
  • the content of the particles is preferably 0 or more and 5% by mass or less, preferably 0 or more, with respect to 100% by mass of the total amount of the non-polymerizable liquid crystal compound (LB) used in the polymer-dispersed liquid crystal composition of the present invention. It is more preferably 3% by mass or less.
  • the chiral compound used in the present invention can be used to impart various functions to the polymer-dispersed liquid crystal element of the present invention.
  • the chiral compound is not particularly limited, but can be used as long as the electro-optical characteristics and adhesion of the liquid crystal element are not impaired.
  • cholesterol pelargonate having a cholesteryl group as a chiral group cholesterol stearate, and "CB-15", "C-15”, and Merck manufactured by BDH having a 2-methylbutyl group as a chiral group.
  • a chiral compound when contained, it depends on the use of the polymer of the polymer-dispersed liquid crystal composition of the present invention, but the value obtained by dividing the thickness (d) of the obtained polymer by the spiral pitch (P) in the polymer. It is preferable to add an amount having (d / P) in the range of 0.1 to 100, and even more preferably an amount in the range of 0.1 to 20.
  • the chiral compound preferably has as little content as possible to obtain the desired spiral pitch in order to bring out the characteristics of the liquid crystal composition.
  • the content of the chiral compound is preferably 0 or more and 8% by mass or less, preferably 0 or more, with respect to 100% by mass of the total amount of the non-polymerizable liquid crystal compound (LB) used in the polymer-dispersed liquid crystal composition of the present invention. It is more preferably 4% by mass or less.
  • the polymer-dispersed liquid crystal composition of the present invention can contain an alignment material in order to control the orientation of the liquid crystal element.
  • an alignment material known and commonly used materials are used as long as they are dissolved in the liquid crystal composition.
  • orientation material include a polymerizable compound having a polar group at one end of the mesogen skeleton and a long-chain alkyl group at the other end, and a polymerizable liquid crystal compound having a polar group at the lateral position of the mesogen skeleton.
  • Examples thereof include a polymerizable compound having a plurality of mesogen skeletons and having a polar group on the side chain of a long-chain alkyl group that binds one mesogen skeleton to the mesogen skeleton.
  • the liquid crystal element using the polymer-dispersed liquid crystal composition of the present invention includes at least a layer (phase-separated liquid crystal layer) in which the liquid crystal and the network polymer are phase-separated, an electrode, and a base material. Alternatively, it includes a phase-separated liquid crystal layer, an alignment film phase, an electrode, and a base material that supports the phase-separated liquid crystal layer, the alignment film phase, and the electrode.
  • the phase-separated liquid crystal phase is a polymer network derived from each polymerizable component contained in the polymerizable compound (MA) by polymerizing the polymerizable compound (MA) contained in the polymer-dispersed liquid crystal composition.
  • the liquid crystal element of the present invention when no voltage is applied, can be in a light scattering state due to a network structure made of a polymer and liquid crystal molecules existing in the voids thereof. On the other hand, when a voltage is applied, the liquid crystal molecules are oriented perpendicularly to the substrate to make the transparent state.
  • the liquid crystal element of the present invention may be configured so that the orientation of the liquid crystal molecules can be controlled by applying a voltage, but it is preferably configured as a vertical electric field type liquid crystal element.
  • the vertical electric field type liquid crystal element is a liquid crystal element in which electrodes are arranged so that an electric field is generated perpendicular to the alignment film.
  • electrodes are usually provided on both of two transparent substrates that sandwich the phase-separated liquid crystal layer.
  • the configuration of the vertical electric field type liquid crystal element according to the present invention includes a first substrate and a second substrate provided with a transparent electrode (layer) made of a transparent conductive material, and the first substrate and the second substrate, respectively. It has a phase-separated liquid crystal layer sandwiched between the two.
  • the phase-separated liquid crystal layer is composed of a polymer-dispersed liquid crystal material composed of liquid crystal molecules and polymer components contained in the liquid crystal composition.
  • the substrate used for the liquid crystal element of the present invention is a substrate usually used for a liquid crystal display element, an organic light emitting display element, other display elements, optical components, a dimming element, a colorant, marking, a printed matter or an optical film, and is described above.
  • a substrate usually used for a liquid crystal display element, an organic light emitting display element, other display elements, optical components, a dimming element, a colorant, marking, a printed matter or an optical film, and is described above.
  • a substrate include a glass base material, a metal base material, a ceramic base material, a plastic base material, and an organic material such as paper.
  • the base material when the base material is an organic material, examples thereof include cellulose derivatives, polyolefins, polyesters, polyolefins, polycarbonates, polyacrylates, polyarylates, polyether sulfone, polyimides, polyphenylene sulfides, polyphenylene ethers, nylons and polystyrenes.
  • a plastic base material such as polyester, polystyrene, polyolefin, cellulose derivative, polyarylate, polycarbonate, and polyimide.
  • one substrate may or may not have transparency that is practical as a liquid crystal element, and the other substrate may or may not have transparency.
  • the shape of the substrate As the shape of the substrate, the shape of a flat plate is shown, but other shapes such as those having a curved surface may be used. Further, the substrate may have an electrode layer, an antireflection function, and a reflection function, if necessary.
  • the surface treatment of these substrates may be performed. Examples of the surface treatment include ozone treatment, plasma treatment, corona treatment, and silane coupling treatment.
  • an organic thin film, an inorganic oxide thin film, a metal thin film, etc. are provided on the surface of the base material by a method such as vapor deposition, or to add optical value.
  • the material may be a pickup lens, a rod lens, an optical disk, a retardation film, a light diffusing film, a microlens sheet, a color filter, or the like.
  • the electrode used in the liquid crystal element of the present invention is provided in the liquid crystal element so as to generate an electric field capable of controlling the orientation of the liquid crystal molecules in the phase-separated liquid crystal layer.
  • the electric field strength is controlled by the degree of voltage application to the electrodes.
  • the shape of the electrode is not particularly limited, and the conductive portion may have a striped shape, a mesh shape, or a random mesh shape.
  • As such an electrode material it is preferable to use a metal material, and specifically, Al, Cu, Au, Ag, Cr, Ta, Ti, Mo, W, Ni or at least one of these is used. Examples thereof include alloys containing Al, and alloys containing Al or Al are preferable.
  • the electrode is composed of the transparent electrode layer 2.
  • a transparent electrode layer can be made of a known transparent conductive material such as ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and IZTO (Indium Zinc Tin Oxide).
  • ITO Indium Tin Oxide
  • IZO Indium Zinc Oxide
  • IZTO Indium Zinc Tin Oxide
  • the substrate may be oriented so that the liquid crystal molecules in the polymer-dispersed liquid crystal element of the present invention are horizontally or vertically aligned, or may be provided with an alignment film.
  • the alignment treatment include stretching treatment, rubbing treatment, polarized ultraviolet-visible light irradiation treatment, ion beam treatment, oblique vapor deposition treatment of SiO 2 on a substrate, and the like.
  • Examples of such an alignment film include polyimide, polysiloxane, polyamide, polyvinyl alcohol, polycarbonate, polystyrene, polyphenylene ether, polyarylate, polyethylene terephthalate, polyether sulfone, epoxy resin, epoxy acrylate resin, acrylic resin, azo compound, and coumarin.
  • Examples thereof include compounds such as compounds, chalcone compounds, cinnamate compounds, flugide compounds, anthraquinone compounds, azo compounds and arylethane compounds, and polymers and copolymers of the above compounds.
  • the compound to be oriented by the rubbing is one in which the crystallization of the material is promoted by the alignment treatment or the heating step after the alignment treatment.
  • the compounds to be subjected to alignment treatment other than rubbing it is preferable to use a photo-alignment material.
  • the liquid crystal composition is brought into contact with a substrate having an alignment function, the liquid crystal molecules are oriented in the vicinity of the substrate along the direction in which the substrate is oriented. Whether the liquid crystal molecules are oriented horizontally, inclined or perpendicular to the substrate is greatly influenced by the orientation treatment method for the substrate.
  • the liquid crystal element of the present invention is obtained by dropping or applying a polymer-dispersed liquid crystal composition onto a substrate by, for example, a roll-to-roll method, and laminating an opposed substrate. , It is preferable to manufacture from a liquid crystal element.
  • the polymer-dispersed liquid crystal composition is placed on a first electrode, a glass base material having an alignment film and a first electrode, or a plastic base material. It is applied and bonded so that the liquid crystal composition is in contact with the electrode side or the alignment film side of the second electrode, or the glass base material having the alignment film and the second electrode, or the plastic base material.
  • the liquid crystal element can also be manufactured by making the thickness uniform.
  • Examples of the method for applying the polymer-dispersed liquid crystal composition used in the present invention include an applicator method, a bar coating method, a roll coating method, a direct gravure coating method, a reverse gravure coating method, an inkjet method, a die coating method, and a cap coating method.
  • Etc. a known and commonly used method can be used.
  • a sealant having an epoxy-based photothermal combination curability is drawn on either the backplane or the frontplane of the hollow element in a closed-loop bank shape using a dispenser.
  • the liquid crystal element can be manufactured by dropping a predetermined amount of the liquid crystal composition into the liquid crystal composition and then joining the front plane and the back plane.
  • the liquid crystal element of the present invention can be manufactured from a liquid crystal element by interposing a spacer for maintaining a gap between two substrates, as in the case of a well-known liquid crystal element.
  • the thickness between the substrates that is, the thickness of the phase separation layer is preferably 2 to 50 ⁇ m, more preferably 10 to 30 ⁇ m.
  • the spacer may be sprayed on the substrate in advance, or may be mixed in the polymer-dispersed liquid crystal composition in advance and applied onto the substrate at the same time as the polymer-dispersed liquid crystal composition.
  • the method for sandwiching the polymer-dispersed liquid crystal composition between the two substrates may be a normal vacuum injection method, but it is preferably performed by dropping or coating such as the ODF method.
  • the polymer-dispersed liquid crystal composition is in a uniform isotropic state from the dropping or coating to the polymerization of the polymerizable composition.
  • the method of sandwiching the polymer-dispersed liquid crystal composition between two substrates can be performed by sandwiching the two substrates with a laminator or the like.
  • the polymer-dispersed liquid crystal composition of the present invention may be used as a composition in which particles for determining the thickness of the liquid crystal element are mixed, and the composition may be held in the hollow element.
  • particles known and commonly used glass particles and polymer particles used in general liquid crystal display elements and liquid crystal displays are used.
  • the polymer-dispersed liquid crystal composition and the composition containing particles that determine the thickness of the liquid crystal element are applied onto a plastic substrate containing the first electrode, and then the second electrode is contained.
  • a method of irradiating ultraviolet rays in a vacuum state in which the second electrodes are bonded so as to face each other is preferable.
  • Ultraviolet irradiation is suitable as a method for polymerizing the polymer-dispersed liquid crystal composition of the present invention.
  • a metal halide lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, or the like can be used as the lamp that generates ultraviolet rays.
  • the wavelength of the ultraviolet rays to be irradiated is an ultraviolet ray in a wavelength region that is the absorption wavelength region of the photopolymerization initiator contained in the polymer-dispersed liquid crystal composition and is not in the absorption wavelength region of the liquid crystal composition contained therein.
  • UV-LED lamp capable of irradiating a single wavelength.
  • the intensity of the ultraviolet rays to be irradiated can be appropriately adjusted in order to obtain the desired dimming layer, but is preferably 1 to 200 mw / cm 2 and more preferably 5 to 50 mw / cm 2 .
  • the time for irradiating the ultraviolet rays is appropriately selected depending on the intensity of the ultraviolet rays to be irradiated, but is preferably 10 to 300 seconds.
  • the temperature at the time of irradiation with ultraviolet rays is an important factor that determines the characteristics of the light control layer, but is preferably a temperature higher than the isotropic-nematic transition point (Tnm) of the polymer-dispersed liquid crystal composition.
  • Tnm isotropic-nematic transition point
  • the liquid crystal element of the present invention can be used as it is or can be used by being bonded to another substrate. Further, an adhesive or an adhesive layer, an adhesive or an adhesive layer, a protective film, a polarizing film or the like may be laminated.
  • a horizontal electric field type or another electric field type may be adopted for the liquid crystal element of the present invention.
  • the fringe electric field adopted in the FFS drive mode may be adopted.
  • a horizontally oriented layer may be provided.
  • the horizontally oriented layer can be made of a known material.
  • the liquid crystal element of the present invention is preferably used for, for example, a building material, a light control glass, a smart window for an automobile, a light control unit in an OLED display, or the like.
  • the liquid crystal display element of the present invention can be used for the same purposes as the conventional polymer-dispersed liquid crystal display element, and can also be particularly preferably used for a transmissive display, a flexible display, and the like.
  • the dimming element of the present invention has a pair of transparent electrode base materials and a composite layer containing a polymer network and a liquid crystal compound arranged between the pair of transparent electrode base materials.
  • the polymer network is a polymer network derived from the polymerizable compound (MA) contained in the polymer-dispersed liquid crystal composition, and the liquid crystal compound is a non-polymerizable liquid crystal contained in the polymer-dispersed liquid crystal composition. It is a compound (LB).
  • the dimming element the above-mentioned liquid crystal element using the polymer-dispersed liquid crystal composition may be used, and the light transmittance of the liquid crystal element may be electrically controlled.
  • This dimming element may simply be the above-mentioned liquid crystal element equipped with a voltage application device, but the liquid crystal element may be PVB (polyvinyl butyral), EVA (ethylene vinyl acetate copolymer resin), TPU (polyurethane type), SGP, etc. It may be a laminated glass sandwiched between two pieces of glass via an interlayer film of. Further, a functional film such as an ultraviolet ray cut or a heat ray cut may be added.
  • Table 1 shows the non-polymerizable liquid crystal compound (LB) used in Examples and Comparative Examples described later. Each component of the polymerizable compound (MA) used in Examples and Comparative Examples described later is shown in Table 2.
  • urethane acrylate UA-1 average molecular weight Mw: 29800.
  • Mn number average molecular weight
  • Mw weight average molecular weight
  • Example 1 As the first component, 20 parts by weight of UA-1 produced in Synthesis Example 1, 30 parts by weight of APG-700 as the fourth component, 35 parts by weight of ACMO as the second component, and 15 parts by weight of ISTA as the fifth component. After mixing, 0.1 part by weight of the additive P-2M was added to Irg. 1 part by weight of 651 was added and dissolved while stirring at 50 ° C. to obtain a polymerizable compound ma-1 as the polymerizable compound (MA) of the present invention. Further, a non-polymerizable liquid crystal compound lb-1 consisting of 100 parts by weight of the liquid crystal composition LC1 shown in Table 1 was prepared.
  • Table 3 shows the main physical property values of the non-polymerizable liquid crystal compound lb-1.
  • the non-polymerizable liquid crystal compound so that the weight ratio (MA / LB weight ratio) of the polymerizable compound (MA) / non-polymerizable liquid crystal compound (LB) to the obtained polymerizable compound ma-1 is 56/44.
  • lb-1 was added and dissolved with stirring at 50 ° C. to obtain a polymer-dispersed liquid crystal composition PL1.
  • the obtained polymer-dispersed liquid crystal composition PL1 is injected into a glass cell having a thickness of 15 ⁇ m (consisting of a glass substrate / transparent electrode layer / air layer / transparent electrode layer / glass substrate) at room temperature, and then at room temperature.
  • a liquid crystal polymer composite was obtained by irradiating with ultraviolet rays. The conditions of ultraviolet rays at this time were that the light source was a UV-LED lamp, the intensity was 10 mW / cm 2 , and the time was 60 seconds.
  • the transmittance (T0) in the 0V state at temperatures of 25 ° C and -20 ° C, respectively, is 0%, and the transmittance (T100) when 100V is applied.
  • the voltage at which the transmittance reaches 90% was defined as the drive voltage (V90) and evaluated when the transmittance was 100%.
  • the drive voltages were 45.2V and 56.8V, respectively.
  • the adhesion was evaluated by the following method. First, glass beads having a particle size of 15 ⁇ m were sprayed on the transparent electrode surface of a PET film with a protective film and a transparent electrode, and the liquid crystal composition was dropped onto the glass beads and applied with an applicator. After that, the transparent electrode surface of the PET film on the coated surface and the coated surface are bonded so as to be in contact with each other, and the film laminate in which pressure is uniformly applied to the entire surfaces of the upper and lower PET films is irradiated with ultraviolet rays at room temperature to obtain a polymer. A distributed liquid crystal element was obtained. The obtained polymer-dispersed liquid crystal element was cut out with a cutter so as to have a width of 1 cm.
  • a 180 ° peeling test was performed using a cut-out polymer-dispersed liquid crystal device.
  • a &D's Forstester MCT2150 was used, and one side sandwiched between PET films with transparent electrodes was peeled off in the 180 ° direction under a sample width of 10 mm, a tensile speed of 50 mm / min, and an atmosphere of 25 ° C. The maximum strength at the time was calculated. The intensity was 0.4 N / cm.
  • Examples 2 to 6, Comparative Examples 1 to 4 Polymer-dispersed liquid crystal compositions PL2 to PL6 of Examples 2 to 6 and Comparative Examples 1 to 4 in the same manner as in Example 1 except that each component was used in the compounding ratios shown in Tables 3 and 4. cPL1 to cPL4 were obtained. Using the obtained polymer-dispersed liquid crystal compositions PL2 to PL6 and cPL1 to cPL4, a polymer-dispersed liquid crystal element was obtained in the same manner as in Example 1. Each evaluation was carried out in the same manner as in Example 1 using the obtained polymer-dispersed liquid crystal device. The results are shown in Tables 3 and 4.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Mathematical Physics (AREA)
  • Dispersion Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Liquid Crystal (AREA)
  • Liquid Crystal Substances (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
PCT/JP2021/046420 2020-12-25 2021-12-16 高分子分散型液晶組成物、液晶素子及び調光素子 Ceased WO2022138418A1 (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020237016421A KR20230122577A (ko) 2020-12-25 2021-12-16 고분자 분산형 액정 조성물, 액정 소자 및 조광 소자
CN202180074950.7A CN116390961A (zh) 2020-12-25 2021-12-16 高分子分散型液晶组合物、液晶元件及调光元件
JP2022544337A JP7276619B2 (ja) 2020-12-25 2021-12-16 高分子分散型液晶組成物、液晶素子及び調光素子

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2020217628 2020-12-25
JP2020-217628 2020-12-25

Publications (1)

Publication Number Publication Date
WO2022138418A1 true WO2022138418A1 (ja) 2022-06-30

Family

ID=82159261

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2021/046420 Ceased WO2022138418A1 (ja) 2020-12-25 2021-12-16 高分子分散型液晶組成物、液晶素子及び調光素子

Country Status (5)

Country Link
JP (1) JP7276619B2 (https=)
KR (1) KR20230122577A (https=)
CN (1) CN116390961A (https=)
TW (1) TWI904302B (https=)
WO (1) WO2022138418A1 (https=)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2026070377A1 (ja) * 2024-09-25 2026-04-02 Ｔｏｐｐａｎホールディングス株式会社 液晶調光素子

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2025072914A (ja) * 2023-10-25 2025-05-12 Ｔｏｐｐａｎホールディングス株式会社 調光シート、調光装置、および、調光シートの製造方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011026526A (ja) * 2009-07-29 2011-02-10 Dic Corp 高分子分散型液晶組成物、及びそれを用いた高分子分散型液晶素子
CN104177539A (zh) * 2014-07-22 2014-12-03 北京大学 一种聚合物分散液晶材料的制备方法
JP2019515989A (ja) * 2016-04-13 2019-06-13 メルク・パテント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ ＧｍｂＨ ナノカプセル化のための組成物および液晶媒体を含むナノカプセル

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0564869A1 (en) 1992-03-31 1993-10-13 MERCK PATENT GmbH Electrooptical liquid crystal systems
JP4794259B2 (ja) 2005-09-28 2011-10-19 株式会社Ａｄｅｋａ 調光性液晶素子
CN101987960B (zh) * 2009-07-29 2015-02-11 Dic株式会社 高分子分散型液晶元件用液晶组合物及使用其的液晶元件
JP2014206715A (ja) * 2013-03-19 2014-10-30 日産化学工業株式会社 横電界駆動型液晶表示素子用液晶配向膜を有する基板の製造方法
US20190177618A1 (en) * 2016-08-24 2019-06-13 Merck Patent Gmbh Liquid crystalline medium and liquid crystal display
JP7346903B2 (ja) * 2019-05-16 2023-09-20 Dic株式会社 液晶素子、及び液晶素子を用いた物品

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011026526A (ja) * 2009-07-29 2011-02-10 Dic Corp 高分子分散型液晶組成物、及びそれを用いた高分子分散型液晶素子
CN104177539A (zh) * 2014-07-22 2014-12-03 北京大学 一种聚合物分散液晶材料的制备方法
JP2019515989A (ja) * 2016-04-13 2019-06-13 メルク・パテント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ ＧｍｂＨ ナノカプセル化のための組成物および液晶媒体を含むナノカプセル

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2026070377A1 (ja) * 2024-09-25 2026-04-02 Ｔｏｐｐａｎホールディングス株式会社 液晶調光素子

Also Published As

Publication number Publication date
JPWO2022138418A1 (https=) 2022-06-30
TW202229524A (zh) 2022-08-01
JP7276619B2 (ja) 2023-05-18
TWI904302B (zh) 2025-11-11
CN116390961A (zh) 2023-07-04
KR20230122577A (ko) 2023-08-22

Similar Documents

Publication Publication Date Title
JP5609054B2 (ja) 高分子分散型液晶素子用液晶組成物、及びそれを用いた液晶素子
CN101987960B (zh) 高分子分散型液晶元件用液晶组合物及使用其的液晶元件
CN111948846B (zh) 高分子分散型液晶元件和高分子分散型液晶元件用液晶组合物
JP7082127B2 (ja) 重合性液晶組成物、それを用いた光学フィルム、及びその製造方法。
JP6828850B2 (ja) 光散乱型液晶素子用液晶組成物、光散乱型液晶素子、及びスマートウィンドウ
JP2011026526A (ja) 高分子分散型液晶組成物、及びそれを用いた高分子分散型液晶素子
JP2023171293A (ja) 高分子分散型液晶組成物及び調光素子
JP7276619B2 (ja) 高分子分散型液晶組成物、液晶素子及び調光素子
TW202438646A (zh) 液晶元件
WO2018225579A1 (ja) 重合性液晶組成物、それを用いた光学フィルム、及びその製造方法
JP7543829B2 (ja) 重合性組成物および液晶調光素子
TWI899404B (zh) 高分子分散型液晶組成物、液晶元件及調光元件
JP7528462B2 (ja) ポリマーネットワーク型液晶素子用液晶組成物、該液晶組成物を用いたポリマーネットワーク型液晶表示素子、及びその製造方法
JP2024002760A (ja) 調光パネル及び調光パネルを用いた窓
JP2021066873A (ja) 重合性液晶組成物、高分子分散型液晶材料、並びに該高分子分散型液晶材料を用いた液晶素子及び調光素子
CN118256254A (zh) 液晶组合物、液晶层和调光元件
JP2022103094A (ja) 高分子分散型液晶組成物、液晶素子及び調光素子
JP2021098847A (ja) 液晶調光素子用重合性組成物、液晶調光素子およびその用途
JP2021183686A (ja) 調光素子用重合性組成物、液晶調光素子、調光窓、スマートウィンドウ、液晶複合体およびその用途
JP2025023690A (ja) 高分子分散型液晶組成物及び調光素子
JP2025100149A (ja) 高分子分散型液晶組成物及び調光素子
JP2025023691A (ja) 高分子分散型液晶組成物及び調光素子
JP2023162737A (ja) 液晶組成物および液晶調光素子
JP2024169924A (ja) 液晶組成物、色素化合物、液晶層及び調光素子
JP2025135062A (ja) 液晶組成物及びこれを用いた液晶調光素子

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2022544337

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21910566

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21910566

Country of ref document: EP

Kind code of ref document: A1