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WO2018168205A1 - Composé polymérisable, et élément d'affichage à cristaux liquides - Google Patents

Composé polymérisable, et élément d'affichage à cristaux liquides Download PDF

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Publication number
WO2018168205A1
WO2018168205A1 PCT/JP2018/001895 JP2018001895W WO2018168205A1 WO 2018168205 A1 WO2018168205 A1 WO 2018168205A1 JP 2018001895 W JP2018001895 W JP 2018001895W WO 2018168205 A1 WO2018168205 A1 WO 2018168205A1
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replaced
formula
hydrogen
halogen
independently
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English (en)
Japanese (ja)
Inventor
智広 矢野
史尚 近藤
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JNC Corp
JNC Petrochemical Corp
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JNC Corp
JNC Petrochemical Corp
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Priority to JP2019505738A priority Critical patent/JP6787478B2/ja
Priority to CN201880012053.1A priority patent/CN110325507B/zh
Publication of WO2018168205A1 publication Critical patent/WO2018168205A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C219/34—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having amino groups and esterified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • 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
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • 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
    • C09K19/18—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
    • C09K19/04—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
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • 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

Definitions

  • the present invention relates to a polymerizable compound, a polymerizable composition containing the polymerizable compound and a liquid crystal composition, a liquid crystal composite prepared from the polymerizable composition, and a liquid crystal display element.
  • the liquid crystal display element utilizes the optical anisotropy and dielectric anisotropy of the liquid crystal molecules in the liquid crystal composition.
  • the classification based on the operation mode of the liquid crystal molecules includes the PC (phase change) mode, TN (twisted nematic) mode, STN (super twisted nematic) mode, BTN (bistable twisted nematic) mode, ECB (electrically controlled birefringence) mode, OCB (Optically-compensated-bend) mode, IPS (in-plane switching) mode, FFS (fringe field switching) mode, VA (vertical alignment) mode, and the like.
  • the initial alignment is generally achieved by a polyimide alignment film.
  • a liquid crystal composition containing a polar compound and a polymer or a polymerizable polar compound is used.
  • a small amount of a polar compound and a small amount of a polymerizable compound or a composition to which a small amount of a polymerizable polar compound is added are injected into the device.
  • liquid crystal molecules may be aligned by the action of the polar compound.
  • the polymerizable compound or the polymerizable polar compound is polymerized by irradiating the composition with ultraviolet rays.
  • the liquid crystal molecules are aligned, and this alignment state is stabilized, or the alignment after injection is stabilized.
  • the orientation of liquid crystal molecules can be controlled by the polar compound and the polymer or the polymerizable polar compound, the response time of the device is shortened, and image burn-in is improved.
  • an element that does not have an alignment film does not require a step of forming an alignment film, and since there is no alignment film, there is an advantage that there is no decrease in the electric resistance of the element due to the interaction between the alignment film and the composition.
  • Such an advantage due to the combination of the polar compound and the polymer can be expected for a device having modes such as TN, ECB, OCB, IPS, VA, FFS, and FPA.
  • the method of combining a polymer with a liquid crystal composition can be applied to liquid crystal display elements of various operation modes such as PS-TN, PS-IPS, PS-FFS, PSA-VA, and PSA-OCB.
  • the polymerizable compound used in the element of such a mode is required to have characteristics such as excellent ability to align liquid crystal molecules, appropriate polymerization reactivity, high conversion, and high solubility in a liquid crystal composition. .
  • Various polymerizable compounds have been developed so far, and it is desired to develop a compound that further improves the above characteristics.
  • the first object of the present invention is to provide a polymerizable compound having at least one of excellent ability to align liquid crystal molecules, appropriate polymerization reactivity, high conversion, high voltage holding ratio, and high solubility in a liquid crystal composition. Is to provide.
  • the second issue is the high upper limit temperature of the nematic phase, the lower lower limit temperature of the nematic phase, small viscosity, appropriate optical anisotropy, large dielectric anisotropy, suitable elastic constant, large specific resistance, suitable pretilt, etc.
  • An object of the present invention is to provide a liquid crystal composite having an appropriate balance regarding at least two physical properties.
  • a third problem is to provide a liquid crystal display element having at least one of a wide temperature range in which the element can be used, a short response time, a low threshold voltage, a large contrast ratio, and a long lifetime.
  • R 1 is hydrogen, halogen, —SP 1 —P 1 or alkyl having 1 to 15 carbons, and in this alkyl, at least one —CH 2 — may be replaced by —O— or —S—.
  • At least one — (CH 2 ) 2 — may be replaced by —CH ⁇ CH— or —C ⁇ C—, in which at least one hydrogen is halogen or —SP 1 —P 1 May be replaced;
  • MES is a mesogenic group having at least one ring and an N atom;
  • SP 1 is a single bond or alkylene having 1 to 10 carbon atoms, in which at least one —CH 2 — is —O—, —CO—, —COO—, —OCO—, or —OCOO—.
  • at least one — (CH 2 ) 2 — may be replaced with —CH ⁇ CH— or —C ⁇ C—, and in these groups at least one hydrogen is replaced with a halogen.
  • At least one hydrogen in the divalent group is halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 1 to 12 carbons, or 1 carbon To 12 alkenyloxy, and in these monovalent hydrocarbon groups at least one hydrogen may be replaced by halogen;
  • P 1 and P 2 are each independently a group represented by the following formula (1a), formula (1b), formula (1c), formula (1d) or formula (1e);
  • M 1 and M 2 are independently hydrogen, halogen, or alkyl having 1 to 10 carbons, in which at least one —CH 2 — may be replaced by —O— or —S—.
  • R 2 , R 3 , R 4 and R 8 are independently hydrogen, or a linear, branched or cyclic alkyl having 1 to 15 carbon atoms, in which at least one —CH 2 — is , —O— or —S—, and at least one — (CH 2 ) 2 — may be replaced with —CH ⁇ CH— or —C ⁇ C—, and in these groups at least One hydrogen may be replaced with a halogen.
  • R 7 is hydrogen, halogen, —SP 1 —P 1 , —SP 2 —P 2 or alkyl having 1 to 15 carbons, in which at least one —CH 2 — is —O— or —S And at least one — (CH 2 ) 2 — may be replaced by —CH ⁇ CH— or —C ⁇ C—, in which at least one hydrogen is a halogen, May be replaced by -SP 1 -P 1 or -SP 2 -P 2 ; Ring A 1 , Ring A 2 , Ring A 3 and Ring A 4 are each independently an alicyclic hydrocarbon having 3 to 18 carbon atoms, an aromatic hydrocarbon having 6 to 18 carbon atoms, or 3 to 18 carbon atoms.
  • Z 1 , Z 2 , Z 3 and Z 4 are each independently a single bond or alkylene having 1 to 10 carbon atoms, in which at least one —CH 2 — is —O—, —CO—, —COO— or —OCO— may be substituted, and at least one — (CH 2 ) 2 — may be —CH ⁇ CH—, —C (CH 3 ) ⁇ CH—, —CH ⁇ C (CH 3 ) —, —C (CH 3 ) ⁇ C (CH 3 ) —, or —CH ⁇ CH—, and in these
  • P 1 and P 2 are each independently a group represented by the following formula (1a), formula (1b), formula (1c), formula (1d) or formula (1e);
  • M 1 and M 2 are independently hydrogen, halogen, or alkyl having 1 to 10 carbons, in which at least one —CH 2 — may be replaced by —O— or —S—.
  • R 2 , R 3 , R 4 and R 8 are independently hydrogen, or a linear, branched or cyclic alkyl having 1 to 15 carbon atoms, in which at least one —CH 2 — is , —O— or —S—, and at least one — (CH 2 ) 2 — may be replaced with —CH ⁇ CH— or —C ⁇ C—, and in these groups at least One hydrogen may be replaced with a halogen.
  • R 7 is hydrogen, halogen, —SP 1 —P 1 , —SP 2 —P 2 or alkyl having 1 to 15 carbons, in which at least one —CH 2 — is —O— or —S And at least one — (CH 2 ) 2 — may be replaced by —CH ⁇ CH— or —C ⁇ C—, in which at least one hydrogen is a halogen, May be replaced by -SP 1 -P 1 or -SP 2 -P 2 ; Ring A 1 , Ring A 2 , Ring A 3 and Ring A 4 are each independently an alicyclic hydrocarbon having 3 to 18 carbon atoms, an aromatic hydrocarbon having 6 to 18 carbon atoms, or 3 to 18 carbon atoms.
  • SP 1 and SP 2 are each independently a single bond or alkylene having 1 to 10 carbon atoms, in which at least one —CH 2 — is —O—, —CO—, —COO—, —OCO.
  • P 1 and P 2 are each independently a group represented by the following formula (1a), formula (1b), formula (1c), formula (1d) or formula (1e);
  • M 1 and M 2 are independently hydrogen, halogen, or alkyl having 1 to 10 carbons, in which at least one —CH 2 — may be replaced by —O— or —S—.
  • R 2 , R 3 , R 4 and R 8 are independently hydrogen, or a linear, branched or cyclic alkyl having 1 to 15 carbon atoms, in which at least one —CH 2 — is , —O— or —S—, and at least one — (CH 2 ) 2 — may be replaced with —CH ⁇ CH— or —C ⁇ C—, and in these groups at least One hydrogen may be replaced with a halogen.
  • R 7 is hydrogen, halogen, —SP 1 —P 1 , —SP 2 —P 2 or alkyl having 1 to 15 carbons, in which at least one —CH 2 — is —O— or —S And at least one — (CH 2 ) 2 — may be replaced by —CH ⁇ CH— or —C ⁇ C—, in which at least one hydrogen is a halogen, May be replaced by -SP 1 -P 1 or -SP 2 -P 2 ; Ring A 1 and Ring A 2 are independently 1,4-phenylene, and at least one hydrogen on these rings may be replaced with a halogen; Ring A 3 and Ring A 4 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, or 1,4-phenylene, and at least one hydrogen on these rings is replaced with a halogen; Ring A 3 and Ring A 4 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, or 1,4-phenylene, and
  • P 1 and P 2 are each independently a group represented by the following formula (1a), formula (1b), formula (1c), formula (1d) or formula (1e);
  • M 1 and M 2 are independently hydrogen, halogen, or alkyl having 1 to 10 carbons, in which at least one —CH 2 — may be replaced by —O— or —S—.
  • R 2 , R 3 , R 4 and R 8 are independently hydrogen, or a linear, branched or cyclic alkyl having 1 to 15 carbon atoms, in which at least one —CH 2 — is , —O— or —S—, and at least one — (CH 2 ) 2 — may be replaced with —CH ⁇ CH— or —C ⁇ C—, and in these groups at least One hydrogen may be replaced with a halogen.
  • Item 6. The polymerizable compound according to item 1, represented by the following formula (1-1-7).
  • Ring A 1 and Ring A 2 are independently 1,4-phenylene, and at least one hydrogen on these rings may be replaced with a halogen;
  • SP 1 and SP 2 are each independently a single bond or alkylene having 1 to 10 carbon atoms, in which at least one —CH 2 — is —O—, —CO—, —COO—, —OCO.
  • P 1 and P 2 are each independently a group represented by the following formula (1a), formula (1b), formula (1c), formula (1d) or formula (1e);
  • M 1 and M 2 are independently hydrogen, halogen, or alkyl having 1 to 10 carbons, in which at least one —CH 2 — may be replaced by —O— or —S—.
  • R 2 , R 3 , R 4 and R 8 are independently hydrogen, or a linear, branched or cyclic alkyl having 1 to 15 carbon atoms, in which at least one —CH 2 — is , —O— or —S—, and at least one — (CH 2 ) 2 — may be replaced with —CH ⁇ CH— or —C ⁇ C—, and in these groups at least One hydrogen may be replaced with a halogen.
  • Item 7 A polymerizable composition comprising at least one polymerizable compound according to any one of items 1 to 6.
  • Item 8 The polymerizable composition according to item 7, further comprising at least one compound selected from compounds represented by any one of the following formulas (2) to (4).
  • R 11 and R 12 are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, in which at least one —CH 2 — is replaced by —O—.
  • Ring B 1 , Ring B 2 , Ring B 3 and Ring B 4 are each independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro- 1,4-phenylene or pyrimidine-2,5-diyl;
  • Z 11 , Z 12 and Z 13 are each independently a single bond, —CH 2 CH 2 —, —CH ⁇ CH—, —C ⁇ C—, or —COO—.
  • Item 9. The polymerizable composition according to Item 7 or 8, further comprising at least one compound selected from compounds represented by any one of the following formulas (5) to (7):
  • R 13 is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, in which at least one —CH 2 — may be replaced by —O—, and at least one hydrogen is May be replaced by fluorine;
  • X 11 is fluorine, chlorine, —OCF 3 , —OCHF 2 , —CF 3 , —CHF 2 , —CH 2 F, —OCF 2 CHF 2 , or —OCF 2 CHFCF 3 ;
  • Ring C 1 , Ring C 2 and Ring C 3 are independently 1,4-cyclohexylene, 1,4-phenylene in which at least one hydrogen may be replaced by fluorine, tetrahydropyran-2,5-diyl 1,3-dioxane-2,5-diyl,
  • Item 10 The polymerizable composition according to any one of Items 7 to 9, further comprising at least one compound selected from the group of compounds represented by the following formula (8).
  • R 14 is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, in which at least one —CH 2 — may be replaced by —O—, and at least one hydrogen May be replaced by fluorine;
  • X 12 is —C ⁇ N or —C ⁇ C—C ⁇ N;
  • Ring D 1 is 1,4-cyclohexylene, 1,4-phenylene in which at least one hydrogen may be replaced with fluorine, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl Or pyrimidine-2,5-diyl;
  • Z 17 is a single bond, - (CH 2) 2 - , - C ⁇ C -, - COO -, - CF 2 O -, - OCF 2
  • Item 11 A liquid crystal composite produced by polymerization of the polymerizable composition according to any one of items 7 to 10.
  • Item 12. An optically anisotropic material produced by polymerization of the polymerizable composition according to any one of items 7 to 10.
  • Item 13 A liquid crystal display device comprising the polymerizable composition according to any one of items 7 to 10 or the liquid crystal composite according to item 11.
  • Item 14 The compound according to any one of items 1 to 6, at least one selected from the group consisting of the polymerizable composition according to any one of items 7 to 10, and the liquid crystal composite according to item 11. Use in liquid crystal display elements.
  • the first advantage of the present invention is a polymerizable compound having at least one of excellent ability to align liquid crystal molecules, suitable polymerization reactivity, high conversion, high voltage holding ratio, and high solubility in a liquid crystal composition. Is to provide.
  • the second advantage is that the liquid crystal composite has a high maximum temperature of the nematic phase, a low minimum temperature of the nematic phase, a small viscosity, a suitable optical anisotropy, a large dielectric anisotropy, a suitable elastic constant, and a large specific resistance. Satisfying at least one of physical properties such as an appropriate pretilt.
  • the advantage is that the liquid crystal composite has an appropriate balance with respect to at least two physical properties.
  • a third advantage is that the liquid crystal display element has at least one of a wide temperature range in which the element can be used, a short response time, a low threshold voltage, a large contrast ratio, and a long lifetime.
  • Liquid crystalline compounds include non-polymerizable compounds having a liquid crystal phase such as a nematic phase and a smectic phase, and liquid crystal compositions having no liquid crystal phase, such as maximum temperature, minimum temperature, viscosity, and dielectric anisotropy. It is a general term for non-polymerizable compounds that are mixed for the purpose of adjusting. This compound has a six-membered ring such as 1,4-cyclohexylene and 1,4-phenylene, and its molecular structure is rod-like.
  • the liquid crystal composition is a mixture of liquid crystal compounds.
  • the polymerizable compound is a compound added to the composition for the purpose of forming a polymer.
  • the polymerizable composition is a mixture of a polymerizable compound, a liquid crystal composition, an additive, and the like.
  • the liquid crystal composite is a composite formed by polymerization of this polymerizable composition.
  • a liquid crystal display element is a general term for a liquid crystal display panel and a liquid crystal display module.
  • the upper limit temperature of the nematic phase is a phase transition temperature of the nematic phase-isotropic phase in the liquid crystal composition, polymerizable composition, or liquid crystal composite, and may be abbreviated as the upper limit temperature.
  • the lower limit temperature of the nematic phase may be abbreviated as the lower limit temperature.
  • Polymerization reactivity refers to the degree of ease with which the reactants polymerize. Conversion is the weight ratio of reactant consumed by a chemical reaction to reactant.
  • the liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds.
  • the ratio (content) of the liquid crystal compound is expressed as a percentage by weight (% by weight) based on the weight of the liquid crystal composition.
  • Additives such as optically active compounds, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors are added to this composition as necessary. Is done.
  • the ratio (addition amount) of the additive is represented by a weight percentage (% by weight) based on the weight of the liquid crystal composition, similarly to the ratio of the liquid crystal compound. Weight parts per million (ppm) may be used.
  • the ratio of the polymerization initiator and the polymerization inhibitor is exceptionally expressed based on the weight of the polymerizable compound.
  • the compound represented by Formula (1) may be abbreviated as Compound (1).
  • At least one compound selected from the group of compounds represented by formula (1) may be abbreviated as “compound (1)”.
  • “Compound (1)” means one compound represented by formula (1), a mixture of two compounds, or a mixture of three or more compounds. The same applies to compounds represented by other formulas.
  • the line crossing the circle means that the —SP 1 —P 1 group can arbitrarily select the bonding position on the ring such as a six-membered ring or a condensed ring To do. This rule also applies to symbols such as -SP 2 -P 2 groups.
  • the expression “at least one“ A ”may be replaced by“ B ”” means that when the number of “A” is one, the position of “A” is arbitrary, and the number of “A” is two. Even when there are more than two, it means that their positions can be freely selected without limitation.
  • the expression “at least one A may be replaced by B, C or D” means that at least one A is replaced by B, at least one A is replaced by C, and at least 1 When one A is replaced with D, it means that a plurality of A are further replaced with at least two of B, C, and D.
  • alkyl in which at least one —CH 2 — (or — (CH 2 ) 2 —) may be replaced by —O— includes alkyl, alkenyl, alkoxy, alkoxyalkyl, Alkoxyalkenyl and alkenyloxyalkyl are included. Note that it is not preferable that two consecutive —CH 2 — are replaced by —O— to form —O—O—. In alkyl and the like, it is not preferable that —CH 2 — in the methyl moiety (—CH 2 —H) is replaced by —O— to become —O—H.
  • 2-Fluoro-1,4-phenylene means the following two divalent groups.
  • fluorine may be leftward (L) or rightward (R). This rule also applies to asymmetric bivalent groups derived by removing two hydrogens from the ring, such as tetrahydropyran-2,5-diyl.
  • Halogen means fluorine, chlorine, bromine and iodine.
  • a preferred halogen is fluorine or chlorine, and a more preferred halogen is fluorine.
  • the present invention also includes the following items.
  • A The above polymerization further comprising at least one additive such as an optically active compound, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, an antifoaming agent, a polymerization initiator, and a polymerization inhibitor Sex composition.
  • B The polymerizable composition as described above, further comprising at least one polymerization initiator.
  • C The polymerizable composition further containing a polymerizable compound not represented by the formula (1).
  • D Use of a compound represented by formula (1) in a polymerizable composition suitable for a liquid crystal display device having a PSA mode.
  • E Use of a compound represented by formula (1) in a liquid crystal display device having a PSA mode.
  • the present invention also includes the following items.
  • the polymerizable compound of the present invention will be described first, and then the synthesis method, the polymerizable composition, the liquid crystal composite, and the liquid crystal display element will be described in this order.
  • R 1 is hydrogen, halogen, —SP 1 —P 1 or alkyl having 1 to 15 carbons, and in this alkyl, at least one —CH 2 — may be replaced by —O— or —S—.
  • At least one — (CH 2 ) 2 — may be replaced by —CH ⁇ CH— or —C ⁇ C—, in which at least one hydrogen is halogen or —SP 1 —P 1 May be replaced;
  • MES is a mesogenic group having at least one ring and an N atom;
  • SP 1 is a single bond or alkylene having 1 to 10 carbon atoms, in which at least one —CH 2 — is —O—, —CO—, —COO—, —OCO—, or —OCOO—.
  • at least one — (CH 2 ) 2 — may be replaced with —CH ⁇ CH— or —C ⁇ C—, and in these groups at least one hydrogen is replaced with a halogen.
  • the compound (1) since the compound (1) has a rod-like molecular structure similar to a liquid crystal compound, the solubility in the liquid crystal composition is high. Therefore, the compound (1) is suitable as a polymerizable compound necessary for a device having a PSA mode. Secondly, the compound (1) has appropriate polymerizability. Therefore, compound (1) can be stored stably. In the polymerization, the rate of the photoreaction can be easily controlled, and the polymerization can be performed by appropriately irradiating ultraviolet rays. Moreover, excessive ultraviolet rays are not required.
  • a preferred structure of the compound (1) is the formula (1-1), and preferred examples of the polymerizable group P, the linking group SP, the ring A, the alkyl R, and the linking group Z in the formula (1-1) are It is as follows. This example also applies to compounds subordinate to compound (1).
  • Compound (1) can have its physical properties arbitrarily adjusted by appropriately combining these types of groups. Since there is no great difference in the physical properties of the compound, the compound (1) may contain an isotope such as 2 H (deuterium) and 13 C in an amount larger than the natural abundance.
  • P 1 and P 2 are independently a polymerizable group.
  • polymerizable groups are acryloyloxy, methacryloyloxy, acrylamide, methacrylamide, vinyloxy, vinylcarbonyl, oxiranyl, oxetanyl, 3,4-epoxycyclohexyl, maleimide or itaconic acid ester.
  • at least one hydrogen may be replaced with fluorine, methyl, or trifluoromethyl.
  • Preferred examples of the polymerizable group include acryloyloxy (the following formula (1a)), oxiranyl (the following formula (1b)), vinyloxy (the following formula (1c)), maleimide (the following formula (1d)) or itaconic acid ester (the following Formula (1e)).
  • M 1 and M 2 are independently hydrogen, halogen, or alkyl having 1 to 10 carbons, in which at least one —CH 2 — may be replaced by —O— or —S—.
  • R 2 , R 3 , R 4 and R 8 are independently hydrogen, or a linear, branched or cyclic alkyl having 1 to 15 carbon atoms, in which at least one —CH 2 — is , —O— or —S—, and at least one — (CH 2 ) 2 — may be replaced with —CH ⁇ CH— or —C ⁇ C—, At least one hydrogen may be replaced with a halogen.
  • Particularly preferred examples include a single bond, —CH 2 —, —CH ⁇ CH—, —CH ⁇ CH—O—, —O—CH ⁇ CH—, —CH 2 CH 2 O—, or —OCH 2 CH 2 —. It is.
  • the most preferred example is a single bond.
  • the configuration of the double bond of —CH ⁇ CH— may be cis or trans. The trans type is preferable to the cis type.
  • R 5 , R 6 and R 7 are independently hydrogen, halogen, —S 1 —P 1 , —S 2 —P 2 , or alkyl having 1 to 15 carbons, In this alkyl, at least one —CH 2 — may be replaced with —O— or —S—, and at least one — (CH 2 ) 2 — may be replaced with —CH ⁇ CH— or —C ⁇ C—. In these groups, at least one hydrogen may be replaced by halogen, -SP 1 -P 1 or -SP 2 -P 2 .
  • a1 and a2 are independently 0, 1, 2, 3, or 4.
  • —SP 1 —P 1 or —SP 2 —P 2 is a monovalent group involved in polymerization.
  • the total number of -SP 1 -P 1 and -SP 2 -P 2 is 1 to 8.
  • Preferred examples are 1 to 6, and more preferred examples are 1 to 3. The most preferred example is 1 or 2.
  • ring A 1 and ring A 2 are independently an alicyclic hydrocarbon from 3 to 18 carbon atoms, aromatic hydrocarbons having 6 to 18 carbon atoms, or a carbon number of 3 18 It is a divalent group derived by removing two hydrogens from a heteroaromatic hydrocarbon. In these divalent groups, at least one hydrogen is replaced with halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 1 to 12 carbons, or alkenyloxy having 1 to 12 carbons. In these monovalent hydrocarbon groups, at least one hydrogen may be replaced with a halogen. Further, ring A 1 has a1 hydrogens replaced with —SP 1 —P 1 , and ring A 2 has a2 hydrogens replaced with —SP 2 —P 2 .
  • Examples of the alicyclic hydrocarbon are cyclopropane, cyclobutane, cyclohexane, cycloheptane, cyclooctane and the like represented by C n H 2n .
  • Other examples are decahydronaphthalene and the like.
  • Examples of aromatic hydrocarbons are benzene, naphthalene, anthracene, phenanthrene, fluorene, indane, indene, tetrahydronaphthalene and the like.
  • Examples of heteroaromatic hydrocarbons are pyridine, pyrimidine, furan, pyran, thiophene, benzofuran and the like.
  • hydrocarbons may be substituted with monovalent groups such as fluorine, chlorine and alkyl.
  • Preferred examples of ring A 1 or ring A 2 are benzene, fluorobenzene, naphthalene, fluorene, or phenanthrene. Further preferred examples are benzene or cyclohexane.
  • Z 1 and Z 2 are each independently a single bond or alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH 2 — is —O—, — CO—, —COO— or —OCO— may be substituted, and at least one — (CH 2 ) 2 — may be —CH ⁇ CH—, —C (CH 3 ) ⁇ CH—, —CH ⁇ C ( CH 3 ) —, —C (CH 3 ) ⁇ C (CH 3 ) —, or —CH ⁇ CH—, in which at least one hydrogen is replaced by a halogen. Also good.
  • Z 1 and Z 2 include a single bond, alkylene having 1 to 4 carbon atoms, —COO—, —OCO—, —CH 2 O—, —OCH 2 —, —CF 2 O—, —OCF 2 —.
  • Further preferred examples are a single bond, ethylene, —COO—, —OCO—, —CH ⁇ CH—, —CH ⁇ CH—COO—, —OCO—CH ⁇ CH—, or —CH ⁇ CH—.
  • the most preferred example is a single bond.
  • b1 and b2 are independently 0, 1, 2, or 3.
  • the compound rings to b1 or perforated for ring A 1.
  • the preferred ring A 1 is a divalent group derived by removing two hydrogens from a condensed ring such as naphthalene, anthracene, phenanthrene, benzene.
  • the compound has a ring A 1 and ring A 2.
  • preferred ring A 1 or ring A 2 is a divalent group derived from benzene substituted with a substituent such as benzene, fluorine or methyl.
  • ring A 1 or ring A 2 are benzene, divalent group derived from benzene substituted with substituents such as fluorine.
  • Examples of a method for generating a bonding group Z in producing compounds of the bonding group Z (1-1) are as follows scheme.
  • MSG 1 (or MSG 2 ) is a monovalent organic group having at least one ring.
  • the monovalent organic groups represented by a plurality of MSG 1 (or MSG 2 ) may be the same or different.
  • Compound (1A) to Compound (1I) correspond to Compound (1).
  • esters a method for synthesizing a compound having —COO— was shown.
  • a compound having —OCO— can also be synthesized by this synthesis method. The same applies to other asymmetrical linking groups.
  • Arylboric acid (21) and compound (22) synthesized by a known method are reacted in an aqueous carbonate solution in the presence of a catalyst such as tetrakis (triphenylphosphine) palladium.
  • Compound (1A) is synthesized.
  • This compound (1A) is prepared by reacting compound (23) synthesized by a known method with n-butyllithium and then with zinc chloride, and in the presence of a catalyst such as dichlorobis (triphenylphosphine) palladium. ) Is also reacted.
  • a compound (1B) of —CF 2 O— is treated with a sulfurizing agent such as Lawesson's reagent to obtain compound (26).
  • Compound (26) is fluorinated with hydrogen fluoride pyridine complex and NBS (N-bromosuccinimide) to synthesize compound (1C) (see M. Kuroboshi et al., Chem. Lett., 1992, 827.).
  • Compound (1C) can also be synthesized by fluorinating compound (26) with (diethylamino) sulfur trifluoride (DAST) (see W. H. Bunnelle et al., J. Org. Chem. 1990, 55, 768.). It is also possible to generate this linking group by the method described in Peer. Kirsch et al., Angew. Chem. Int. Ed. 2001, 40, 1480.
  • a phosphorus ylide is prepared by reacting a base such as sodium hydride with ethyl diethylphosphonoacetate, and this phosphorus ylide is reacted with an aldehyde (32) to obtain an ester (33). .
  • Ester (33) is hydrolyzed in the presence of a base such as sodium hydroxide to give carboxylic acid (34). This compound and compound (25) are dehydrated and condensed to synthesize compound (1F).
  • Linking Group SP and Polymerizable Group P Preferred examples of the polymerizable group P are acryloyloxy (1a), oxiranyl (1b), vinyloxy (1c) maleimide (1d) or itaconic acid ester (1e).
  • An example of a method for synthesizing a compound in which this polymerizable group is bonded to a ring with a linking group SP is as follows. First, an example in which the linking group SP is a single bond is shown.
  • MSG 1 is a monovalent organic group having at least one ring. From compound (1S) to compound (1Z) corresponds to compound (1).
  • MES in MES Formation Compound (1) is a mesogenic group having at least one ring and an N atom.
  • a preferred example is (1J) below.
  • Compound (1J) corresponds to compound (1).
  • ring A 1 and ring A 2 are both aromatic hydrocarbons, they can be synthesized, for example, according to the following scheme.
  • Compound (1) has an appropriate polymerization reactivity, a high conversion rate, and a high solubility in a liquid crystal composition as compared with a similar compound. Compound (1) has an appropriate balance regarding at least two of these physical properties. Therefore, the compound (1) can be added to the liquid crystal composition for the PSA mode.
  • the polymerizable composition contains at least one of the compounds (1) as a first component.
  • the component of this composition may be only the first component.
  • the composition may contain other components such as a second component and a third component.
  • the type of the second component depends on the intended use of the polymer.
  • This polymerizable composition may further contain another polymerizable compound different from the compound (1) as the second component.
  • Preferred examples of the other polymerizable compound are acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, epoxy compound (oxirane, oxetane), and vinyl ketone.
  • Further preferred examples are compounds having at least one acryloyloxy and compounds having at least one methacryloyloxy. Further preferred examples include compounds having both acryloyloxy and methacryloyloxy.
  • R 25 , R 26 and R 27 are independently hydrogen or methyl; u, x and y are independently 0 or 1, v and w is independently an integer from 1 to 10; L 21 , L 22 , L 23 , L 24 , L 25 , and L 26 are independently hydrogen or fluorine.
  • an optical anisotropic body is formed by polymerization while controlling the alignment of liquid crystal molecules.
  • This optical anisotropic body can be used for a retardation film, a polarizing element, a circularly polarizing element, an elliptically polarizing element, an antireflection film, a selective reflection film, a color compensation film, a viewing angle compensation film, and the like.
  • An additive such as a polymerization initiator may be added to the polymerizable composition for the purpose of adjusting the physical properties of the optical anisotropic body.
  • the polymerizable composition may contain a liquid crystal composition as the second component.
  • the polymerizable composition contains the compound (1) as It is preferable to further include a compound selected from the components B, C and D shown in FIG.
  • Component B is compound (2) to compound (4).
  • Component C is compound (5) to compound (7).
  • Component D is compound (8).
  • a polymerizable composition with appropriately selected components has a high maximum temperature, a low minimum temperature, a small viscosity, a suitable optical anisotropy (ie, a large optical anisotropy or a small optical anisotropy), positively or negatively large It has a dielectric anisotropy and an appropriate elastic constant (ie, a large elastic constant or a small elastic constant).
  • the polymerizable composition is prepared by adding the compound (1) to the liquid crystal composition. Additives may be added to the composition as necessary. In such a composition, the addition amount of the compound (1), that is, the component A is in the range of 0.01 wt% to 20 wt% based on the weight of the liquid crystal composition. A more preferable addition amount is in the range of 0.0133 wt% to 10 wt%. The most preferred addition amount is in the range of 0.05% to 5% by weight. At least one of other polymerizable compounds different from the compound (1) may be further added. In this case, the total amount of addition of the compound (1) and other polymerizable compounds is preferably within the above range.
  • the physical properties of the polymer to be produced can be adjusted by appropriately selecting other polymerizable compounds. Examples of other polymerizable compounds are acrylates and methacrylates as described above. Examples thereof also include compound (M-1) to compound (M-12).
  • Component B is a compound in which two terminal groups are alkyl or the like.
  • Preferred examples of component B include compound (2-1) to compound (2-11), compound (3-1) to compound (3-19), or compound (4-1) to compound (4-7).
  • R 11 and R 12 are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, in which at least one —CH 2 — is —O - May be replaced with at least one hydrogen may be replaced with fluorine.
  • Component B is a compound close to neutrality because the absolute value of dielectric anisotropy is small.
  • the compound (2) is mainly effective in adjusting the viscosity or the optical anisotropy.
  • the compounds (3) and (4) have an effect of increasing the temperature range of the nematic phase by increasing the maximum temperature or adjusting the optical anisotropy.
  • the content of component B is preferably 30% by weight or more, more preferably 40%, based on the weight of the liquid crystal composition. % By weight or more.
  • Component C is a compound having a halogen or fluorine-containing group at the right end.
  • Preferred examples of Component C include Compound (5-1) to Compound (5-16), Compound (6-1) to Compound (6-113), or Compound (7-1) to Compound (7-57).
  • R 13 is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one —CH 2 — may be replaced by —O—.
  • At least one hydrogen may be replaced by fluorine;
  • X 11 is fluorine, chlorine, —OCF 3 , —OCHF 2 , —CF 3 , —CHF 2 , —CH 2 F, —OCF 2 CHF 2 , or -OCF is a 2 CHFCF 3.
  • component C Since component C has a positive dielectric anisotropy and is very stable against heat, light, etc., a composition for a mode such as PS-IPS, PS-FFS, or PSA-OCB is prepared. Used in cases.
  • the content of component C is suitably in the range of 1% to 99% by weight based on the weight of the liquid crystal composition, preferably in the range of 10% to 97% by weight, more preferably in the range of 40% to 95%. % Range.
  • the content of component C is preferably 30% by weight or less based on the weight of the liquid crystal composition.
  • Component D is a compound (8) in which the right terminal group is —C ⁇ N or —C ⁇ C—C ⁇ N.
  • Preferred examples of component D include compounds (8-1) to (8-64).
  • R 14 is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one —CH 2 — may be replaced by —O—.
  • At least one hydrogen may be replaced by fluorine;
  • X 12 is —C ⁇ N or —C ⁇ C—C ⁇ N.
  • component D Since component D has a positive dielectric anisotropy and a large value, it is mainly used when a composition for a mode such as PS-TN is prepared. By adding this component D, the dielectric anisotropy of the composition can be increased.
  • Component D has the effect of expanding the temperature range of the liquid crystal phase, adjusting the viscosity, or adjusting the optical anisotropy. Component D is also useful for adjusting the voltage-transmittance curve of the device.
  • the content of component D is suitably in the range of 1 to 99% by weight, preferably 10% by weight based on the weight of the liquid crystal composition. % To 97% by weight, more preferably 40% to 95% by weight.
  • the content of component D is preferably 30% by weight or less based on the weight of the liquid crystal composition.
  • the polymerizable composition is prepared by a method of dissolving necessary components at a temperature higher than room temperature.
  • additives may be added to the composition.
  • additives include optically active compounds, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, antifoaming agents, polymerization initiators, polymerization inhibitors, and the like. Such additives are well known to those skilled in the art and are described in the literature.
  • the optically active compound has an effect of preventing reverse twisting by inducing a helical structure in liquid crystal molecules to give a necessary twist angle.
  • the helical pitch can be adjusted by adding an optically active compound.
  • Two or more optically active compounds may be added for the purpose of adjusting the temperature dependence of the helical pitch.
  • Preferable examples of the optically active compound include the following compounds (Op-1) to (Op-18).
  • ring J is 1,4-cyclohexylene or 1,4-phenylene
  • R 28 is alkyl having 1 to 10 carbons.
  • An antioxidant is effective for maintaining a large voltage holding ratio.
  • Preferred examples of the antioxidant include the following compound (AO-1) and compound (AO-2); IRGANOX 415, IRGANOX 565, IRGANOX 1010, IRGANOX 1035, IRGANOX 3114, and IRGANOX 1098 (trade name: BASF) Can be mentioned.
  • the ultraviolet absorber is effective for preventing a decrease in the maximum temperature.
  • Preferred examples of the ultraviolet absorber include benzophenone derivatives, benzoate derivatives, triazole derivatives and the like.
  • TINUVIN 329 As specific examples, the following compound (AO-3) and compound (AO-4): TINUVIN 329, TINUVIN P, TINUVIN 326, TINUVIN 234, TINUVIN 213, TINUVIN 400, TINUVIN 328, and TINUVIN 328, and TINUVIN 99-2 (trade name: BASF) And 1,4-diazabicyclo [2.2.2] octane (DABCO).
  • a light stabilizer such as an amine having steric hindrance is preferable in order to maintain a large voltage holding ratio.
  • Preferred examples of the light stabilizer include the following compound (AO-5) and compound (AO-6); TINUVIN 144, TINUVIN 765, and TINUVIN 770DF (trade name: BASF).
  • a thermal stabilizer is also effective for maintaining a large voltage holding ratio, and a preferred example is IRGAFOS 168 (trade name: BASF).
  • Antifoaming agents are effective for preventing foaming.
  • Preferred examples of the antifoaming agent include dimethyl silicone oil and methylphenyl silicone oil.
  • R 29 is alkyl having 1 to 20 carbons, alkoxy having 1 to 20 carbons, —COOR 32 , or —CH 2 CH 2 COOR 32 , where R 32 is 1 carbon atom To 20 alkyls.
  • R 30 is alkyl having 1 to 20 carbons.
  • R 31 is hydrogen, methyl or O ⁇ (oxygen radical)
  • ring K and ring L is 1,4-cyclohexylene or 1,4-phenylene
  • x is 0, 1 or 2.
  • the liquid crystal composite compound (1) has appropriate polymerization reactivity, high conversion, and high solubility in the liquid crystal composition.
  • a liquid crystal composite is formed by polymerizing a polymerizable composition containing the compound (1) and the liquid crystal composition.
  • Compound (1) forms a polymer in the liquid crystal composition by polymerization. This polymer has the effect of stabilizing the initial alignment of the liquid crystal molecules.
  • pretil can be generated by performing polymerization while applying an electric field. Polymerization occurs by heat, light, and the like. A preferred reaction is photopolymerization. Polymerization may be carried out with an electric or magnetic field applied.
  • the polymerization reactivity and conversion rate of the compound (1) can be adjusted.
  • Compound (1) is suitable for radical polymerization.
  • Compound (1) can be rapidly polymerized by adding a polymerization initiator. By optimizing the reaction temperature, the amount of the remaining compound (1) can be reduced.
  • photoradical polymerization initiators are TPO, 1173 and 4265 from DASFURE series of BASF, and 184, 369, 500, 651, 784, 819, 907, 1300, 1700, 1800, 1850, from Irgacure series. And 2959.
  • photo radical polymerization initiators include 4-methoxyphenyl-2,4-bis (trichloromethyl) triazine, 2- (4-butoxystyryl) -5-trichloromethyl-1,3,4-oxadiazole, 9-phenylacridine, 9,10-benzphenazine, benzophenone / Michler's ketone mixture, hexaarylbiimidazole / mercaptobenzimidazole mixture, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, benzyl Dimethyl ketal, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2,4-diethylxanthone / methyl p-dimethylaminobenzoate, benzophenone / methyltriethanolamine mixture It is.
  • polymerization After adding a radical photopolymerization initiator to the polymerizable composition, polymerization can be carried out by irradiating with ultraviolet rays in an applied electric field. However, the unreacted polymerization initiator or the decomposition product of the polymerization initiator may cause display defects such as image burn-in on the device. In order to avoid this, photopolymerization may be performed without adding a polymerization initiator.
  • a preferable wavelength of the irradiation light is in the range of 150 nm to 500 nm. A more preferable wavelength is in the range of 250 nm to 450 nm, and a most preferable wavelength is in the range of 300 nm to 400 nm.
  • a polymerization inhibitor When storing the polymerizable compound, a polymerization inhibitor may be added to prevent polymerization.
  • the polymerizable compound is usually added to the composition without removing the polymerization inhibitor.
  • the polymerization inhibitor include hydroquinone derivatives such as hydroquinone and methylhydroquinone, 4-tert-butylcatechol, 4-methoxyphenol, phenothiazine and the like.
  • Liquid crystal display element The effect of the polymer in a liquid crystal display element is interpreted as follows.
  • the polymerizable composition is a mixture of a liquid crystal compound, a polymerizable compound and the like.
  • this composition is injected into a liquid crystal cell, various initial orientations are exhibited depending on the characteristics of the cell and the composition used.
  • the composition is irradiated with ultraviolet rays to polymerize the polymerizable compound.
  • an electric field may be applied to the cell. This results in the formation of a polymer network in the polymerizable composition. Due to this network effect, the liquid crystal molecules are stabilized in a state before the ultraviolet irradiation.
  • the initial alignment is a random alignment, but an ordered alignment such as a homogeneous alignment or a homeotropic alignment can be formed by ultraviolet irradiation.
  • an ordered alignment such as a homogeneous alignment or a homeotropic alignment can be formed by ultraviolet irradiation.
  • Polymerization of the polymerizable composition is preferably performed in a display element.
  • An example is as follows.
  • a display element having two glass substrates provided with a transparent electrode on at least one of them is prepared.
  • a polymerizable composition containing the compound (1), a liquid crystal composition, an additive and the like as components is prepared. This composition is injected into the display element.
  • the display element is irradiated with ultraviolet rays to polymerize the compound (1).
  • a liquid crystal composite is formed by this polymerization.
  • a liquid crystal display element having a liquid crystal composite can be easily produced.
  • the rubbing treatment of the alignment film may be omitted, and the alignment film may be omitted.
  • a PSA mode liquid crystal display element When the addition amount of the polymerizable compound is in the range of 0.1 wt% to 2 wt% based on the weight of the liquid crystal composition, a PSA mode liquid crystal display element is produced.
  • a PSA mode element can be driven by a driving system such as AM (active matrix) or PM (passive matrix). Such an element can be applied to any of a reflection type, a transmission type, and a transflective type.
  • a polymer-dispersed mode element By increasing the addition amount of the polymerizable compound, a polymer-dispersed mode element can also be produced.
  • the present invention will be described in more detail with reference to examples. The invention is not limited by these examples.
  • the present invention includes a mixture of the composition of Example 1 and the composition of Example 2.
  • the invention also includes a mixture of at least two of the example compositions.
  • the synthesized compound was identified by a method such as NMR analysis. The physical properties of the compound, composition and device were measured by the methods described below.
  • NMR analysis For measurement, DRX-500 manufactured by Bruker BioSpin Corporation was used. In the 1 H-NMR measurement, the sample was dissolved in a deuterated solvent such as CDCl 3, and the measurement was performed at room temperature, 500 MHz, and 16 times of integration. Tetramethylsilane was used as an internal standard. For 19 F-NMR measurement, CFCl 3 was used as an internal standard and the number of integrations was 24.
  • s is a singlet
  • d is a doublet
  • t is a triplet
  • q is a quartet
  • quint is a quintet
  • sex a sextet
  • m is a multiplet
  • br is broad.
  • LC-20AD Prominence (LC-20AD; SPD-20A) manufactured by Shimadzu Corporation was used.
  • the column used was YMC-Pack ODS-A (length 150 mm, inner diameter 4.6 mm, particle diameter 5 ⁇ m) manufactured by YMC.
  • a detector a UV detector, an RI detector, a CORONA detector, or the like was appropriately used.
  • the detection wavelength was 254 nm.
  • a sample was dissolved in acetonitrile to prepare a 0.1 wt% solution, and 1 ⁇ L of this solution was introduced into the sample chamber.
  • a recorder a C-R7Aplus manufactured by Shimadzu Corporation was used.
  • UV-visible spectroscopic analysis PharmaSpec UV-1700 manufactured by Shimadzu Corporation was used.
  • the detection wavelength was 190 nm to 700 nm.
  • the sample was dissolved in acetonitrile to prepare a 0.01 mmol / L solution, and the sample was placed in a quartz cell (optical path length 1 cm) and measured.
  • Measurement Sample When measuring the phase structure and transition temperature (clearing point, melting point, polymerization initiation temperature, etc.), the compound itself was used as a sample. When measuring physical properties such as the maximum temperature, viscosity, optical anisotropy and dielectric anisotropy of the liquid crystalline compound, a mixture of this compound and mother liquid crystals was used as a sample. When measuring the physical properties of the liquid crystal composition, the composition itself was used as a sample.
  • mother liquid crystals As the mother liquid crystals, the following mother liquid crystals (A) or mother liquid crystals (B) were used. The ratio of the components of the mother liquid crystals (A) and (B) is shown in wt%.
  • Measurement method Physical properties were measured by the following methods. Many of these are the methods described in the JEITA standard (JEITA ED-2521B) established by the Japan Electronics and Information Technology Industries Association (JEITA) or a modified method thereof. there were. No thin film transistor (TFT) was attached to the TN device used for the measurement.
  • Phase structure A sample was placed on a hot plate (METTLER FP-52 type hot stage) of a melting point measuring apparatus equipped with a polarizing microscope. While this sample was heated at a rate of 3 ° C./min, the phase state and its change were observed with a polarizing microscope to identify the type of phase.
  • the crystal was represented as C. When the types of crystals can be distinguished, they are represented as C 1 and C 2 , respectively.
  • the smectic phase is represented as S and the nematic phase is represented as N.
  • the smectic phase when a smectic A phase, a smectic B phase, a smectic C phase, or a smectic F phase can be distinguished, they are represented as S A , S B , S C , or S F , respectively.
  • the liquid (isotropic) was designated as I.
  • the transition temperature is expressed as “C 50.0 N 100.0 I”, for example. This indicates that the transition temperature from the crystal to the nematic phase is 50.0 ° C., and the transition temperature from the nematic phase to the liquid is 100.0 ° C.
  • Viscosity (bulk viscosity; ⁇ ; measured at 20 ° C .; mPa ⁇ s) The viscosity was measured using an E-type rotational viscometer manufactured by Tokyo Keiki Co., Ltd.
  • VHR-1 Voltage holding ratio
  • the TN device used for the measurement had a polyimide alignment film, and the distance (cell gap) between the two glass substrates was 5 ⁇ m.
  • This element was sealed with an adhesive that was cured by ultraviolet rays after the sample was placed.
  • This element was irradiated with ultraviolet rays for 400 seconds.
  • An EXERCURE 4000-D type mercury xenon lamp manufactured by HOYA CANDEO OPTRONICS Co., Ltd. was used for ultraviolet irradiation.
  • the device was charged by applying a pulse voltage (60 microseconds at 5 V).
  • the decaying voltage was measured for 16.7 milliseconds with a high-speed voltmeter, and the area A between the voltage curve and the horizontal axis in a unit cycle was determined. Area B was the area when it was not attenuated. The voltage holding ratio was expressed as a percentage of area A with respect to area B.
  • VHR-2 Voltage holding ratio (VHR-2; measured at 80 ° C .;%) The voltage holding ratio was measured by the above method except that the measurement was performed at 80 ° C. instead of 25 ° C. The results are indicated by the VHR-2 symbol.
  • Viscosity (Rotational viscosity; ⁇ 1; measured at 25 ° C .; mPa ⁇ s) The measurement followed the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). A sample was put in a TN device in which the twist angle was 0 degree and the distance between two glass substrates (cell gap) was 5 ⁇ m. A voltage was applied to this device in steps of 0.5 V in the range of 16 V to 19.5 V. After no application for 0.2 seconds, the application was repeated under the condition of only one rectangular wave (rectangular pulse; 0.2 seconds) and no application (2 seconds). The peak current and peak time of the transient current generated by this application were measured.
  • Threshold voltage (Vth; measured at 25 ° C .; V)
  • An LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement.
  • the light source was a halogen lamp.
  • a sample was put in a normally white mode TN device in which the distance between two glass substrates (cell gap) was 0.45 / ⁇ n ( ⁇ m) and the twist angle was 80 degrees.
  • the voltage (32 Hz, rectangular wave) applied to this element was increased stepwise from 0V to 10V by 0.02V.
  • the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured.
  • a voltage-transmittance curve was created in which the transmittance was 100% when the light amount reached the maximum and the transmittance was 0% when the light amount was the minimum.
  • the threshold voltage was expressed as a voltage when the transmittance reached 90%.
  • the rise time ( ⁇ r: rise time; millisecond) is the time required for the transmittance to change from 90% to 10%.
  • the fall time ( ⁇ f: fall time; millisecond) is the time required to change the transmittance from 10% to 90%.
  • the response time was expressed as the sum of the rise time and the fall time thus obtained.
  • the physical properties of the compound (No. 1) were as follows. Transition temperature: C 91.0 C 99.2 I Room temperature compatibility: 5% by weight Voltage holding ratio: 95% The composition used when measuring the voltage holding ratio was obtained by adding 0.4% of the compound (No. 1) to the mother liquid crystal (B).
  • a liquid crystal display device having a mode such as PSA By polymerizing a polymerizable composition containing the polymerizable compound (1) and a liquid crystal composition, a liquid crystal display device having a mode such as PSA can be produced.
  • the device has a wide temperature range in which the device can be used, a short response time, a high voltage holding ratio, a low threshold voltage, a large contrast ratio, and a long lifetime. Therefore, the compound (1) can be used for a liquid crystal projector, a liquid crystal television and the like.
  • Compound (1) can also be used as a raw material for optical anisotropic bodies.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Liquid Crystal Substances (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention fournit un composé polymérisable représenté par la formule (1) qui possède des propriétés de réaction de polymérisation adéquates, un taux de maintien de tension élevé, et une solubilité élevée dans une composition de cristaux liquides. L'invention fournit également une composition polymérisable contenant ce composé et une composition de cristaux liquides, un composite de cristaux liquides préparé à partir de cette composition polymérisable, et un élément d'affichage à cristaux liquides possédant ce composite de cristaux liquides. Dans la formule (1), par exemple, Ｒ１ représente un hydrogène, un halogène, －ＳＰ１－Ｐ１, ou un alkyle de 1 à 15 atomes de carbone, ＭＥＳ représente un groupe mésogène possédant au moins un cycle et un atome N, ＳＰ１ représente une liaison simple ou un alkylène de 1 à 10 atomes de carbone, Ｐ１ représente un groupe polymérisable, a représente 0, 1, 2, 3 ou 4, et c représente 0, 1, 2, 3 ou 4.
PCT/JP2018/001895 2017-03-14 2018-01-23 Composé polymérisable, et élément d'affichage à cristaux liquides Ceased WO2018168205A1 (fr)

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JP2019073589A (ja) * 2017-10-13 2019-05-16 Jnc株式会社 液晶組成物および液晶表示素子
WO2019111845A1 (fr) * 2017-12-05 2019-06-13 Jnc株式会社 Composé polaire polymérisable, composition de cristaux liquides, et élément d'affichage à cristaux liquides
WO2019220673A1 (fr) * 2018-05-15 2019-11-21 Jnc株式会社 Composé, composition de cristaux liquides, et élément d'affichage à cristaux liquides

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WO2019111845A1 (fr) * 2017-12-05 2019-06-13 Jnc株式会社 Composé polaire polymérisable, composition de cristaux liquides, et élément d'affichage à cristaux liquides
WO2019220673A1 (fr) * 2018-05-15 2019-11-21 Jnc株式会社 Composé, composition de cristaux liquides, et élément d'affichage à cristaux liquides

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CN110325507A (zh) 2019-10-11
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TW201840829A (zh) 2018-11-16
JP6787478B2 (ja) 2020-11-18
CN110325507B (zh) 2022-08-16

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