WO2014192657A1 - Polymerisable liquid crystal composition, phase difference film, phase difference patterning film, and homogeneously aligned liquid crystal film - Google Patents

Polymerisable liquid crystal composition, phase difference film, phase difference patterning film, and homogeneously aligned liquid crystal film Download PDF

Info

Publication number
WO2014192657A1
WO2014192657A1 PCT/JP2014/063698 JP2014063698W WO2014192657A1 WO 2014192657 A1 WO2014192657 A1 WO 2014192657A1 JP 2014063698 W JP2014063698 W JP 2014063698W WO 2014192657 A1 WO2014192657 A1 WO 2014192657A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
liquid crystal
polymerizable
general formula
crystal composition
Prior art date
Application number
PCT/JP2014/063698
Other languages
French (fr)
Japanese (ja)
Inventor
秀俊 中田
桑名 康弘
長谷部 浩史
美花 山本
浩一 延藤
小谷 邦彦
小野 善之
Original Assignee
Dic株式会社
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株式会社 filed Critical Dic株式会社
Priority to JP2014557905A priority Critical patent/JPWO2014192657A1/en
Publication of WO2014192657A1 publication Critical patent/WO2014192657A1/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00Liquid crystal materials
    • C09K19/04Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06Non-steroidal liquid crystal compounds
    • C09K19/08Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/20Non-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
    • C09K19/2007Non-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 the chain containing -COO- or -OCO- groups
    • C09K19/2014Non-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 the chain containing -COO- or -OCO- groups containing additionally a linking group other than -COO- or -OCO-, e.g. -CH2-CH2-, -CH=CH-, -C=C-; containing at least one additional carbon atom in the chain containing -COO- or -OCO- groups, e.g. -(CH2)m-COO-(CH2)n-
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers 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
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/26Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C08F220/303Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one or more carboxylic moieties in the chain
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00Liquid crystal materials
    • C09K19/04Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06Non-steroidal liquid crystal compounds
    • C09K19/32Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00Liquid crystal materials
    • C09K19/04Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06Non-steroidal liquid crystal compounds
    • C09K19/32Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
    • C09K19/322Compounds containing a naphthalene ring or a completely or partially hydrogenated naphthalene ring
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00Liquid crystal materials
    • C09K19/52Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/60Pleochroic dyes
    • C09K19/601Azoic
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/30Polarising elements
    • G02B5/3016Polarising elements involving passive liquid crystal elements
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL 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
    • G02F1/00Devices 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
    • G02F1/01Devices 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 
    • G02F1/13Devices 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
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1337Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00Liquid crystal materials
    • C09K19/04Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K2019/0444Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
    • C09K2019/0448Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00Liquid crystal materials
    • C09K19/04Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06Non-steroidal liquid crystal compounds
    • C09K19/08Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/20Non-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
    • C09K19/2007Non-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 the chain containing -COO- or -OCO- groups
    • C09K2019/2078Ph-COO-Ph-COO-Ph
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00Liquid crystal materials
    • C09K19/52Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K2019/528Surfactants
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL 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
    • G02F1/00Devices 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
    • G02F1/01Devices 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 
    • G02F1/13Devices 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
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1335Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13363Birefringent elements, e.g. for optical compensation
    • G02F1/133631Birefringent elements, e.g. for optical compensation with a spatial distribution of the retardation value
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL 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
    • G02F1/00Devices 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
    • G02F1/01Devices 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 
    • G02F1/13Devices 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
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1337Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133715Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films by first depositing a monomer
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL 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
    • G02F1/00Devices 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
    • G02F1/01Devices 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 
    • G02F1/13Devices 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
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1337Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133738Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers for homogeneous alignment
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL 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
    • G02F1/00Devices 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
    • G02F1/01Devices 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 
    • G02F1/13Devices 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
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1337Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/13378Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
    • G02F1/133788Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation by light irradiation, e.g. linearly polarised light photo-polymerisation
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL 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
    • G02F2202/00Materials and properties
    • G02F2202/02Materials and properties organic material
    • G02F2202/022Materials and properties organic material polymeric
    • G02F2202/023Materials and properties organic material polymeric curable

Definitions

  • the present invention relates to a polymerizable liquid crystal composition, a retardation film, a retardation patterning film, and a homogeneous alignment liquid crystal film.
  • the molecular shape is made bulky (made bulky).
  • the polymerizable liquid crystal compound is made asymmetrical, which not only leads to an increase in cost, but also reduces the liquid crystallinity and causes a phenomenon in which the alignment is disturbed when polymerized.
  • Addition of a non-liquid crystalline compound also improves the solubility and storage stability, but the liquid crystallinity deteriorates and the orientation deteriorates.
  • Many chiral compounds are non-liquid crystalline by themselves. Even when these chiral compounds are added, the storage stability is improved, but there is a problem that they can be used only for polymerizable cholesteric liquid crystal materials.
  • the present invention has been made in view of the above circumstances, is a polymerizable liquid crystal composition that is excellent in storage stability and does not cause disorder in alignment when polymerized, and a position formed using the polymerizable liquid crystal composition.
  • An object is to provide a phase difference film, a phase difference patterning film, and a homogeneous alignment (horizontal alignment) liquid crystal film.
  • the first aspect of the present invention includes two or more polymerizable compounds represented by the following general formula (I) and an organic solvent, and m of any two polymerizable compounds among the polymerizable compounds is A polymerizable liquid crystal composition characterized by satisfying
  • 1 or 2 when SA and SB are satisfied, and satisfying SA + SB ⁇ 10.
  • P 1 and P 2 represent a reactive functional group
  • MG represents a mesogenic group or a mesogenic support group
  • two m represent the same numerical value of 1 to 6.
  • the second aspect of the present invention is a retardation film using the polymerizable liquid crystal composition of the first aspect.
  • the third aspect of the present invention is a retardation patterning film using the polymerizable liquid crystal composition of the first aspect.
  • a fourth aspect of the present invention is a homogeneously aligned liquid crystal film using the polymerizable liquid crystal composition of the first aspect.
  • the liquid crystal composition according to the present invention has excellent storage stability and excellent orientation when polymerized. By using this liquid crystal composition, it is possible to produce a retardation film, a retardation patterning film, and a homogeneous alignment liquid crystal film excellent in orientation.
  • the polymerizable liquid crystal composition of the first embodiment of the present invention includes two or more polymerizable compounds (polymerizable liquid crystal compounds) represented by the following general formula (I) and an organic solvent, and among the polymerizable compounds:
  • 1 or 2
  • SA + SB ⁇ 10 is satisfied.
  • P 1 and P 2 represent reactive functional groups
  • MG represents a mesogenic group or a mesogenic supporting group
  • two m represent the same numerical value of 1 to 6.
  • Examples of the reactive functional group represented by P 1 and P 2 in the general formula (I) include the following general formula (II-c), general formula (II-d), and general formula (II-e).
  • P 1 and P 2 in a single molecule are preferably the same.
  • R 21 , R 22, R 23, R 31, R 32, R 33, R 41, R 42 and R Each of 43 independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms, and n represents 0 or 1.
  • R 31 in the general formula (II-d) represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms.
  • the left end of the substituent (reactive functional group) represented by the above general formula is bonded to the carbon atom of the methylene group of the general formula (I).
  • the alkyl group is preferably a linear or branched alkyl group, and more preferably a linear alkyl group.
  • Examples of the reactive group represented by the general formula (II-c), general formula (II-d) or general formula (II-e) include the following reactive groups (P-1) and (P-2). , (P-3), (P-5), (P-6), (P-9), and (P-10). Of these reactive functional groups, the following (P-1) or (P-2) is preferred, and the following (P-1) is more preferred from the viewpoint of enhancing the polymerizability and storage stability.
  • Examples of the mesogenic group or mesogenic support group represented by MG in the general formula (I) include groups represented by the following general formula (II-b).
  • A1, A2 and A3 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5- Diyl group, 1,3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2,6- Diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2, 6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,
  • the polymerizable liquid crystal composition of this embodiment contains two or more polymerizable compounds represented by the general formula (I).
  • “m” in the general formula (I) representing the first polymerizable compound is “SA”.
  • “m” in the general formula (I) representing the second polymerizable compound is represented as “SB”, at least one set satisfying
  • 1 or 2 and satisfying SA + SB ⁇ 10 There are combinations of two polymerizable compounds.
  • the polymerizable liquid crystal composition of the present embodiment preferably contains 2 to 4 polymerizable compounds represented by the general formula (I), more preferably 2 to 3 types, more preferably 2 types. More preferably.
  • the relationship between SA and SB is established in any combination of the polymerizable compounds. If you do.
  • the polymerizable compound represented by the general formula (I) contained in the polymerizable liquid crystal composition of the present embodiment is preferably a polymerizable compound represented by the following general formula (I-1).
  • Y 21 represents a hydrogen atom or a methyl group.
  • E 21 represents an alkylene group having 1 to 8 carbon atoms.
  • Z 21 and Z 22 are each independently —COO—, —OCO—, —CH 2 CH 2 COO—, —CH 2 CH 2 OCO—, —COOCH 2 CH 2 —, —OCOCH 2 CH 2 —, Or it represents a single bond.
  • X 13 to X 24 each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, a methoxy group, a CF 3 group, or an OCF 3 group, and 1 to 3 of X 13 to X 24 Represents a fluorine atom, a chlorine atom, a methyl group, a methoxy group, a CF 3 group, or an OCF 3 group.
  • n 1 is 0, 1 or 2. When n 1 is 2 and a plurality of Z 21 are present, they may be the same or different, and when there are a plurality of 1,4-phenylene groups having substituents X17 to X20, they are the same. May be different.
  • Z 21 and Z 22 are preferably each independently —COO— or —OCO—.
  • Preferable specific examples represented by the general formula (I-1) include polymerizable compounds represented by the following general formulas (I-1-1) to (I-1-5).
  • Y 22 represents a hydrogen atom or a methyl group
  • RI 1 to RI 14 each independently represents a fluorine atom, a chlorine atom, a methyl group or a methoxy group.
  • Nr 1 to nr 14 are each independently an integer of 0 to 2, and when nr 1 to nr 14 is 2 and there are a plurality of RI 1 to RI 14, they may be the same or different
  • m represents an integer of 1 to 8.
  • m is preferably from 2 to 7, and more preferably from 3 to 6.
  • the bonding positions of RI 1 to RI 3 and RI 5 to RI 14 are not particularly limited, and nr 1 ⁇ nr 3, if nr 5 ⁇ nr 14 is 1, lateral position is preferred.
  • nr 1 to nr 3 and nr 5 to nr 14 are 2, arbitrary substitution positions can be combined.
  • polymerizable compounds represented by the general formulas (I-1-1) to (I-1-5) those represented by any one of the general formulas (I-1-1) to (I-1-4)
  • a polymerizable compound represented by any one of the general formulas (I-1-2) to (I-1-4) is more preferable.
  • a compound in which Y 22 is a hydrogen atom, RI 4 is a hydrogen atom or a methyl group, and nr 4 is 0 or 1 is preferable.
  • a compound in which Y 22 is a hydrogen atom and nr 5 to nr 11 are 0 is preferable.
  • the polymerizable compound represented by the general formula (I) has three ring structures, if the lateral hydrogen atom of the ring structure is substituted with a substituent, the polymerizable compound
  • the solubility of the compound in the solvent is improved, and the storage stability of the polymerizable liquid crystal composition of this embodiment is improved, which is preferable.
  • the polymerizable liquid crystal composition of the present embodiment includes the above general formulas (I-1-1) to (I-1-4) as the two or more polymerizable compounds represented by the general formula (I). Any two or more polymerizable compounds selected from the group consisting of the polymerizable compounds represented by formula (I) are preferred, and the polymerizable compounds represented by the above general formulas (I-1-2) to (I-1-4) Any two or more polymerizable compounds selected from the group consisting of are more preferred. Further, two or more compounds represented by the above general formula (I-1-2), two or more compounds represented by the above general formula (I-1-3), and the above general formula (I-1-) It is more preferable to contain two or more compounds represented by 4).
  • the total weight of the polymerizable compounds (including monofunctional compounds described later) contained in the polymerizable liquid crystal composition of the present embodiment is 100 parts by weight
  • the total of the polymerizable compounds represented by the general formula (I) The content of is preferably more than 30% by weight and less than 95% by weight, more preferably 50 to 95% by weight, still more preferably 60 to 90% by weight.
  • the total weight of the polymerizable compounds contained in the polymerizable liquid crystal composition is 100 parts by weight
  • the content of each polymerizable compound represented by the general formula (I) is independently preferably more than 30 and 60% by weight or less, more preferably more than 30 and 50% by weight or less, more than 30 and 45% by weight. The following is more preferable. When the content is in these preferred ranges, the storage stability of the polymerizable liquid crystal composition of the present embodiment is further improved.
  • the first polymerizable compound represented by the general formula (I) and the second polymerizable compound when two kinds of polymerizable compounds represented by the general formula (I) are included, the first polymerizable compound represented by the general formula (I) and the second polymerizable compound.
  • the difference in the compound content is preferably 0 to 30 parts by weight, more preferably 0 to 20 parts by weight, and still more preferably 0 to 10 parts by weight.
  • the storage stability of the polymerizable liquid crystal composition of the present embodiment is further improved when the contents of the two polymerizable compounds are equal.
  • the liquid crystal composition of the present embodiment preferably includes a monofunctional compound having one reactive functional group in the molecule.
  • a monofunctional compound By containing a monofunctional compound, the storage stability of the polymerizable liquid crystal composition of the present embodiment is further improved, and the use of polymer base material lamination (for example, retardation film and retardation patterning in the field of liquid crystal display) When used for a film and a homogeneous alignment (horizontal alignment) liquid crystal film, etc., properties such as excellent alignment can be imparted.
  • the substrate on which the solution containing the polymerizable liquid crystal composition of the present invention is applied is a substrate that is usually used for liquid crystal devices, displays, optical components and optical films, and after the application of the polymerizable liquid crystal composition of the present invention.
  • a substrate that is usually used for liquid crystal devices, displays, optical components and optical films, and after the application of the polymerizable liquid crystal composition of the present invention.
  • a material having heat resistance that can withstand heating during the drying of the liquid crystal or during the manufacture of the liquid crystal device.
  • examples of such a substrate include organic materials such as a glass substrate, a metal substrate, a ceramic substrate, and a polymer substrate.
  • the polymer base material is preferable because it can be produced by roll-to-roll and is easy to handle as compared with a glass substrate or the like.
  • the base material (polymer base material) made of a polymer compound has excellent affinity with the polymerizable compound of the present embodiment, and after applying and drying a solution containing the polymerizable compound to the polymer base material,
  • the polymerizable compound of the present embodiment is also suitable for applications that are laminated on a polymer substrate because it is easy to impart excellent orientation.
  • the polymer compound constituting such a preferable polymer substrate include cellulose derivatives, polyolefin-based, polyester-based, polyethylene terephthalate, polycarbonate, polyacrylate-based, polyarylate, polyethersulfone, polyimide, polyphenylene sulfide, and polyphenylene ether. , Nylon, or polystyrene. Particularly preferred are cycloolefin polymer, triacetyl cellulose, and polymethyl methacrylate resin.
  • the substrate may be subjected to an alignment treatment so that the polymerizable liquid crystal composition is easily aligned when the polymerizable liquid crystal composition of the present invention is applied and dried.
  • an alignment treatment in addition to the method of directly rubbing the substrate, an alignment film used in a general liquid crystal device may be applied and the rubbing treatment may be performed.
  • a particularly preferable method is a publicly known method using a photo-alignment film. When the photo-alignment film is used, a patterned retardation film can be produced.
  • the polymerizable compound represented by the following general formula (X) may be referred to as a “monofunctional compound”.
  • Examples of the monofunctional compound include polymerizable compounds represented by the following general formula (X).
  • the polymerizable liquid crystal composition of the present embodiment has a polymerizable compound (monofunctional compound) represented by the following general formula (X) from the viewpoint of improving storage stability and improving alignment when polymerized. It is preferable to include one or more types, and it is more preferable to include two or more types.
  • the polymerizable liquid crystal composition of this embodiment contains two or more monofunctional compounds represented by the general formula (X), m x of any two monofunctional compounds is respectively SAx and SBx. In this case, it is preferable that 1 ⁇
  • P x represents a reactive functional group
  • m x represents an integer of 1 to 8
  • MG represents a mesogenic group or a mesogenic supporting group
  • R 1 represents a hydrogen atom, a halogen atom, A cyano group or an alkyl group having 1 to 25 carbon atoms, wherein one or more hydrogen atoms bonded to the alkyl group may be substituted with a halogen atom or CN, and one CH present in the group;
  • Two groups or two or more CH 2 groups that are not adjacent to each other are independently of each other in a form in which oxygen atoms, sulfur atoms, and oxygen atoms and sulfur atoms are not directly bonded to each other.
  • R 1 is the reactivity Except for the case of a functional group).
  • R 1 is an alkyl group having 1 to 8 carbon atoms (one CH 2 group present in this group or two or more non-adjacent CH 2 groups are independently of each other, And may be replaced by —O—, —CO—, —COO—, —OCO—, —OCOO—, —CH ⁇ CH—, or —C ⁇ C— in a form that is not directly bonded to each other. It is preferable.
  • Examples of the reactive functional group represented by P x in the general formula (X) include a substituent represented by the general formula (II-c), (II-d), or (II-e). And substituents selected from the group.
  • Examples of the mesogenic group or mesogenic supporting group represented by MG in the general formula (X) include the same groups as MG in the general formula (II-b).
  • the polymerizable liquid crystal composition of the present embodiment may contain two or more polymerizable compounds represented by the general formula (X).
  • “m x ” in the general formula (X) representing the first polymerizable compound is changed to “SA x. represents a ", if the formula representing the second polymerizable compound" m x "in (X) represented as" SB x ", 1 ⁇
  • polymerizable liquid crystal composition of the present embodiment it is preferable to contain 2 to 4 types of polymerizable compounds represented by the general formula (X), more preferably 2 to 3 types, and more preferably 2 types. More preferably.
  • the relationship between SA and SB is established in any combination of the polymerizable compounds. If you do.
  • Examples of the two or more polymerizable compounds represented by the general formula (X) contained in the polymerizable liquid crystal composition of the present embodiment include the following general formulas (X-1) to (X-4) and the following general formulas: Any two or more polymerizable compounds selected from the group consisting of polymerizable compounds represented by (X-31) to (X-32) are preferred, Two or more compounds represented by the following general formula (X-1), two or more compounds represented by the following general formula (X-2), and a compound represented by the following general formula (X-3) Two or more compounds, two or more compounds represented by the following general formula (X-4), two or more compounds represented by the following general formula (X-31), or the following general formula (X-32) It is more preferable that 2 or more types of compounds represented by these are contained.
  • Y 21 , Y 31 , Y 41 , and Y 51 each independently represent a hydrogen atom or a methyl group.
  • E 21 , E 31 , E 41 , and E 51 each independently represent an alkylene group having 1 to 8 carbon atoms.
  • Z 21 , Z 22 , Z 31 , Z 32 , Z 41 , Z 42 , Z 51 , and Z 52 are each independently —COO—, —OCO—, —C ⁇ C—, —CH ⁇ CH—. , —CH 2 —CH 2 —, —CH ⁇ CH—COO—, —OCO—CH ⁇ CH—, or a single bond.
  • X 13 to X 24 each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, a methoxy group, a CF 3 group, or an OCF 3 group, and 1 to 3 of X 13 to X 24 Preferably represents a fluorine atom, a chlorine atom, a methyl group, a methoxy group, a CF 3 group, or an OCF 3 group.
  • X 25 to X 39 each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, a methoxy group, a CF 3 group, or an OCF 3 group, and 1 to 3 of X 25 to X 39 Preferably represents a fluorine atom, a chlorine atom, a methyl group, a methoxy group, a CF 3 group, or an OCF 3 group.
  • X 40 to X 53 each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, a methoxy group, a CF 3 group, or an OCF 3 group, and 1 to 3 of X 40 to X 53 Preferably represents a fluorine atom, a chlorine atom, a methyl group, a methoxy group, a CF 3 group, or an OCF 3 group.
  • X 54 to X 68 each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, a methoxy group, a CF 3 group, or an OCF 3 group, and 1 to 3 of X 54 to X 68 Preferably represents a fluorine atom, a chlorine atom, a methyl group, a methoxy group, a CF 3 group, or an OCF 3 group.
  • R 2 to R 5 each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, or an alkyl group having 1 to 15 carbon atoms, and one or two or more present in the alkyl group
  • the methylene group is substituted with an oxygen atom (—O—), —CO—, —OCO—, —COO—, —C ⁇ C—, or —CH ⁇ CH—, assuming that the oxygen atoms are not directly bonded to each other. (Except when R 2 to R 5 are the reactive functional group).
  • Z 21 , Z 22 , Z 31 , Z 32 , Z 41 , Z 42 , Z 51 , and Z 52 are each independently a single bond, —COO—, or —OCO—, and R 2 to R More preferably, each of 5 is independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.
  • polymerizable compounds represented by the general formulas (X-1) to (X-4) polymerizable compounds represented by the following general formulas (X-5) to (X-21) Is mentioned.
  • Y 22 represents a hydrogen atom or a methyl group
  • R 21 represents an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.
  • R 23 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms,
  • R 22 represents a fluorine atom, a chlorine atom, a methyl group, or a methoxy group
  • n 21 represents an integer of 1 to 8.
  • Y 61 and Y 71 each independently represent a hydrogen atom or a methyl group.
  • E 61 and E 71 each independently represents an alkylene group having 1 to 8 carbon atoms.
  • Z 61 represents —COO—, —OCO—, or a single bond.
  • Z 62 represents —C ⁇ C—.
  • Z 71 and Z 72 each independently represent —COO—, —OCO—, or a single bond.
  • X 71 to X 82 each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, a methoxy group, a CF 3 group, or an OCF 3 group, and 1 to 3 of X 71 to X 82 Preferably represents a fluorine atom, a chlorine atom, a methyl group, a methoxy group, a CF 3 group, or an OCF 3 group.
  • X 85 to X 96 each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, a methoxy group, a CF 3 group, or an OCF 3 group.
  • R 7 to R 8 each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, or an alkyl group having 1 to 15 carbon atoms, and one or two or more present in the alkyl group
  • the methylene group may be substituted with an oxygen atom (—O—), —CO—, —OCO—, —COO—, or —CH ⁇ CH—, provided that the oxygen atoms are not directly bonded to each other (provided that R 7 to R 8 are the reactive functional groups).
  • Z 61 is —COO— or —OCO—
  • Z 62 is —C ⁇ C—
  • R 7 has 1 to 10 carbon atoms.
  • a compound having an alkyl group or an alkoxy group having 1 to 10 carbon atoms is more preferred.
  • Z 71 is —COO— or —OCO—
  • Z 72 is a single bond
  • R 8 is an alkyl group having 1 to 10 carbon atoms.
  • a compound which is an alkoxy group having 1 to 10 carbon atoms is more preferable.
  • polymerizable compounds represented by the general formulas (X-31) to (X-32) include polymerizable compounds represented by the following general formulas (X-33) to (X-44). Can be mentioned.
  • Y 62 and Y 72 represent a hydrogen atom or a methyl group
  • R 61 and R 63 represent an alkyl group having 1 to 10 carbon atoms or a carbon atom number of 1 to 10 represents an alkoxy group
  • R 62 and R 64 represent a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group or a methoxy group
  • n 61 represents an integer of 1 to 8.
  • polymerizable compounds represented by the general formulas (X-33) to (X-44) those represented by the general formulas (X-33), (X-34), (X-39) and (X-40) are preferred.
  • the polymerizable compound represented by the general formula (X) is preferably a compound represented by the following general formula (X-50).
  • Y 82 represents a hydrogen atom or a methyl group
  • n 81 is an integer of 0 to 8
  • n 82 is 1 or 2
  • Z 83 is —COO— or —OCO—. , —C ⁇ C—, or a single bond
  • a 83 represents a 1,4-phenylene group or a 1,4-cyclohexylene group
  • R 83 represents an alkyl group having 1 to 5 carbon atoms or an alkoxyl group.
  • Z 83 is preferably a single bond
  • a 83 is a 1,4-phenylene group
  • R 83 is a cyano group, a methyl group, an ethyl group, or a methoxy group.
  • n 82 is 2 and a plurality of Z 83 are present, they may be the same or different, and when a plurality of A 83 are present, they may be the same or different.
  • the compound of the general formula (X-50) is an effective compound when it is desired to reduce the viscosity. However, if too much is added, the orientation deteriorates.
  • the addition amount is preferably 0 to 30% by mass, and more preferably 0 to 10% by mass, when the total amount of the polymerizable compound is 100% by mass.
  • the polymerizable compound represented by the general formula (X) has three ring structures
  • the lateral hydrogen atom of the ring structure is substituted with a substituent
  • the polymerizable compound The solubility of the compound in the solvent is improved, and the storage stability of the polymerizable liquid crystal composition of this embodiment is improved, which is preferable.
  • the polymerizable liquid crystal composition of the present embodiment contains two or more polymerizable compounds represented by the general formula (X-5), and the polymerizable property represented by the general formula (X-12).
  • the total weight of the polymerizable compounds (including the bifunctional compound described above) contained in the polymerizable liquid crystal composition of the present embodiment is 100 parts by weight
  • the content of is preferably 5 parts by weight or more and less than 70 parts by weight, more preferably 5 to 50 parts by weight, still more preferably 10 to 40 parts by weight.
  • the total weight of the polymerizable compounds contained in the polymerizable liquid crystal composition is 100 parts by weight
  • the content of each polymerizable compound represented by the general formula (X) is preferably 5 to 70% by weight, more preferably 5 to 50% by weight, and still more preferably 10 to 40% by weight. When the content is in these preferred ranges, the storage stability of the polymerizable liquid crystal composition of the present embodiment is further improved.
  • the first polymerizable compound represented by the general formula (X) and the second polymerizable compound when two kinds of polymerizable compounds represented by the general formula (X) are included, the first polymerizable compound represented by the general formula (X) and the second polymerizable compound.
  • the difference in the compound content is preferably 0 to 30 parts by weight, more preferably 0 to 20 parts by weight, and still more preferably 0 to 10 parts by weight.
  • the storage stability of the polymerizable liquid crystal composition of the present embodiment is further improved when the contents of the two polymerizable compounds are equal.
  • the total content of the bifunctional compound represented by the general formula (I) and the monofunctional compound represented by the general formula (X) with respect to the total weight of the polymerizable liquid crystal composition of the present embodiment is 5 to 50 wt% is preferable, 10 to 40 wt% is more preferable, and 20 to 40 wt% is still more preferable.
  • the lower limit is determined from the viewpoint of improving the coating property of the composition on the substrate, and the upper limit is determined from the viewpoint of increasing the storage stability of the composition.
  • the polymerizable composition solution of the present invention may contain a polymerizable discotic liquid crystal compound in addition to the bifunctional compound represented by the general formula (I).
  • the polymerizable discotic liquid crystal compound used in the present invention preferably has one or more polymerizable functional groups. Examples of such compounds include polymerizability as described in JP-A-7-281028, JP-A-7-287120, JP-A-7-333431, and JP-A-8-27284. Examples include discotic liquid crystal compounds.
  • the compounding quantity of a polymerizable discotic liquid crystal compound can be suitably adjusted with a compound.
  • Examples of the general formula of the polymerizable discotic liquid crystal compound include general formulas (4-1) to (4-3), but are not limited to the following general formula.
  • Sp 4 represents an alkylene group having 0 to 18 carbon atoms, and the alkylene group is substituted with one or more halogen atoms, CN group, or an alkyl group having 1 to 8 carbon atoms having a polymerizable functional group.
  • a 4 represents 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, 1,3-dioxane-2,5-diyl group, tetrahydro Thiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2,6-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5 -Diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene- 2,7-diyl group, 9,10-dihydrophenanthrene-2,7-
  • P 4a represents a polymerizable functional group
  • Sp 3a represents the same meaning as Sp 1
  • P 4a preferably represents a substituent selected from the polymerizable groups represented by the following formulas (P-1) to (P-20).
  • the formula (P-1) or the formulas (P-2), (P-7), (P-12), (P-13) ) are preferred, and formulas (P-1), (P-7), and (P-12) are more preferred.
  • Specific examples of the polymerizable discotic liquid crystal compound include compounds (4-4) to (4-8), but are not limited to the following compounds.
  • q represents an integer of 1 to 18.
  • Organic solvent constituting the polymerizable liquid crystal composition of the present embodiment is not particularly limited as long as it can dissolve the general formula (I), but is a solvent that can be evaporated at a temperature of 100 ° C. or lower and dried. It is preferable that it is present, and it is preferable that the substrate used is not eroded.
  • solvents examples include aromatic hydrocarbons such as toluene, xylene, cumene, and mesitylene, ester solvents such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclohexane, and the like.
  • Ketone solvents such as pentanone, ether solvents such as tetrahydrofuran, 1,2-dimethoxyethane and anisole, amide solvents such as N, N-dimethylformamide and N-methyl-2-pyrrolidone, propylene glycol monomethyl ether acetate, Examples include diethylene glycol monomethyl ether acetate, ⁇ -butyrolactone, and chlorobenzene. These organic solvents can be used alone or in combination of two or more.
  • the solubility of the polymerizable compound represented by the general formula (I) is excellent, the orientation of the film obtained by polymerizing the composition is also excellent, and it is easy to dry at 100 ° C. or less. More preferred are toluene, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether acetate, and N-methyl-2-pyrrolidone and combinations thereof.
  • the content of the organic solvent relative to the total weight of the polymerizable liquid crystal composition of the present embodiment is preferably a content that facilitates application of the composition to a substrate, for example, 40 to 90% by weight. Preferably, it is 50 to 80% by weight.
  • the polymerizable liquid crystal composition of the present embodiment preferably contains at least one polymerization initiator.
  • the polymerization initiator is a useful compound for efficiently polymerizing the polymerizable liquid crystal composition.
  • a photopolymerization initiator is preferable, and specifically, the following compounds are preferable. Irgacure 651, Irgacure 184, Irgacure 907, Irgacure 127, Irgacure 369, Irgacure 379, Irgacure 819, Irgacure OXE01, Irgacure OXE02, Lucyrin TPO, Darocur 1173 manufactured by BASF.
  • These polymerization initiators may be used alone or in combination of two or more, and a sensitizer or the like may be added.
  • the content of the polymerization initiator with respect to the total weight of the polymerizable liquid crystal composition of the present embodiment is, for example, preferably 0.1 to 10% by weight, more preferably 1 to 7% by weight, and still more preferably 3 to 7% by weight. .
  • the polymerizable liquid crystal composition of this embodiment preferably contains a surfactant or a compound having a repeating unit represented by the following general formula (3) and having a weight average molecular weight of 100 or more.
  • R 11 , R 12 , R 13 and R 14 each independently represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and one or more hydrogen atoms in the hydrocarbon group
  • the atom may be substituted with a halogen atom.
  • the surfactant and the compound represented by the general formula (3) impart an effect of reducing the tilt angle of the liquid crystal compound at the air interface.
  • surfactant examples include alkyl carboxylates, alkyl phosphates, alkyl sulfonates, fluoroalkyl carboxylates, fluoroalkyl phosphates, fluoroalkyl sulfonates, polyoxyethylene derivatives, fluoroalkylethylene oxide derivatives, Examples include polyethylene glycol derivatives, alkyl ammonium salts, fluoroalkyl ammonium salts, silicone derivatives, and the like. Of these, fluorine-containing surfactants and silicone derivatives are particularly preferable.
  • MEGAFAC F-110 “MEGAFACCF-113”, “MEGAFAC F-120”, “MEGAFAC F-812”, “MEGAFAC F-142D”, “MEGAFAC F-144D”, “MEGAFAC F-” 150 “,” MEGAFAC F-171 “,” MEGAFACF-173 “,” MEGAFAC F-177 “,” MEGAFAC F-183 “,” MEGAFAC F-195 “,” MEGAFAC F-824 “,” MEGAFAC F-833 “ , “MEGAFAC F-114”, “MEGAFAC F-410”, “MEGAFAC F-493”, “MEGAFAC F-494”, “MEGAFAC F-443”, “MEGAFAC F-444”, “MEGAFAC F-445”, “ME “GAFAC F-446”, “MEGAFAC F-470”, “MEGAFAC F-471”, “MEGAFAC F-474”, “MEGAFAC F-475”, “MEGAFAC F-477”, “MEGAFAC F-110
  • the weight average molecular weight of the compound represented by the general formula (3) is preferably 200 to 100,000, more preferably 300 to 10,000, and further preferably 500 to 5,000.
  • the surfactant and the compound represented by the general formula (3) may be used singly or in combination of two or more. Moreover, you may use combining the said surfactant and the compound represented by the said General formula (3).
  • the total content of the surfactant and the compound represented by the general formula (3) with respect to the total weight of the polymerizable liquid crystal composition of the present embodiment is preferably 0.01 to 1% by weight, More preferably, it is 0.05 to 0.6% by weight.
  • a chain transfer agent is preferably added to the polymerizable liquid crystal composition of the present embodiment as another component in order to further improve the adhesion to the substrate.
  • the chain transfer agent is preferably a thiol compound, more preferably a monothiol, dithiol, trithiol, or tetrathiol compound, and even more preferably a trithiol compound.
  • compounds represented by the following general formulas (5-1) to (5-12) are preferable.
  • the content of these thiol compounds is preferably 0.5 to 5.0% by weight, more preferably 1.0 to 3.0% by weight, based on the total weight of the composition. .
  • R 66 is a carbon Represents an alkylene group having 2 to 18 atoms, and one or more methylene groups in the alkylene group are oxygen atoms, sulfur atoms, —CO—, —OCO on the assumption that an oxygen atom and a sulfur atom are not directly bonded to each other. It may be substituted with —, —COO—, or —CH ⁇ CH—.
  • a polymerization inhibitor an antioxidant or the like in order to improve storage stability.
  • examples of such compounds include hydroquinone derivatives and hindered phenol antioxidants. More specifically, p-methoxyphenol, IRGANOX1010, IRGANOX1035, IRGANOX1076, IRGANOX1098, IRGANOX1135, IRGANOX1325, IRGANOX1520, IRGANOX2457, IRGANOX3957, IRGANOX3590, IRGANOX3590, IRGANOX3590, IRGANOX3590, IRGANOX3590, IRGANOX3590, IRGANOX3590, IRGANOX3590, IRGANOX3590, IRGANOX3590, IRGANOX3590, IRGANOX3590, IRGANOX3590, IRGANOX3590, IRGANOX3590, IRGANOX3590, IRGANOX
  • the content of the polymerization inhibitor and the antioxidant is preferably 0.01 to 1.0% by mass, and 0.05 to 0.2% by mass with respect to the total weight of the composition. It is more preferable.
  • a non-polymerizable liquid crystal compound, a non-liquid crystal polymerizable compound, or the like can be added as necessary.
  • the content of these compounds is preferably 20% by weight or less, more preferably 10% by weight or less, and still more preferably 5% by weight or less based on the total weight of the composition.
  • optical anisotropic body manufacturing method (Optical anisotropic)
  • the optical anisotropic body of the present invention is obtained by sequentially laminating a base material, an orientation film as necessary, and a polymer of a polymerizable composition solution.
  • a base material, an orientation film as necessary, and a polymerization composition solution of a polymerizable composition solution are sequentially laminated, and an orientation film and a polymerizable composition that may be different from the above or above as necessary.
  • a product solution is sequentially laminated.
  • an alignment film and a polymerizable composition solution that may be different from the above or the above may be sequentially laminated thereon as necessary.
  • the base material used for the optical anisotropic body of the present invention is a base material usually used for liquid crystal devices, displays, optical elements, optical components, colorants, security markings, laser emission members, and optical films.
  • the material is not particularly limited as long as it is a material having heat resistance capable of withstanding heating during drying after the application of the polymerizable composition solution of the present invention.
  • Examples of such a substrate include organic materials such as a glass substrate, a metal substrate, a ceramic substrate, and a plastic substrate.
  • the substrate when the substrate is an organic material, examples thereof include cellulose derivatives, polyolefins, polyesters, polyolefins, polycarbonates, polyacrylates, polyarylates, polyether sulfones, polyimides, polyphenylene sulfides, polyphenylene ethers, nylons, and polystyrenes.
  • plastic substrates such as polyester, polystyrene, polyolefin, cellulose derivatives, polyarylate, and polycarbonate are preferable.
  • surface treatment of these substrates may be performed.
  • the surface treatment examples include ozone treatment, plasma treatment, corona treatment, silane coupling treatment, and the like.
  • an organic thin film, an inorganic oxide thin film, a metal thin film, etc. are provided on the surface of the substrate by a method such as vapor deposition, or in order to add optical added value.
  • the material may be a pickup lens, a rod lens, an optical disk, a retardation film, a light diffusion film, a color filter, or the like. Among these, a pickup lens, a retardation film, a light diffusion film, and a color filter that have higher added value are preferable.
  • the alignment treatment include stretching treatment, rubbing treatment, polarized ultraviolet visible light irradiation treatment, ion beam treatment, and the like.
  • the alignment film a known and conventional alignment film is used.
  • alignment films include polyimide, polysiloxane, polyamide, polyvinyl alcohol, polycarbonate, polystyrene, polyphenylene ether, polyarylate, polyethylene terephthalate, polyether sulfone, epoxy resin, epoxy acrylate resin, acrylic resin, coumarin compound, chalcone.
  • the compound examples include compounds, cinnamate compounds, fulgide compounds, anthraquinone compounds, azo compounds, and arylethene compounds.
  • the compound subjected to the alignment treatment by rubbing is preferably an alignment treatment or a compound in which crystallization of the material is promoted by inserting a heating step after the alignment treatment.
  • an applicator method As an application method for obtaining the optical anisotropic body of the present invention, an applicator method, a bar coating method, a spin coating method, a gravure printing method, a flexographic printing method, an ink jet method, a die coating method, a cap coating method, dipping, etc. are known. Conventional methods can be performed. The polymerizable composition solution is applied and then dried.
  • the polymerization treatment of the dried polymerizable composition is generally performed by irradiation with light such as ultraviolet rays or heating in a state where the polymerizable compound represented by the general formula (1) in the polymerizable composition is planarly aligned.
  • light irradiation specifically, it is preferable to irradiate ultraviolet light having a wavelength of 390 nm or less, and most preferable to irradiate light having a wavelength of 250 to 370 nm.
  • the polymerizable composition causes decomposition or the like due to ultraviolet light of 390 nm or less, it may be preferable to perform polymerization treatment with ultraviolet light of 390 nm or more. This light is preferably diffused light and unpolarized light.
  • the retardation film of the present invention is prepared in the same manner as the optical anisotropic body of the present invention.
  • the polymerizable compound represented by the general formula (1) in the polymerizable composition is polymerized in a planar alignment state, a retardation film having in-plane birefringence with respect to the substrate is obtained.
  • the retardation film can be used as a homogeneous liquid crystal film.
  • the polymerizable compound represented by the general formula (1) in the polymerizable composition and the polymerizable chiral compound are polymerized in a planar alignment state, the birefringence is out of plane with respect to the substrate. A phase difference film is obtained.
  • the polymerizable compound represented by the general formula (1) in the polymerizable composition containing a polymerizable discotic compound is polymerized in a planar orientation state, it is compounded both in-plane and out-of-plane with respect to the substrate.
  • a retardation film having refractive properties can be obtained.
  • the substrate has a retardation
  • a retardation film having birefringence obtained by adding the birefringence of the substrate and the birefringence of the retardation film of the present invention can be obtained.
  • the birefringence of the base material and the birefringence of the retardation film may be in the same direction or different directions in the plane of the base material.
  • the liquid crystal device, the display, the optical element, the optical component, the colorant, the marking for security, the member for laser emission, the optical film, and the compensation film are applied in a form suitable for the application.
  • the retardation patterning film of the present invention is obtained by sequentially laminating a base material, an alignment film, and a polymer of a polymerizable composition solution in the same manner as the optical anisotropic body of the present invention. Are patterned so as to obtain different phase differences.
  • the patterning may be in different directions, such as linear patterning, lattice patterning, circular patterning, polygonal patterning, and the like.
  • the liquid crystal device, display, optical element, optical component, colorant, security marking, laser emission member, optical film, compensation film, and the like are used.
  • an alignment film is provided on the substrate, and the polymerizable composition solution of the present invention is applied and dried during the alignment treatment so that the polymerizable composition is patterned and aligned.
  • an alignment treatment include a fine rubbing treatment, a polarized ultraviolet visible light irradiation treatment through a photomask, and a fine shape processing treatment.
  • the alignment film known and conventional ones are used.
  • Such alignment films include polyimide, polysiloxane, polyamide, polyvinyl alcohol, polycarbonate, polystyrene, polyphenylene ether, polyarylate, polyethylene terephthalate, polyether sulfone, epoxy resin, epoxy acrylate resin, acrylic resin, coumarin compound, chalcone.
  • the compound include compounds, cinnamate compounds, fulgide compounds, anthraquinone compounds, azo compounds, and arylethene compounds.
  • the compound subjected to the alignment treatment by fine rubbing is preferably an alignment treatment or a compound in which crystallization of the material is promoted by adding a heating step after the alignment treatment.
  • homogeneous alignment is achieved by appropriately selecting a polymerizable liquid crystal compound and adjusting the amount of the surfactant or the compound having a repeating unit represented by the general formula (3) and having a weight average molecular weight of 100 or more. can do.
  • a UCL composition was prepared by mixing each compound at the ratio shown in the following table. Each additive was further added to the UCL solution in which 30 parts by weight of the UCL composition and 70 parts by weight of each solvent were mixed to prepare sample solutions for the examples and comparative examples.
  • composition A After dissolving 0.5 parts by weight of the compound represented by the above formula (A) in 49.5 parts by weight of 2- (2-ethoxyethoxy) ethanol, 49 parts by weight of 2-butoxyethanol is added to form a photo-alignment film. A solution of composition A was obtained. This solution was filtered through a 0.45 ⁇ m membrane filter to obtain a composition (A-1) for photo-alignment films.
  • the composition for photo-alignment film (A-1) was applied onto a film made of an 80 ⁇ m triacetyl cellulose derivative as a base material with a bar coater and dried at 80 ° C. for 2 minutes. The dry film thickness at this time was 15 nm.
  • the ultra-high pressure mercury lamp is passed through a wavelength cut filter, a band-pass filter, and a polarizing filter, and visible ultraviolet light having a wavelength of around 365 nm (irradiation intensity: 20 mW / cm 2 ) is applied to the substrate as linearly polarized parallel light.
  • the photo-alignment film was obtained by irradiating from the vertical direction. The irradiation amount was 100 mJ / cm 2 .
  • the polymerizable liquid crystal composition according to the present invention is widely applicable in the field of liquid crystal displays.

Landscapes

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

Abstract

Provided are: a polymerisable liquid crystal composition which has excellent storage stability, and in which disordering of alignment does not occur when polymerised; and a phase difference film, a phase difference patterning film, and a homogeneously aligned (horizontally aligned) liquid crystal film which are formed using the polymerisable liquid crystal composition. The polymerisable liquid crystal composition is characterised by: including two or more polymerisable compounds represented by general formula (I), and an organic solvent; and satisfying |SA-SB|=1,2, and SA+SB ≤ 10, where SA and SB are, respectively, m of any two polymerisable compounds from among the polymerisable compounds (in the formula, P1 and P2 represent reactive functional groups, MG represents a mesogenic group or a mesogenity-supporting group, and the two m represent the same numerical value from 1-6).

Description

重合性液晶組成物、位相差膜、位相差パターニング膜、及びホモジニアス配向液晶フィルムPolymerizable liquid crystal composition, retardation film, retardation patterning film, and homogeneous alignment liquid crystal film
 本発明は、重合性液晶組成物、位相差膜、位相差パターニング膜、及びホモジニアス配向液晶フィルムに関する。 The present invention relates to a polymerizable liquid crystal composition, a retardation film, a retardation patterning film, and a homogeneous alignment liquid crystal film.
 近年、重合性液晶材料を用いた、偏光板、位相差板等の開発が盛んに行われている。これらは、ラビング処理を施した基材や光配向させた光配向膜を成膜した基材に、重合可能な液晶材料を含む溶液を塗布し、溶剤を乾燥させた後、紫外線又は熱により重合させることによって得られる。これらの重合性液晶材料は、一般的に溶剤で希釈された形で使用されるため、溶剤への溶解性及び保存安定性が求められる。 In recent years, development of polarizing plates, retardation plates, etc. using polymerizable liquid crystal materials has been actively conducted. These are applied to a base material that has been subjected to rubbing treatment or a base material on which a photo-alignment photo-alignment film has been formed, and after applying a solution containing a polymerizable liquid crystal material, drying the solvent, and then polymerizing by ultraviolet rays or heat. To obtain. Since these polymerizable liquid crystal materials are generally used in a form diluted with a solvent, solubility in a solvent and storage stability are required.
一般的に、重合性液晶化合物を有機溶媒中に溶解させてなる液晶組成物の保存安定性を向上させるためには、分子の形状を嵩高くする(バルキーにする)ことが行われている。また、特許文献1~2では、重合性液晶化合物を非対称にすること行われているが、コストアップにつながるだけでなく、液晶性が低下すると共に、重合した時に配向が乱れる現象が発生してしまう問題がある。非液晶性化合物を添加することでも溶解性・保存安定性は向上するが、液晶性が悪くなり配向性が悪化してしまう。また、多くのキラル化合物は単独では非液晶性である。これらキラル化合物を添加しても保存安定性は向上するが、重合性コレステリック液晶材料に対してのみにしか使用できないという問題があった。 Generally, in order to improve the storage stability of a liquid crystal composition obtained by dissolving a polymerizable liquid crystal compound in an organic solvent, the molecular shape is made bulky (made bulky). In Patent Documents 1 and 2, the polymerizable liquid crystal compound is made asymmetrical, which not only leads to an increase in cost, but also reduces the liquid crystallinity and causes a phenomenon in which the alignment is disturbed when polymerized. There is a problem. Addition of a non-liquid crystalline compound also improves the solubility and storage stability, but the liquid crystallinity deteriorates and the orientation deteriorates. Many chiral compounds are non-liquid crystalline by themselves. Even when these chiral compounds are added, the storage stability is improved, but there is a problem that they can be used only for polymerizable cholesteric liquid crystal materials.
特開2008-127336号公報JP 2008-127336 A 特開2010-159324号公報JP 2010-159324 A
本発明は、上記事情に鑑みてなされたものであり、保存安定性に優れ、重合させた時の配向性に乱れが生じない重合性液晶組成物、該重合性液晶組成物を用いてなる位相差膜、位相差パターニング膜及びホモジニアス配向(水平配向)液晶フィルムの提供を課題とする。 The present invention has been made in view of the above circumstances, is a polymerizable liquid crystal composition that is excellent in storage stability and does not cause disorder in alignment when polymerized, and a position formed using the polymerizable liquid crystal composition. An object is to provide a phase difference film, a phase difference patterning film, and a homogeneous alignment (horizontal alignment) liquid crystal film.
 本発明者らが鋭意検討した結果、組成物中に含まれる2種以上の重合性化合物における、反応性官能基(重合性基)とメソゲン基又はメソゲン性指示基とをつなぐ連結基の長さが、所定の条件を満たすことにより、当該組成物の保存安定性が向上することを見出し、本発明を完成させた。 As a result of intensive studies by the present inventors, the length of a linking group connecting a reactive functional group (polymerizable group) and a mesogenic group or mesogenic indicator group in two or more polymerizable compounds contained in the composition. However, it has been found that the storage stability of the composition is improved by satisfying predetermined conditions, and the present invention has been completed.
 本発明の第一の態様は、下記一般式(I)で表される重合性化合物を2種以上と有機溶媒を含み、当該重合性化合物のうち、任意の2つの重合性化合物のmをそれぞれSAとSBとした場合に|SA-SB|=1又は2であり、かつ、SA+SB≦10を満たすことを特徴とする重合性液晶組成物である。 The first aspect of the present invention includes two or more polymerizable compounds represented by the following general formula (I) and an organic solvent, and m of any two polymerizable compounds among the polymerizable compounds is A polymerizable liquid crystal composition characterized by satisfying | SA−SB | = 1 or 2 when SA and SB are satisfied, and satisfying SA + SB ≦ 10.
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
 上記式中、P及びPは反応性官能基を表し、MGはメソゲン基又はメソゲン性支持基を表し、2つのmは1~6の同一の数値を表す。 In the above formula, P 1 and P 2 represent a reactive functional group, MG represents a mesogenic group or a mesogenic support group, and two m represent the same numerical value of 1 to 6.
 本発明の第二の態様は、第一の態様の重合性液晶組成物を用いてなる位相差膜である。
 本発明の第三の態様は、第一の態様の重合性液晶組成物を用いてなる位相差パターニング膜である。
 本発明の第四の態様は、第一の態様の重合性液晶組成物を用いてなるホモジニアス配向液晶フィルムである。
The second aspect of the present invention is a retardation film using the polymerizable liquid crystal composition of the first aspect.
The third aspect of the present invention is a retardation patterning film using the polymerizable liquid crystal composition of the first aspect.
A fourth aspect of the present invention is a homogeneously aligned liquid crystal film using the polymerizable liquid crystal composition of the first aspect.
 本発明にかかる液晶組成物は、保存安定性に優れ、重合させた時の配向性に優れる。この液晶組成物を用いることにより、配向性に優れた位相差膜、位相差パターニング膜、ホモジニアス配向液晶フィルムを製造することができる。 The liquid crystal composition according to the present invention has excellent storage stability and excellent orientation when polymerized. By using this liquid crystal composition, it is possible to produce a retardation film, a retardation patterning film, and a homogeneous alignment liquid crystal film excellent in orientation.
 以下、好適な実施の形態に基づき、本発明を説明するが、本発明はかかる実施形態に限定されない。 Hereinafter, although the present invention will be described based on preferred embodiments, the present invention is not limited to such embodiments.
《重合性液晶組成物》
 本発明の第一実施形態の重合性液晶組成物は、下記一般式(I)で表される重合性化合物(重合性液晶化合物)を2種以上と有機溶媒を含み、当該重合性化合物のうち、任意の2つの重合性化合物のmをそれぞれSAとSBとした場合に|SA-SB|=1又は2であり、かつ、SA+SB≦10を満たす。
<< Polymerizable liquid crystal composition >>
The polymerizable liquid crystal composition of the first embodiment of the present invention includes two or more polymerizable compounds (polymerizable liquid crystal compounds) represented by the following general formula (I) and an organic solvent, and among the polymerizable compounds: When m of any two polymerizable compounds is SA and SB, respectively, | SA−SB | = 1 or 2, and SA + SB ≦ 10 is satisfied.
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
一般式(I)中、P及びPは反応性官能基を表し、MGはメソゲン基又はメソゲン性支持基を表し、2つのmは1~6の同一の数値を表す。 In general formula (I), P 1 and P 2 represent reactive functional groups, MG represents a mesogenic group or a mesogenic supporting group, and two m represent the same numerical value of 1 to 6.
一般式(I)中のP及びPで表される反応性官能基としては、例えば、下記一般式(II-c)、一般式(II-d)及び一般式(II-e)で表される置換基からなる群より選ばれる置換基を表す。単一の分子におけるP及びPは、同一であることが好ましい。 Examples of the reactive functional group represented by P 1 and P 2 in the general formula (I) include the following general formula (II-c), general formula (II-d), and general formula (II-e). Represents a substituent selected from the group consisting of the substituents represented. P 1 and P 2 in a single molecule are preferably the same.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
一般式(II-c)、一般式(II-d)及び一般式(II-e)中、R21、R22、R23、R31、R32、R33、R41、R42及びR43はそれぞれ独立的に水素原子、ハロゲン原子、炭素原子数1~5のアルキル基を表し、nは0又は1を表す。
また、一般式(II-d)のR31は、水素原子、ハロゲン原子、炭素原子数1~5のアルキル基又は炭素原子数1~5のハロゲン化アルキル基を表す。
上記一般式で表される置換基(反応性官能基)は、その左端が一般式(I)のメチレン基の炭素原子に結合する。
前記アルキル基は直鎖状又は分岐鎖状アルキル基であることが好ましく、直鎖状アルキル基であることがより好ましい。前記アルキル基に結合する水素原子の一部又は全部がハロゲン原子によって置換されていてもよい。
In the general formula (II-c), formula (II-d) and formula (II-e), R 21 , R 22, R 23, R 31, R 32, R 33, R 41, R 42 and R Each of 43 independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms, and n represents 0 or 1.
R 31 in the general formula (II-d) represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms.
The left end of the substituent (reactive functional group) represented by the above general formula is bonded to the carbon atom of the methylene group of the general formula (I).
The alkyl group is preferably a linear or branched alkyl group, and more preferably a linear alkyl group. Some or all of the hydrogen atoms bonded to the alkyl group may be substituted with halogen atoms.
一般式(II-c)、一般式(II-d)又は一般式(II-e)で表される反応性基としては、例えば以下の反応性基(P-1)、(P-2)、(P-3)、(P-5)、(P-6)、(P-9)、(P-10)、が挙げられる。これらの反応性官能基のうち、重合性および保存安定性を高める観点から、下記(P-1)又は(P-2)が好ましく、下記(P-1)がより好ましい。 Examples of the reactive group represented by the general formula (II-c), general formula (II-d) or general formula (II-e) include the following reactive groups (P-1) and (P-2). , (P-3), (P-5), (P-6), (P-9), and (P-10). Of these reactive functional groups, the following (P-1) or (P-2) is preferred, and the following (P-1) is more preferred from the viewpoint of enhancing the polymerizability and storage stability.
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
一般式(I)中のMGで表されるメソゲン基又はメソゲン性支持基としては、例えば、下記一般式(II-b)で表される基が挙げられる。 Examples of the mesogenic group or mesogenic support group represented by MG in the general formula (I) include groups represented by the following general formula (II-b).
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
一般式(II-b)中、A1、A2及びA3はそれぞれ独立的に、1,4-フェニレン基、1,4-シクロヘキシレン基、1,4-シクロヘキセニル基、テトラヒドロピラン-2,5-ジイル基、1,3-ジオキサン-2,5-ジイル基、テトラヒドロチオピラン-2,5-ジイル基、1,4-ビシクロ(2,2,2)オクチレン基、デカヒドロナフタレン-2,6-ジイル基、ピリジン-2,5-ジイル基、ピリミジン-2,5-ジイル基、ピラジン-2,5-ジイル基、1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基、2,6-ナフチレン基、フェナントレン-2,7-ジイル基、9,10-ジヒドロフェナントレン-2,7-ジイル基、1,2,3,4,4a,9,10a-オクタヒドロフェナントレン2,7-ジイル基又はフルオレン2,7-ジイル基を表し、
該1,4-フェニレン基、1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基、2,6-ナフチレン基、フェナントレン-2,7-ジイル基、9,10-ジヒドロフェナントレン-2,7-ジイル基、1,2,3,4,4a,9,10a-オクタヒドロフェナントレン2,7-ジイル基及びフルオレン2,7-ジイル基に結合する1つ以上の水素原子は、F、Cl、CF、OCF、シアノ基、炭素原子数1~8のアルキル基、アルコキシ基、アルカノイル基、アルカノイルオキシ基、炭素原子数2~8のアルケニル基、アルケニルオキシ基、アルケノイル基又はアルケノイルオキシ基により置換されていても良く、
Z0及びZ3はそれぞれ独立的に、-COO-、-OCO-、-CH=CH-、-C≡C-、-CH=CHCOO-、-OCOCH=CH-、-CONH-、-NHCO-、-O-、-S-、-NH-、-N(CH)-、-CO-、-OCOO-、-SCO-、-COS-又は単結合を表し、
Z1及びZ2はそれぞれ独立して、-COO-、-OCO-、-CHCH-、-OCH-、-CHO-、-CH=CH-、-C≡C-、-CH=CHCOO-、-OCOCH=CH-、-CHCHCOO-、-CHCHOCO-、-COOCHCH-、-OCOCHCH-、-CONH-、-NHCO-、-O-、-S-、-NH-、-N(CH)-、-CO-、-OCOO-、-SCO-、-COS-又は単結合を表し、nは0、1又は2を表す。
In general formula (II-b), A1, A2 and A3 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5- Diyl group, 1,3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2,6- Diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2, 6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a, 9,10a-octahydrophenanthrene 2,7-diyl Group or a fluorene 2,7-diyl group,
The 1,4-phenylene group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2 , 7-diyl group, 1,2,3,4,4a, 9,10a-octahydrophenanthrene 2,7-diyl group and one or more hydrogen atoms bonded to fluorene 2,7-diyl group are F, Cl, CF 3 , OCF 3 , cyano group, alkyl group having 1 to 8 carbon atoms, alkoxy group, alkanoyl group, alkanoyloxy group, alkenyl group having 2 to 8 carbon atoms, alkenyloxy group, alkenoyl group or alkenoyl May be substituted by an oxy group,
Z0 and Z3 are each independently —COO—, —OCO—, —CH═CH—, —C≡C—, —CH═CHCOO—, —OCOCH═CH—, —CONH—, —NHCO—, — O—, —S—, —NH—, —N (CH 3 ) —, —CO—, —OCOO—, —SCO—, —COS— or a single bond,
Z1 and Z2 are each independently —COO—, —OCO—, —CH 2 CH 2 —, —OCH 2 —, —CH 2 O—, —CH═CH—, —C≡C—, —CH═ CHCOO—, —OCOCH═CH—, —CH 2 CH 2 COO—, —CH 2 CH 2 OCO—, —COOCH 2 CH 2 —, —OCOCH 2 CH 2 —, —CONH—, —NHCO—, —O— , -S -, - NH -, - n (CH 3) -, - CO -, - OCOO -, - SCO -, - COS- or a single bond, n b represents 0, 1 or 2.
本実施形態の重合性液晶組成物は、一般式(I)で表される重合性化合物を2種以上含有する。当該重合性液晶組成物に含まれる2種以上の一般式(I)で表される重合性化合物のうち、第一の重合性化合物を表す一般式(I)の「m」を「SA」と表し、第二の重合性化合物を表す一般式(I)の「m」を「SB」と表した場合、|SA-SB|=1又は2であり、かつ、SA+SB≦10を満たす少なくとも1組の2種の重合性化合物の組み合わせが存在する。 The polymerizable liquid crystal composition of this embodiment contains two or more polymerizable compounds represented by the general formula (I). Of the polymerizable compounds represented by the general formula (I) contained in the polymerizable liquid crystal composition, “m” in the general formula (I) representing the first polymerizable compound is “SA”. And when “m” in the general formula (I) representing the second polymerizable compound is represented as “SB”, at least one set satisfying | SA−SB | = 1 or 2 and satisfying SA + SB ≦ 10 There are combinations of two polymerizable compounds.
本実施形態の重合性液晶組成物においては、一般式(I)で表される重合性化合物を2~4種含有することが好ましく、2~3種含有することがより好ましく、2種含有することが更に好ましい。一般式(I)で表される重合性化合物を3種又は4種を含有する場合は、それらの重合性化合物の任意の組み合わせのうち、何れかの組み合わせで、上記SAとSBの関係が成立していれば良い。 The polymerizable liquid crystal composition of the present embodiment preferably contains 2 to 4 polymerizable compounds represented by the general formula (I), more preferably 2 to 3 types, more preferably 2 types. More preferably. When 3 or 4 polymerizable compounds represented by the general formula (I) are contained, the relationship between SA and SB is established in any combination of the polymerizable compounds. If you do.
本実施形態の重合性液晶組成物が含有する、一般式(I)で表される重合性化合物としては、下記一般式(I-1)で表される重合性化合物が好ましい。 The polymerizable compound represented by the general formula (I) contained in the polymerizable liquid crystal composition of the present embodiment is preferably a polymerizable compound represented by the following general formula (I-1).
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
 以下に、上記一般式(I-1)について説明する。
21は、水素原子、又はメチル基を表す。
21は、炭素原子数1~8のアルキレン基を表す。
21、Z22は、それぞれ独立して、-COO-、-OCO-、-CHCHCOO-、-CHCHOCO-、-COOCHCH-、-OCOCHCH-、又は単結合を表す。
13~X24は、それぞれ独立して、水素原子、フッ素原子、塩素原子、メチル基、メトキシ基、CF基、又はOCF基を表すが、X13~X24のうち1~3個はフッ素原子、塩素原子、メチル基、メトキシ基、CF基、又はOCF基を表す。
は、0、1又は2である。nが2でありZ21が複数存在する場合それらは同一であっても異なっていてもよく、置換基X17~X20を有する1,4-フェニレン基が複数存在する場合それらは同一であっても異なっていてもよい。
Hereinafter, the general formula (I-1) will be described.
Y 21 represents a hydrogen atom or a methyl group.
E 21 represents an alkylene group having 1 to 8 carbon atoms.
Z 21 and Z 22 are each independently —COO—, —OCO—, —CH 2 CH 2 COO—, —CH 2 CH 2 OCO—, —COOCH 2 CH 2 —, —OCOCH 2 CH 2 —, Or it represents a single bond.
X 13 to X 24 each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, a methoxy group, a CF 3 group, or an OCF 3 group, and 1 to 3 of X 13 to X 24 Represents a fluorine atom, a chlorine atom, a methyl group, a methoxy group, a CF 3 group, or an OCF 3 group.
n 1 is 0, 1 or 2. When n 1 is 2 and a plurality of Z 21 are present, they may be the same or different, and when there are a plurality of 1,4-phenylene groups having substituents X17 to X20, they are the same. May be different.
 また、Z21、Z22は、それぞれ独立して-COO-、又は-OCO-であることが好ましい。 Z 21 and Z 22 are preferably each independently —COO— or —OCO—.
上記一般式(I-1)で表される好適な具体例として、下記一般式(I-1-1)~(I-1-5)で表される重合性化合物が挙げられる。 Preferable specific examples represented by the general formula (I-1) include polymerizable compounds represented by the following general formulas (I-1-1) to (I-1-5).
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
前記式(I-1-1)~(I-1-5)中、Y22は水素原子又はメチル基を示し、RI~RI14はそれぞれ独立にフッ素原子、塩素原子、メチル基又はメトキシ基を表し、nr~nr14はそれぞれ独立に0~2の整数であり、nr~nr14が2でありRI~RI14が複数存在する場合それらは同一であっても異なっていてもよく、mは1~8の整数を示す。
mは2~7が好ましく、3~6がより好ましい。
In the formulas (I-1-1) to (I-1-5), Y 22 represents a hydrogen atom or a methyl group, and RI 1 to RI 14 each independently represents a fluorine atom, a chlorine atom, a methyl group or a methoxy group. Nr 1 to nr 14 are each independently an integer of 0 to 2, and when nr 1 to nr 14 is 2 and there are a plurality of RI 1 to RI 14, they may be the same or different In general, m represents an integer of 1 to 8.
m is preferably from 2 to 7, and more preferably from 3 to 6.
前記一般式(I-1-1)、(I-1-3)~(I-1-5)中、RI~RI、RI~RI14の結合位置は特に限定されず、nr~nr、nr~nr14が1である場合には、ラテラル位が好ましい。nr~nr、nr~nr14が2の場合には、任意の置換位置を組み合わせることができる。 In the general formulas (I-1-1), (I-1-3) to (I-1-5), the bonding positions of RI 1 to RI 3 and RI 5 to RI 14 are not particularly limited, and nr 1 ~ nr 3, if nr 5 ~ nr 14 is 1, lateral position is preferred. When nr 1 to nr 3 and nr 5 to nr 14 are 2, arbitrary substitution positions can be combined.
一般式(I-1-1)~(I-1-5)で表される重合性化合物のうち、一般式(I-1-1)~(I-1-4)のいずれかで表される重合性化合物が好ましく、一般式(I-1-2)~(I-1-4)のいずれかで表される重合性化合物がより好ましい。 Of the polymerizable compounds represented by the general formulas (I-1-1) to (I-1-5), those represented by any one of the general formulas (I-1-1) to (I-1-4) A polymerizable compound represented by any one of the general formulas (I-1-2) to (I-1-4) is more preferable.
これらの重合性化合物のうち、より好ましい化合物としては、
一般式(I-1-2)において、Y22が水素原子であり、RIは水素原子又はメチル基であり、nrが0、又は1である化合物が好ましい。
一般式(I-1-3)又は(I-1-4)において、Y22が水素原子であり、且つnr~nr11が0である化合物が好ましい。
Among these polymerizable compounds, as a more preferable compound,
In the general formula (I-1-2), a compound in which Y 22 is a hydrogen atom, RI 4 is a hydrogen atom or a methyl group, and nr 4 is 0 or 1 is preferable.
In the general formula (I-1-3) or (I-1-4), a compound in which Y 22 is a hydrogen atom and nr 5 to nr 11 are 0 is preferable.
以下に、一般式(I-1-1)~(I-1-5)で表される重合性化合物の具体例を示す。 Specific examples of the polymerizable compounds represented by the general formulas (I-1-1) to (I-1-5) are shown below.
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
 以上で例示したように、一般式(I)で表される重合性化合物が3つの環構造を有する場合、当該環構造のラテラル位の水素原子が置換基によって置換されていると、当該重合性化合物の溶媒に対する溶解性が向上し、本実施形態の重合性液晶組成物の保存安定性が向上するので好ましい。さらに、この保存安定性を一層向上させるためには、複数の重合性化合物同士の溶解性(相溶性)を高めることが好ましい。 As exemplified above, when the polymerizable compound represented by the general formula (I) has three ring structures, if the lateral hydrogen atom of the ring structure is substituted with a substituent, the polymerizable compound The solubility of the compound in the solvent is improved, and the storage stability of the polymerizable liquid crystal composition of this embodiment is improved, which is preferable. Furthermore, in order to further improve the storage stability, it is preferable to increase the solubility (compatibility) between a plurality of polymerizable compounds.
この相溶性を高める観点から、複数の重合性化合物の骨格構造を互いに近似させる又は同一にすることが好ましい。すなわち、本実施形態の重合性液晶組成物は、一般式(I)で表される2種以上の重合性化合物としては、上記一般式(I-1-1)~(I-1-4)で表される重合性化合物からなる群より選ばれる何れか2種以上の重合性化合物が好ましく、上記一般式(I-1-2)~(I-1-4)で表される重合性化合物からなる群より選ばれる何れか2種以上の重合性化合物がより好ましい。
また、上記一般式(I-1-2)で表される化合物を2種以上、上記一般式(I-1-3)で表される化合物を2種以上、上記一般式(I-1-4)で表される化合物を2種以上含有することがより好ましい。
From the viewpoint of increasing the compatibility, it is preferable that the skeleton structures of the plurality of polymerizable compounds are approximated or the same. That is, the polymerizable liquid crystal composition of the present embodiment includes the above general formulas (I-1-1) to (I-1-4) as the two or more polymerizable compounds represented by the general formula (I). Any two or more polymerizable compounds selected from the group consisting of the polymerizable compounds represented by formula (I) are preferred, and the polymerizable compounds represented by the above general formulas (I-1-2) to (I-1-4) Any two or more polymerizable compounds selected from the group consisting of are more preferred.
Further, two or more compounds represented by the above general formula (I-1-2), two or more compounds represented by the above general formula (I-1-3), and the above general formula (I-1-) It is more preferable to contain two or more compounds represented by 4).
 本実施形態の重合性液晶組成物に含有される重合性化合物(後述する単官能化合物を含む)の全重量を100重量部とした場合、一般式(I)で表される重合性化合物の合計の含有量は、30重量%より多く95重量%未満が好ましく、50~95重量%がより好ましく、60~90重量%が更に好ましい。 When the total weight of the polymerizable compounds (including monofunctional compounds described later) contained in the polymerizable liquid crystal composition of the present embodiment is 100 parts by weight, the total of the polymerizable compounds represented by the general formula (I) The content of is preferably more than 30% by weight and less than 95% by weight, more preferably 50 to 95% by weight, still more preferably 60 to 90% by weight.
 本実施形態の重合性液晶組成物において、一般式(I)で表される重合性化合物を2種含む場合、重合性液晶組成物に含有される重合性化合物の全重量を100重量部として、一般式(I)で表される各重合性化合物の含有量は、それぞれ独立して、30より多く60重量%以下が好ましく、30より多く50重量%以下がより好ましく、30より多く45重量%以下が更に好ましい。これらの好ましい範囲の含有量であると、本実施形態の重合性液晶組成物の保存安定性がより向上する。 In the polymerizable liquid crystal composition of the present embodiment, when two kinds of polymerizable compounds represented by the general formula (I) are included, the total weight of the polymerizable compounds contained in the polymerizable liquid crystal composition is 100 parts by weight, The content of each polymerizable compound represented by the general formula (I) is independently preferably more than 30 and 60% by weight or less, more preferably more than 30 and 50% by weight or less, more than 30 and 45% by weight. The following is more preferable. When the content is in these preferred ranges, the storage stability of the polymerizable liquid crystal composition of the present embodiment is further improved.
本実施形態の重合性液晶組成物において、一般式(I)で表される重合性化合物を2種含む場合、一般式(I)で表される第一の重合性化合物と第二の重合性化合物の含有量の差は、0~30重量部が好ましく、0~20重量部がより好ましく、0~10重量部がさらに好ましい。このように、2種の重合性化合物の含有量が均等であると、本実施形態の重合性液晶組成物の保存安定性がより向上する。 In the polymerizable liquid crystal composition of the present embodiment, when two kinds of polymerizable compounds represented by the general formula (I) are included, the first polymerizable compound represented by the general formula (I) and the second polymerizable compound. The difference in the compound content is preferably 0 to 30 parts by weight, more preferably 0 to 20 parts by weight, and still more preferably 0 to 10 parts by weight. Thus, the storage stability of the polymerizable liquid crystal composition of the present embodiment is further improved when the contents of the two polymerizable compounds are equal.
また、本実施形態の液晶組成は、分子内に1つの反応性官能基を有する単官能化合物を含むことが好ましい。単官能化合物を含有することにより、本実施形態の重合性液晶組成物の保存安定性をより一層高めるとともに、高分子基材積層の用途(例えば、液晶ディスプレイの分野における位相差膜、位相差パターニング膜及びホモジニアス配向(水平配向)液晶フィルム等の用途)に使用した場合に、優れた配向性等の特性を付与することができる。 In addition, the liquid crystal composition of the present embodiment preferably includes a monofunctional compound having one reactive functional group in the molecule. By containing a monofunctional compound, the storage stability of the polymerizable liquid crystal composition of the present embodiment is further improved, and the use of polymer base material lamination (for example, retardation film and retardation patterning in the field of liquid crystal display) When used for a film and a homogeneous alignment (horizontal alignment) liquid crystal film, etc., properties such as excellent alignment can be imparted.
本発明の重合性液晶組成物を含有する溶液を塗布する基材は、液晶デバイス、ディスプレイ、光学部品や光学フィルムに通常使用する基材であって、本発明の重合性液晶組成物の塗布後の乾燥時、あるいは、液晶デバイス製造時における加熱に耐えうる耐熱性を有する材料であれば、特に制限はない。そのような基材としては、ガラス基材、金属基材、セラミックス基材や高分子基材等の有機材料が挙げられる。中でも、高分子基材は、ロールトゥーロールで作製可能であり、ガラス基板等に比べて取扱いがしやすいことから、好ましい。 The substrate on which the solution containing the polymerizable liquid crystal composition of the present invention is applied is a substrate that is usually used for liquid crystal devices, displays, optical components and optical films, and after the application of the polymerizable liquid crystal composition of the present invention. There is no particular limitation as long as it is a material having heat resistance that can withstand heating during the drying of the liquid crystal or during the manufacture of the liquid crystal device. Examples of such a substrate include organic materials such as a glass substrate, a metal substrate, a ceramic substrate, and a polymer substrate. Among these, the polymer base material is preferable because it can be produced by roll-to-roll and is easy to handle as compared with a glass substrate or the like.
さらに、高分子化合物からなる基材(高分子基材)は、本実施形態の重合性化合物との親和性に優れ、当該重合性化合物を含む溶液を高分子基材に塗布及び乾燥した後に、優れた配向性を付与することが容易である点からも、本実施形態の重合性化合物は高分子基材の上に積層させる用途に好適である。このような好ましい高分子基材を構成する高分子化合物としては、セルロース誘導体、ポリオレフィン系、ポリエステル系、ポリエチレンテレフタレート、ポリカーボネート、ポリアクリレート系、ポリアリレート、ポリエーテルサルホン、ポリイミド、ポリフェニレンスルフィド、ポリフェニレンエーテル、ナイロン、又はポリスチレン等が挙げられる。特に好ましくは、シクロオレフィンポリマー、トリアセチルセルロース、ポリメタクリル酸メチル樹脂である。 Furthermore, the base material (polymer base material) made of a polymer compound has excellent affinity with the polymerizable compound of the present embodiment, and after applying and drying a solution containing the polymerizable compound to the polymer base material, The polymerizable compound of the present embodiment is also suitable for applications that are laminated on a polymer substrate because it is easy to impart excellent orientation. Examples of the polymer compound constituting such a preferable polymer substrate include cellulose derivatives, polyolefin-based, polyester-based, polyethylene terephthalate, polycarbonate, polyacrylate-based, polyarylate, polyethersulfone, polyimide, polyphenylene sulfide, and polyphenylene ether. , Nylon, or polystyrene. Particularly preferred are cycloolefin polymer, triacetyl cellulose, and polymethyl methacrylate resin.
さらに、上記基材には、本発明の重合性液晶組成物を塗布乾燥した際に重合性液晶組成物が配向しやすいように、配向処理を施しておいても良い。配向処理としては基材を直接ラビング処理をする方法以外に、一般的な液晶デバイスに使用される配向膜を塗布して、ラビング処理を施しても良い。特に好ましい方法は、光配向膜を用いる公知手法であり、該光配向膜を用いるとパターン化された位相差膜が作製可能となる。 Further, the substrate may be subjected to an alignment treatment so that the polymerizable liquid crystal composition is easily aligned when the polymerizable liquid crystal composition of the present invention is applied and dried. As the alignment treatment, in addition to the method of directly rubbing the substrate, an alignment film used in a general liquid crystal device may be applied and the rubbing treatment may be performed. A particularly preferable method is a publicly known method using a photo-alignment film. When the photo-alignment film is used, a patterned retardation film can be produced.
以下では、前記「2官能化合物」に対して、下記一般式(X)で表される重合性化合物は「単官能化合物」と呼ぶことがある。
前記単官能化合物としては、例えば下記一般式(X)で表される重合性化合物が挙げられる。
Hereinafter, with respect to the “bifunctional compound”, the polymerizable compound represented by the following general formula (X) may be referred to as a “monofunctional compound”.
Examples of the monofunctional compound include polymerizable compounds represented by the following general formula (X).
<単官能化合物>
 本実施形態の重合性液晶組成物は、保存安定性を向上させ、重合させた時の配向性を向上させる観点から、下記一般式(X)で表される重合性化合物(単官能化合物)を1種以上含むことが好ましく、2種又は2種以上を含むことがより好ましい。
<Monofunctional compound>
The polymerizable liquid crystal composition of the present embodiment has a polymerizable compound (monofunctional compound) represented by the following general formula (X) from the viewpoint of improving storage stability and improving alignment when polymerized. It is preferable to include one or more types, and it is more preferable to include two or more types.
 本実施形態の重合性液晶組成物に、一般式(X)で表される単官能化合物を2種又は2種以上含有させる場合において、任意の2つの単官能化合物のmをそれぞれSAxとSBxとした場合に、1≦|SAx-SBx|≦3であり、かつ、3≦SAx+SBx≦10を満たすことが好ましい。 In the case where the polymerizable liquid crystal composition of this embodiment contains two or more monofunctional compounds represented by the general formula (X), m x of any two monofunctional compounds is respectively SAx and SBx. In this case, it is preferable that 1 ≦ | SAx−SBx | ≦ 3 and 3 ≦ SAx + SBx ≦ 10.
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
(一般式(X)中、Pは反応性官能基を表し、mは1~8の整数を表し、MGはメソゲン基又はメソゲン性支持基を表し、Rは水素原子、ハロゲン原子、シアノ基又は炭素原子数1~25のアルキル基を表すが、該アルキル基に結合する1つ以上の水素原子はハロゲン原子又はCNにより置換されていても良く、この基中に存在する1つのCH基又は隣接していない2つ以上のCH基はそれぞれ相互に独立して、酸素原子同士、硫黄原子同士及び酸素原子と硫黄原子とが相互に直接結合しない形で、-O-、-S-、-NH-、-N(CH)-、-CO-、-COO-、-OCO-、-OCOO-、-SCO-、-COS-、-CH=CH-、又は-C≡C-により置き換えられていても良い(ただし、Rが前記反応性官能基である場合を除く)。)
としては、炭素原子数1~8のアルキル基(この基中に存在する1つのCH基又は隣接していない2つ以上のCH基はそれぞれ相互に独立して、酸素原子同士が相互に直接結合しない形で、-O-、-CO-、-COO-、-OCO-、-OCOO-、-CH=CH-、又は-C≡C-により置き換えられていても良い)であることが好ましい。
(In the general formula (X), P x represents a reactive functional group, m x represents an integer of 1 to 8, MG represents a mesogenic group or a mesogenic supporting group, R 1 represents a hydrogen atom, a halogen atom, A cyano group or an alkyl group having 1 to 25 carbon atoms, wherein one or more hydrogen atoms bonded to the alkyl group may be substituted with a halogen atom or CN, and one CH present in the group; Two groups or two or more CH 2 groups that are not adjacent to each other are independently of each other in a form in which oxygen atoms, sulfur atoms, and oxygen atoms and sulfur atoms are not directly bonded to each other. S—, —NH—, —N (CH 3 ) —, —CO—, —COO—, —OCO—, —OCOO—, —SCO—, —COS—, —CH═CH—, or —C≡C. - may be replaced by (wherein, R 1 is the reactivity Except for the case of a functional group).)
R 1 is an alkyl group having 1 to 8 carbon atoms (one CH 2 group present in this group or two or more non-adjacent CH 2 groups are independently of each other, And may be replaced by —O—, —CO—, —COO—, —OCO—, —OCOO—, —CH═CH—, or —C≡C— in a form that is not directly bonded to each other. It is preferable.
一般式(X)中のPで表される反応性官能基としては、例えば、前記一般式(II-c)、(II-d)又は(II-e)で表される置換基からなる群より選択される置換基が挙げられる。 Examples of the reactive functional group represented by P x in the general formula (X) include a substituent represented by the general formula (II-c), (II-d), or (II-e). And substituents selected from the group.
一般式(X)中のMGで表されるメソゲン基又はメソゲン性支持基としては、例えば、前記一般式(II-b)におけるMGと同様の基が挙げられる。 Examples of the mesogenic group or mesogenic supporting group represented by MG in the general formula (X) include the same groups as MG in the general formula (II-b).
本実施形態の重合性液晶組成物は、一般式(X)で表される重合性化合物を2種以上含有してもよい。当該重合性液晶組成物に含まれる2種以上の一般式(X)で表される重合性化合物のうち、第一の重合性化合物を表す一般式(X)の「m」を「SA」と表し、第二の重合性化合物を表す一般式()の「m」を「SB」と表した場合、1≦|SA-SB|≦3であり、かつ、3≦SA+SB≦10を満たすことが好ましい。 The polymerizable liquid crystal composition of the present embodiment may contain two or more polymerizable compounds represented by the general formula (X). Of the polymerizable compounds represented by the general formula (X) contained in the polymerizable liquid crystal composition, “m x ” in the general formula (X) representing the first polymerizable compound is changed to “SA x. represents a ", if the formula representing the second polymerizable compound" m x "in (X) represented as" SB x ", 1 ≦ | SA x -SB x | a ≦ 3, and, 3 ≦ It is preferable that SA x + SB x ≦ 10 is satisfied.
本実施形態の重合性液晶組成物においては、一般式(X)で表される重合性化合物を2~4種含有することが好ましく、2~3種含有することがより好ましく、2種含有することが更に好ましい。一般式(X)で表される重合性化合物を3種又は4種を含有する場合は、それらの重合性化合物の任意の組み合わせのうち、何れかの組み合わせで、上記SAとSBの関係が成立していれば良い。 In the polymerizable liquid crystal composition of the present embodiment, it is preferable to contain 2 to 4 types of polymerizable compounds represented by the general formula (X), more preferably 2 to 3 types, and more preferably 2 types. More preferably. When three or four polymerizable compounds represented by the general formula (X) are contained, the relationship between SA and SB is established in any combination of the polymerizable compounds. If you do.
本実施形態の重合性液晶組成物が含有する、一般式(X)で表される2種以上の重合性化合物としては、下記一般式(X-1)~(X-4)及び下記一般式(X-31)~(X-32)で表される重合性化合物からなる群より選ばれる何れか2種以上の重合性化合物が好ましく、
下記一般式(X-1)で表される化合物を2種以上、下記一般式(X-2)で表される化合物を2種以上、下記一般式(X-3)で表される化合物を2種以上、下記一般式(X-4)で表される化合物を2種以上、下記一般式(X-31)で表される化合物を2種以上、又は、下記一般式(X-32)で表される化合物を2種以上、を含有することがより好ましい。
Examples of the two or more polymerizable compounds represented by the general formula (X) contained in the polymerizable liquid crystal composition of the present embodiment include the following general formulas (X-1) to (X-4) and the following general formulas: Any two or more polymerizable compounds selected from the group consisting of polymerizable compounds represented by (X-31) to (X-32) are preferred,
Two or more compounds represented by the following general formula (X-1), two or more compounds represented by the following general formula (X-2), and a compound represented by the following general formula (X-3) Two or more compounds, two or more compounds represented by the following general formula (X-4), two or more compounds represented by the following general formula (X-31), or the following general formula (X-32) It is more preferable that 2 or more types of compounds represented by these are contained.
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
 以下に、上記一般式(X-1)~(X-4)について説明する。
21、Y31、Y41、及びY51は、それぞれ独立して水素原子又はメチル基を表す。
21、E31、E41、及びE51は、それぞれ独立して、炭素原子数1~8のアルキレン基を表す。
21、Z22、Z31、Z32、Z41、Z42、Z51、及びZ52は、それぞれ独立して、-COO-、-OCO-、-C≡C-、-CH=CH-、-CH-CH-、-CH=CH-COO-、-OCO-CH=CH-、又は単結合を表す。
13~X24は、それぞれ独立して、水素原子、フッ素原子、塩素原子、メチル基、メトキシ基、CF基、又はOCF基を表すが、X13~X24のうち1~3個はフッ素原子、塩素原子、メチル基、メトキシ基、CF基、又はOCF基を表すことが好ましい。
25~X39は、それぞれ独立して、水素原子、フッ素原子、塩素原子、メチル基、メトキシ基、CF基、又はOCF基を表すが、X25~X39のうち1~3個はフッ素原子、塩素原子、メチル基、メトキシ基、CF基、又はOCF基を表すことが好ましい。
40~X53は、それぞれ独立して、水素原子、フッ素原子、塩素原子、メチル基、メトキシ基、CF基、又はOCF基を表すが、X40~X53のうち1~3個はフッ素原子、塩素原子、メチル基、メトキシ基、CF基、又はOCF基を表すことが好ましい。
54~X68は、それぞれ独立して、水素原子、フッ素原子、塩素原子、メチル基、メトキシ基、CF基、又はOCF基を表すが、X54~X68のうち1~3個はフッ素原子、塩素原子、メチル基、メトキシ基、CF基、又はOCF基を表すことが好ましい。
~Rは、それぞれ独立して、水素原子、フッ素原子、塩素原子、シアノ基、炭素原子数1~15のアルキル基を表し、該アルキル基中に存在する1個又は2個以上のメチレン基は、酸素原子が相互に直接結合しないものとして、酸素原子(-O-)、-CO-、-OCO-、-COO-、-C≡C-、又は-CH=CH-で置換されていてもよい(ただし、R~Rが前記反応性官能基である場合を除く)。
The general formulas (X-1) to (X-4) will be described below.
Y 21 , Y 31 , Y 41 , and Y 51 each independently represent a hydrogen atom or a methyl group.
E 21 , E 31 , E 41 , and E 51 each independently represent an alkylene group having 1 to 8 carbon atoms.
Z 21 , Z 22 , Z 31 , Z 32 , Z 41 , Z 42 , Z 51 , and Z 52 are each independently —COO—, —OCO—, —C≡C—, —CH═CH—. , —CH 2 —CH 2 —, —CH═CH—COO—, —OCO—CH═CH—, or a single bond.
X 13 to X 24 each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, a methoxy group, a CF 3 group, or an OCF 3 group, and 1 to 3 of X 13 to X 24 Preferably represents a fluorine atom, a chlorine atom, a methyl group, a methoxy group, a CF 3 group, or an OCF 3 group.
X 25 to X 39 each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, a methoxy group, a CF 3 group, or an OCF 3 group, and 1 to 3 of X 25 to X 39 Preferably represents a fluorine atom, a chlorine atom, a methyl group, a methoxy group, a CF 3 group, or an OCF 3 group.
X 40 to X 53 each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, a methoxy group, a CF 3 group, or an OCF 3 group, and 1 to 3 of X 40 to X 53 Preferably represents a fluorine atom, a chlorine atom, a methyl group, a methoxy group, a CF 3 group, or an OCF 3 group.
X 54 to X 68 each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, a methoxy group, a CF 3 group, or an OCF 3 group, and 1 to 3 of X 54 to X 68 Preferably represents a fluorine atom, a chlorine atom, a methyl group, a methoxy group, a CF 3 group, or an OCF 3 group.
R 2 to R 5 each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, or an alkyl group having 1 to 15 carbon atoms, and one or two or more present in the alkyl group The methylene group is substituted with an oxygen atom (—O—), —CO—, —OCO—, —COO—, —C≡C—, or —CH═CH—, assuming that the oxygen atoms are not directly bonded to each other. (Except when R 2 to R 5 are the reactive functional group).
 また、Z21、Z22、Z31、Z32、Z41、Z42、Z51、及びZ52は、それぞれ独立して単結合、-COO-、又は-OCO-であり、R~Rは、それぞれ独立して、炭素原子数1~10のアルキル基、又は炭素原子数1~10のアルコキシ基であることがより好ましい。 Z 21 , Z 22 , Z 31 , Z 32 , Z 41 , Z 42 , Z 51 , and Z 52 are each independently a single bond, —COO—, or —OCO—, and R 2 to R More preferably, each of 5 is independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.
 上記一般式(X-1)~(X-4)で表される重合性化合物のより好適な具体例として、下記一般式(X-5)~(X-21)で表される重合性化合物が挙げられる。 As more preferred specific examples of the polymerizable compounds represented by the general formulas (X-1) to (X-4), polymerizable compounds represented by the following general formulas (X-5) to (X-21) Is mentioned.
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
一般式(X-5)~(X-21)中、Y22は水素原子又はメチル基を表し、R21は炭素原子数1~10のアルキル基、又は炭素原子数1~10のアルコキシ基を表し、R23は水素原子、炭素原子数1~10のアルキル基、又は炭素原子数1~10のアルコキシ基を表し、R22はフッ素原子、塩素原子、メチル基、又はメトキシ基を表し、n21は1~8の整数を表す。 In the general formulas (X-5) to (X-21), Y 22 represents a hydrogen atom or a methyl group, R 21 represents an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. R 23 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, R 22 represents a fluorine atom, a chlorine atom, a methyl group, or a methoxy group, n 21 represents an integer of 1 to 8.
一般式(X-5)~(X-21)で表される重合性化合物のうち、一般式(X-5)、(X-7)、(X-10)、(X-12)、(X-14)及び(X-19)で表される化合物が好ましく、一般式(X-5)、(X-10)、(X-12)、(X-14)及び(X-19)で表される化合物がより好ましく、一般式(X-5)、(X-10)、及び(X-14)で表される化合物が更により好ましい。一般式(X-5)で表される化合物が最も好ましい。 Of the polymerizable compounds represented by the general formulas (X-5) to (X-21), the general formulas (X-5), (X-7), (X-10), (X-12), (X X-14) and (X-19) are preferred, and in general formulas (X-5), (X-10), (X-12), (X-14) and (X-19) The compounds represented by formulas (X-5), (X-10), and (X-14) are even more preferred. The compound represented by the general formula (X-5) is most preferable.
これらの重合性化合物のうち、より好ましい化合物としては、
一般式(X-5)において、R21及びR22がメチル基である化合物、
一般式(X-7)において、R21がメチル基、エチル基又はプロピル基であり、且つ、R22がメトキシ基又は塩素原子である化合物、
一般式(X-10)において、R21及びR22がメチル基である化合物、
一般式(X-12)において、R21がメチル基、エチル基又はプロピル基であり、且つ、R22がメトキシ基又は塩素原子である化合物、
一般式(X-14)において、R21及びR22がメチル基である化合物、並びに、
一般式(X-19)において、R21が水素原子、メチル基、エチル基又はプロピル基であり、且つ、R22がメトキシ基又は塩素原子である化合物が挙げられる。
Among these polymerizable compounds, as a more preferable compound,
In the general formula (X-5), compounds wherein R 21 and R 22 are methyl groups,
In the general formula (X-7), a compound wherein R 21 is a methyl group, an ethyl group or a propyl group, and R 22 is a methoxy group or a chlorine atom,
In the general formula (X-10), compounds wherein R 21 and R 22 are methyl groups,
In the general formula (X-12), a compound wherein R 21 is a methyl group, an ethyl group or a propyl group, and R 22 is a methoxy group or a chlorine atom,
In the general formula (X-14), a compound wherein R 21 and R 22 are methyl groups, and
In the general formula (X-19), a compound in which R 21 is a hydrogen atom, a methyl group, an ethyl group, or a propyl group, and R 22 is a methoxy group or a chlorine atom can be given.
これらの重合性化合物のうち、更に好ましい化合物としては、
一般式(X-5)において、R21及びR22がメチル基である化合物、
一般式(X-12)において、R21がメチル基であり、且つ、R22がメトキシ基である化合物、
一般式(X-14)において、R21及びR22がメチル基である化合物が挙げられる。
Among these polymerizable compounds, as a more preferable compound,
In the general formula (X-5), compounds wherein R 21 and R 22 are methyl groups,
In the general formula (X-12), a compound wherein R 21 is a methyl group and R 22 is a methoxy group,
In the general formula (X-14), compounds in which R 21 and R 22 are methyl groups can be given.
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
 以下に、上記一般式(X-31)~(X-32)について説明する。
61及びY71は、それぞれ独立して水素原子、又はメチル基を表す。
61及びE71は、それぞれ独立して、炭素原子数1~8のアルキレン基を表す。
61は、-COO-、-OCO-、又は単結合を表す。
62は、-C≡C-を表す。
71及びZ72は、それぞれ独立して、-COO-、-OCO-、又は単結合を表す。
The general formulas (X-31) to (X-32) will be described below.
Y 61 and Y 71 each independently represent a hydrogen atom or a methyl group.
E 61 and E 71 each independently represents an alkylene group having 1 to 8 carbon atoms.
Z 61 represents —COO—, —OCO—, or a single bond.
Z 62 represents —C≡C—.
Z 71 and Z 72 each independently represent —COO—, —OCO—, or a single bond.
71~X82は、それぞれ独立して、水素原子、フッ素原子、塩素原子、メチル基、メトキシ基、CF基、又はOCF基を表すが、X71~X82のうち1~3個はフッ素原子、塩素原子、メチル基、メトキシ基、CF基、又はOCF基を表すことが好ましい。
85~X96は、それぞれ独立して、水素原子、フッ素原子、塩素原子、メチル基、メトキシ基、CF基、又はOCF基を表す。
X 71 to X 82 each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, a methoxy group, a CF 3 group, or an OCF 3 group, and 1 to 3 of X 71 to X 82 Preferably represents a fluorine atom, a chlorine atom, a methyl group, a methoxy group, a CF 3 group, or an OCF 3 group.
X 85 to X 96 each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, a methoxy group, a CF 3 group, or an OCF 3 group.
~Rは、それぞれ独立して、水素原子、フッ素原子、塩素原子、シアノ基、炭素原子数1~15のアルキル基を表し、該アルキル基中に存在する1個又は2個以上のメチレン基は、酸素原子が相互に直接結合しないものとして、酸素原子(-O-)、-CO-、-OCO-、-COO-、又は-CH=CH-で置換されていてもよい(ただし、R~Rが前記反応性官能基である場合を除く)。 R 7 to R 8 each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, or an alkyl group having 1 to 15 carbon atoms, and one or two or more present in the alkyl group The methylene group may be substituted with an oxygen atom (—O—), —CO—, —OCO—, —COO—, or —CH═CH—, provided that the oxygen atoms are not directly bonded to each other (provided that R 7 to R 8 are the reactive functional groups).
 一般式(X-31)で表される重合性化合物のうち、Z61は-COO-又は-OCO-であり、Z62は-C≡C-であり、Rは炭素原子数1~10のアルキル基、又は炭素原子数1~10のアルコキシ基である化合物がより好ましい。 Among the polymerizable compounds represented by the general formula (X-31), Z 61 is —COO— or —OCO—, Z 62 is —C≡C—, and R 7 has 1 to 10 carbon atoms. Of these, a compound having an alkyl group or an alkoxy group having 1 to 10 carbon atoms is more preferred.
 一般式(X-32)で表される重合性化合物のうち、Z71は-COO-又は-OCO-であり、Z72は単結合であり、Rは炭素原子数1~10のアルキル基、又は炭素原子数1~10のアルコキシ基である化合物がより好ましい。 Among the polymerizable compounds represented by the general formula (X-32), Z 71 is —COO— or —OCO—, Z 72 is a single bond, and R 8 is an alkyl group having 1 to 10 carbon atoms. Or a compound which is an alkoxy group having 1 to 10 carbon atoms is more preferable.
 一般式(X-31)~(X-32)で表される重合性化合物のより好適な具体例として、下記一般式(X-33)~(X-44)で表される重合性化合物が挙げられる。 More preferred specific examples of the polymerizable compounds represented by the general formulas (X-31) to (X-32) include polymerizable compounds represented by the following general formulas (X-33) to (X-44). Can be mentioned.
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
一般式(X-33)~(X-44)中、Y62及びY72は水素原子又はメチル基を表し、R61及びR63は炭素原子数1~10のアルキル基又は炭素原子数1~10のアルコキシ基を表し、R62及びR64は、水素原子、フッ素原子、塩素原子、メチル基又はメトキシ基を表し、n61は1~8の整数を表す。 In the general formulas (X-33) to (X-44), Y 62 and Y 72 represent a hydrogen atom or a methyl group, and R 61 and R 63 represent an alkyl group having 1 to 10 carbon atoms or a carbon atom number of 1 to 10 represents an alkoxy group, R 62 and R 64 represent a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group or a methoxy group, and n 61 represents an integer of 1 to 8.
一般式(X-33)~(X-44)で表される重合性化合物のうち、一般式(X-33)、(X-34)、(X-39)及び(X-40)で表される化合物が好ましい。 Of the polymerizable compounds represented by the general formulas (X-33) to (X-44), those represented by the general formulas (X-33), (X-34), (X-39) and (X-40) Are preferred.
これらの重合性化合物のうち、より好ましい化合物としては、
一般式(X-33)及び(X-34)において、R61がメトキシ基又はエトキシ基であり、且つ、R62が塩素原子又はフッ素原子である化合物、
一般式(X-39)及び(X-40)において、R63が炭素原子数2~5の直鎖アルキル基であり、且つ、R64が水素原子又はメチル基である化合物が挙げられる。
Among these polymerizable compounds, as a more preferable compound,
In the general formulas (X-33) and (X-34), a compound in which R 61 is a methoxy group or an ethoxy group, and R 62 is a chlorine atom or a fluorine atom,
In the general formulas (X-39) and (X-40), compounds in which R 63 is a linear alkyl group having 2 to 5 carbon atoms and R 64 is a hydrogen atom or a methyl group can be mentioned.
これらの重合性化合物のうち、更に好ましい化合物としては、
一般式(X-33)において、R61がメトキシ基であり、且つ、R62が塩素原子である化合物、
一般式(X-39)において、R63がプロピル基であり、且つ、R64が水素原子である化合物が挙げられる。
Among these polymerizable compounds, as a more preferable compound,
In the general formula (X-33), a compound wherein R 61 is a methoxy group and R 62 is a chlorine atom,
In the general formula (X-39), a compound in which R 63 is a propyl group and R 64 is a hydrogen atom can be given.
 また、前記一般式(X)で表される重合性化合物としては、下記一般式(X-50)で表される化合物であることが好ましい。 The polymerizable compound represented by the general formula (X) is preferably a compound represented by the following general formula (X-50).
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
 一般式(X-50)中、Y82は水素原子又はメチル基を表し、n81は0~8の整数であり、n82は1又は2であり、Z83は-COO-、-OCO-、-C≡C-、又は単結合を表し、A83は1,4-フェニレン基、1,4-シクロヘキシレン基を表し、R83は炭素原子数1~5のアルキル基、又はアルコキシル基を表し、好ましくは、Z83は単結合、A83は1,4-フェニレン基、R83はシアノ基、メチル基、エチル基、又はメトキシ基である。
82が2でありZ83が複数存在する場合それらは同一であっても異なっていてもよく、A83が複数存在する場合それらは同一であっても異なっていてもよい。
一般式(X-50)の化合物は、粘度を下げたい場合に効果的な化合物である。しかし、あまり多く添加しすぎると配向性が悪化する。添加量としては、重合性化合物全体量を100質量%とした場合、0~30質量%であることが好ましく、0~10質量%であることがさらに好ましい。
In General Formula (X-50), Y 82 represents a hydrogen atom or a methyl group, n 81 is an integer of 0 to 8, n 82 is 1 or 2, and Z 83 is —COO— or —OCO—. , —C≡C—, or a single bond, A 83 represents a 1,4-phenylene group or a 1,4-cyclohexylene group, and R 83 represents an alkyl group having 1 to 5 carbon atoms or an alkoxyl group. Z 83 is preferably a single bond, A 83 is a 1,4-phenylene group, and R 83 is a cyano group, a methyl group, an ethyl group, or a methoxy group.
When n 82 is 2 and a plurality of Z 83 are present, they may be the same or different, and when a plurality of A 83 are present, they may be the same or different.
The compound of the general formula (X-50) is an effective compound when it is desired to reduce the viscosity. However, if too much is added, the orientation deteriorates. The addition amount is preferably 0 to 30% by mass, and more preferably 0 to 10% by mass, when the total amount of the polymerizable compound is 100% by mass.
 以上で例示したように、一般式(X)で表される重合性化合物が3つの環構造を有する場合、当該環構造のラテラル位の水素原子が置換基によって置換されていると、当該重合性化合物の溶媒に対する溶解性が向上し、本実施形態の重合性液晶組成物の保存安定性が向上するので好ましい。さらに、この保存安定性を一層向上させるためには、複数の重合性化合物同士の溶解性(相溶性)を高めることが好ましい。 As exemplified above, when the polymerizable compound represented by the general formula (X) has three ring structures, when the lateral hydrogen atom of the ring structure is substituted with a substituent, the polymerizable compound The solubility of the compound in the solvent is improved, and the storage stability of the polymerizable liquid crystal composition of this embodiment is improved, which is preferable. Furthermore, in order to further improve the storage stability, it is preferable to increase the solubility (compatibility) between a plurality of polymerizable compounds.
この相溶性を高める観点から、複数の重合性化合物の骨格構造を互いに近似させる又は同一にすることが好ましい。例えば、本実施形態の重合性液晶組成物は、一般式(X-5)で表される重合性化合物を2種又は2種以上含むこと、一般式(X-12)で表される重合性化合物を2種又は2種以上含むこと、一般式(X-14)で表される重合性化合物を2種又は2種以上含むこと、一般式(X-33)で表される重合性化合物を2種又は2種以上含むこと、或いは、一般式(X-39)で表される重合性化合物を2種又は2種以上含むこと、がより好ましい。 From the viewpoint of increasing the compatibility, it is preferable that the skeleton structures of the plurality of polymerizable compounds are approximated or the same. For example, the polymerizable liquid crystal composition of the present embodiment contains two or more polymerizable compounds represented by the general formula (X-5), and the polymerizable property represented by the general formula (X-12). A compound containing two or more compounds, two or more polymerizable compounds represented by general formula (X-14), and a polymerizable compound represented by general formula (X-33). It is more preferable to include two or more kinds, or to include two or more polymerizable compounds represented by the general formula (X-39).
 本実施形態の重合性液晶組成物に含有される重合性化合物(前述した2官能化合物を含む)の全重量を100重量部とした場合、一般式(X)で表される重合性化合物の合計の含有量は、5重量部以上70重量部未満が好ましく、5~50重量部がより好ましく、10~40重量部が更に好ましい。 When the total weight of the polymerizable compounds (including the bifunctional compound described above) contained in the polymerizable liquid crystal composition of the present embodiment is 100 parts by weight, the total of the polymerizable compounds represented by the general formula (X) The content of is preferably 5 parts by weight or more and less than 70 parts by weight, more preferably 5 to 50 parts by weight, still more preferably 10 to 40 parts by weight.
 本実施形態の重合性液晶組成物において、一般式(X)で表される重合性化合物を2種含む場合、重合性液晶組成物に含有される重合性化合物の全重量を100重量部として、一般式(X)で表される各重合性化合物の含有量は、5~70重量%が好ましく、5~50重量%がより好ましく、10~40重量%が更により好ましい。
これらの好ましい範囲の含有量であると、本実施形態の重合性液晶組成物の保存安定性がより向上する。
In the polymerizable liquid crystal composition of the present embodiment, when two kinds of polymerizable compounds represented by the general formula (X) are included, the total weight of the polymerizable compounds contained in the polymerizable liquid crystal composition is 100 parts by weight, The content of each polymerizable compound represented by the general formula (X) is preferably 5 to 70% by weight, more preferably 5 to 50% by weight, and still more preferably 10 to 40% by weight.
When the content is in these preferred ranges, the storage stability of the polymerizable liquid crystal composition of the present embodiment is further improved.
本実施形態の重合性液晶組成物において、一般式(X)で表される重合性化合物を2種含む場合、一般式(X)で表される第一の重合性化合物と第二の重合性化合物の含有量の差は、0~30重量部が好ましく、0~20重量部がより好ましく、0~10重量部がさらに好ましい。このように、2種の重合性化合物の含有量が均等であると、本実施形態の重合性液晶組成物の保存安定性がより向上する。 In the polymerizable liquid crystal composition of the present embodiment, when two kinds of polymerizable compounds represented by the general formula (X) are included, the first polymerizable compound represented by the general formula (X) and the second polymerizable compound. The difference in the compound content is preferably 0 to 30 parts by weight, more preferably 0 to 20 parts by weight, and still more preferably 0 to 10 parts by weight. Thus, the storage stability of the polymerizable liquid crystal composition of the present embodiment is further improved when the contents of the two polymerizable compounds are equal.
本実施形態の重合性液晶組成物の全重量に対して、一般式(I)で表される2官能化合物と一般式(X)で表される単官能化合物の合計の含有量は、5~50重量%が好ましく、10~40重量%がより好ましく、20~40重量%が更に好ましい。
これらの好適な範囲について、下限値は当該組成物の基材への塗工性を高める観点から定めており、上限値は当該組成物の保存安定性を高める観点から定めている。
The total content of the bifunctional compound represented by the general formula (I) and the monofunctional compound represented by the general formula (X) with respect to the total weight of the polymerizable liquid crystal composition of the present embodiment is 5 to 50 wt% is preferable, 10 to 40 wt% is more preferable, and 20 to 40 wt% is still more preferable.
About these suitable ranges, the lower limit is determined from the viewpoint of improving the coating property of the composition on the substrate, and the upper limit is determined from the viewpoint of increasing the storage stability of the composition.
本発明の重合性組成物溶液において、一般式(I)で表される2官能化合物以外に、重合性ディスコチック液晶化合物を含有することもできる。
本発明に使用する重合性ディスコチック液晶化合物としては、重合性官能基を1つ以上有することが好ましい。このような化合物としては、例えば、特開平7-281028号公報、特開平7-287120号公報、特開平7-333431号公報、特開兵8-27284号公報に記載されているような重合性ディスコチック液晶化合物が挙げられる。
重合性ディスコチック液晶化合物の配合量は、化合物によって適宜調整することができる。
The polymerizable composition solution of the present invention may contain a polymerizable discotic liquid crystal compound in addition to the bifunctional compound represented by the general formula (I).
The polymerizable discotic liquid crystal compound used in the present invention preferably has one or more polymerizable functional groups. Examples of such compounds include polymerizability as described in JP-A-7-281028, JP-A-7-287120, JP-A-7-333431, and JP-A-8-27284. Examples include discotic liquid crystal compounds.
The compounding quantity of a polymerizable discotic liquid crystal compound can be suitably adjusted with a compound.
重合性ディスコチック液晶化合物の一般式の一例として、一般式(4-1)~(4-3)を挙げることができるが、下記の一般式に限定されるわけではない。 Examples of the general formula of the polymerizable discotic liquid crystal compound include general formulas (4-1) to (4-3), but are not limited to the following general formula.
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
式中、Spは炭素原子数0~18のアルキレン基を表し、該アルキレン基は1つ以上のハロゲン原子、CN基、又は重合性官能基を有する炭素原子数1~8のアルキル基により置換されていても良く、この基中に存在する1つのCH2基又は隣接していない2つ以上のCH2基はそれぞれ相互に独立して、酸素原子が相互に直接結合しない形で、-O-、-S-、-NH-、-N(CH)-、-CO-、-COO-、-OCO-、-OCOO-、-SCO-、-COS-又は-C≡C-により置き換えられていても良く、
は1,4-フェニレン基、1,4-シクロヘキシレン基、1,4-シクロヘキセニル基、テトラヒドロピラン-2,5-ジイル基、1,3-ジオキサン-2,5-ジイル基、テトラヒドロチオピラン-2,5-ジイル基、1,4-ビシクロ(2,2,2)オクチレン基、デカヒドロナフタレン-2,6-ジイル基、ピリジン-2,5-ジイル基、ピリミジン-2,5-ジイル基、ピラジン-2,5-ジイル基、チオフェン-2,5-ジイル基-、1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基、2,6-ナフチレン基、フェナントレン-2,7-ジイル基、9,10-ジヒドロフェナントレン-2,7-ジイル基、1,2,3,4,4a,9,10a-オクタヒドロフェナントレン-2,7-ジイル基、1,4-ナフチレン基、ベンゾ[1,2-b:4,5-b‘]ジチオフェン-2,6-ジイル基、ベンゾ[1,2-b:4,5-b‘]ジセレノフェン-2,6-ジイル基、[1]ベンゾチエノ[3,2-b]チオフェン-2,7-ジイル基、[1]ベンゾセレノフェノ[3,2-b]セレノフェン-2,7-ジイル基、又はフルオレン-2,7-ジイル基を表し、
n5は0又は1を表し、
4aは、-CO-、-CH2 CH2-、-CH2O-、-CH=CH-、-CH=CHCOO-、-CH2CH2COO-、-CH2CH2OCO-、-COCH2CH2-、炭素数2~10のハロゲン原子を有してもよいアルキル基又は単結合を表し、
4bは-COO-、-OCO-、-OCH2-、-CH2O-、-CH=CH-、-C≡C-、-CH=CHCOO-、-OCOCH=CH-、-CH2CH2COO-、-CH2CH2OCO-、-COOCH2CH2-、-OCOCH2CH2-、-CONH-、-NHCO-、-OCOO-、炭素数2~10のハロゲン原子を有してもよいアルキル基又は単結合を表し、
は、水素原子、ハロゲン原子、シアノ基又は炭素原子数1~18のアルキル基を表すが、該アルキル基は1つ以上のハロゲン原子又はCNにより置換されていても良く、この基中に存在する1つのCH2基又は隣接していない2つ以上のCH2基はそれぞれ相互に独立して、酸素原子が相互に直接結合しない形で、-O-、-S-、-NH-、-N(CH)-、-CO-、-COO-、-OCO-、-OCOO-、-SCO-、-COS-又は-C≡C-により置き換えられていても良く、
あるいはRは一般式(4-a)
In the formula, Sp 4 represents an alkylene group having 0 to 18 carbon atoms, and the alkylene group is substituted with one or more halogen atoms, CN group, or an alkyl group having 1 to 8 carbon atoms having a polymerizable functional group. may be, independently each two or more CH 2 groups not one CH 2 group or adjacent present in this group to each other, in a manner that oxygen atoms are not directly bonded to each other, -O Replaced by —, —S—, —NH—, —N (CH 3 ) —, —CO—, —COO—, —OCO—, —OCOO—, —SCO—, —COS— or —C≡C—. You may,
A 4 represents 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, 1,3-dioxane-2,5-diyl group, tetrahydro Thiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2,6-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5 -Diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene- 2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a, 9,10a-octahydrophenanthrene-2,7-diyl group, 1,4- Naphthile Benzo [1,2-b: 4,5-b ′] dithiophene-2,6-diyl group, benzo [1,2-b: 4,5-b ′] diselenophen-2,6-diyl group [1] benzothieno [3,2-b] thiophene-2,7-diyl group, [1] benzoselenopheno [3,2-b] selenophene-2,7-diyl group, or fluorene-2,7- Represents a diyl group,
n5 represents 0 or 1,
Z 4a represents —CO—, —CH 2 CH 2 —, —CH 2 O—, —CH═CH—, —CH═CHCOO—, —CH 2 CH 2 COO—, —CH 2 CH 2 OCO—, — COCH 2 CH 2 — represents an alkyl group which may have a halogen atom having 2 to 10 carbon atoms or a single bond,
Z 4b is —COO—, —OCO—, —OCH 2 —, —CH 2 O—, —CH═CH—, —C≡C—, —CH═CHCOO—, —OCOCH═CH—, —CH 2 CH 2 COO -, - CH 2 CH 2 OCO -, - COOCH 2 CH 2 -, - OCOCH 2 CH 2 -, - CONH -, - NHCO -, - OCOO-, a halogen atom having 2 to 10 carbon atoms Represents a good alkyl group or a single bond,
R 6 represents a hydrogen atom, a halogen atom, a cyano group or an alkyl group having 1 to 18 carbon atoms, and the alkyl group may be substituted with one or more halogen atoms or CN, One CH 2 group present or two or more non-adjacent CH 2 groups are each independently of each other in a form in which oxygen atoms are not directly bonded to each other, —O—, —S—, —NH—, May be replaced by —N (CH 3 ) —, —CO—, —COO—, —OCO—, —OCOO—, —SCO—, —COS— or —C≡C—,
Or R 6 represents the general formula (4-a)
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
(式中、P4aは重合性官能基を表し、Sp3aはSpと同じ意味を表す。)
 P4aは、下記の式(P-1)から式(P-20)で表される重合性基から選ばれる置換基を表すのが好ましい。
(In the formula, P 4a represents a polymerizable functional group, and Sp 3a represents the same meaning as Sp 1 ).
P 4a preferably represents a substituent selected from the polymerizable groups represented by the following formulas (P-1) to (P-20).
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
 これらの重合性官能基のうち、重合性および保存安定性を高める観点から、式(P-1)又は式(P-2)、(P-7)、(P-12)、(P-13)が好ましく、式(P-1)、(P-7)、(P-12)がより好ましい。
重合性ディスコチック液晶化合物の具体的例としては、化合物(4-4)~(4-8)の化合物を挙げることができるが、下記の化合物に限定されるものではない。
Among these polymerizable functional groups, from the viewpoint of enhancing the polymerizability and storage stability, the formula (P-1) or the formulas (P-2), (P-7), (P-12), (P-13) ) Are preferred, and formulas (P-1), (P-7), and (P-12) are more preferred.
Specific examples of the polymerizable discotic liquid crystal compound include compounds (4-4) to (4-8), but are not limited to the following compounds.
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031
式中、qは1~18の整数を表す。 In the formula, q represents an integer of 1 to 18.
<有機溶媒>
 本実施形態の重合性液晶組成物を構成する有機溶媒は、一般式(I)を溶解可能であれば特に制限されないが、100℃以下の温度で揮発させて、当該組成物を乾燥できる溶媒であることが好ましく、用いる基材を侵食しないことが好ましい。そのような溶剤としては、例えば、トルエン、キシレン、クメン、メシチレン等の芳香族系炭化水素、酢酸メチル、酢酸エチル、酢酸プロピル、酢酸ブチル等のエステル系溶剤、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、シクロペンタノン等のケトン系溶剤、テトラヒドロフラン、1,2-ジメトキシエタン、アニソール等のエーテル系溶剤、N,N-ジメチルホルムアミド、N-メチル-2-ピロリドン等のアミド系溶剤、プロピレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノメチルエーテルアセテート、γ-ブチロラクトン、クロロベンゼン等が挙げられる。これらの有機溶媒は、1種を単独で使用することもできるし、2種類以上を混合して使用することもできる。
<Organic solvent>
The organic solvent constituting the polymerizable liquid crystal composition of the present embodiment is not particularly limited as long as it can dissolve the general formula (I), but is a solvent that can be evaporated at a temperature of 100 ° C. or lower and dried. It is preferable that it is present, and it is preferable that the substrate used is not eroded. Examples of such solvents include aromatic hydrocarbons such as toluene, xylene, cumene, and mesitylene, ester solvents such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclohexane, and the like. Ketone solvents such as pentanone, ether solvents such as tetrahydrofuran, 1,2-dimethoxyethane and anisole, amide solvents such as N, N-dimethylformamide and N-methyl-2-pyrrolidone, propylene glycol monomethyl ether acetate, Examples include diethylene glycol monomethyl ether acetate, γ-butyrolactone, and chlorobenzene. These organic solvents can be used alone or in combination of two or more.
例示した有機溶媒のうち、一般式(I)で表される重合性化合物の溶解性に優れ、当該組成物を重合させて得られる膜の配向性にも優れ、100℃以下で乾燥させ易いことから、トルエン、酢酸エチル、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、シクロペンタノン、プロピレングリコールモノメチルエーテルアセテート、及びN-メチル-2-ピロリドン及びこれらの組合せがより好ましい。 Among the exemplified organic solvents, the solubility of the polymerizable compound represented by the general formula (I) is excellent, the orientation of the film obtained by polymerizing the composition is also excellent, and it is easy to dry at 100 ° C. or less. More preferred are toluene, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether acetate, and N-methyl-2-pyrrolidone and combinations thereof.
 本実施形態の重合性液晶組成物の全重量に対する有機溶媒の含有量は、当該組成物を基材に塗布し易くなる含有量であることが好ましく、例えば40~90重量%であることがより好ましく、50~80重量%であることが更に好ましい。 The content of the organic solvent relative to the total weight of the polymerizable liquid crystal composition of the present embodiment is preferably a content that facilitates application of the composition to a substrate, for example, 40 to 90% by weight. Preferably, it is 50 to 80% by weight.
<重合開始剤>
本実施形態の重合性液晶組成物は、重合開始剤を少なくとも1種類以上含有することが好ましい。
 重合開始剤は、重合性液晶組成物を効率よく重合させるために有用な化合物である。重合開始剤としては、光重合開始剤が好ましく、具体的には以下の化合物が好ましい。
BASF社製のイルガキュア651、イルガキュア184、イルガキュア907、イルガキュア127、イルガキュア369、イルガキュア379、イルガキュア819、イルガキュアOXE01、イルガキュアOXE02、ルシリンTPO、ダロキュア1173。LAMBSON社製のエサキュア1001M、エサキュアKIP150、スピードキュアBEM、スピードキュアBMS、スピードキュアPBZ、ベンゾフェノン。
 これらの重合開始剤は、1種類を単独で使用しても良いが、2種類以上を併用しても良く、更に増感剤等を添加しても良い。
 本実施形態の重合性液晶組成物の全重量に対する重合開始剤の含有量は、例えば0.1~10重量%が好ましく、1~7重量%がより好ましく、3~7重量%が更により好ましい。
<Polymerization initiator>
The polymerizable liquid crystal composition of the present embodiment preferably contains at least one polymerization initiator.
The polymerization initiator is a useful compound for efficiently polymerizing the polymerizable liquid crystal composition. As the polymerization initiator, a photopolymerization initiator is preferable, and specifically, the following compounds are preferable.
Irgacure 651, Irgacure 184, Irgacure 907, Irgacure 127, Irgacure 369, Irgacure 379, Irgacure 819, Irgacure OXE01, Irgacure OXE02, Lucyrin TPO, Darocur 1173 manufactured by BASF. LAMBSON's Esacure 1001M, Esacure KIP150, Speed Cure BEM, Speed Cure BMS, Speed Cure PBZ, Benzophenone.
These polymerization initiators may be used alone or in combination of two or more, and a sensitizer or the like may be added.
The content of the polymerization initiator with respect to the total weight of the polymerizable liquid crystal composition of the present embodiment is, for example, preferably 0.1 to 10% by weight, more preferably 1 to 7% by weight, and still more preferably 3 to 7% by weight. .
<界面活性剤等>
 本実施形態の重合性液晶組成物は、界面活性剤、又は下記一般式(3)で表される繰り返し単位を有する重量平均分子量が100以上である化合物を含有することが好ましい。
<Surfactants>
The polymerizable liquid crystal composition of this embodiment preferably contains a surfactant or a compound having a repeating unit represented by the following general formula (3) and having a weight average molecular weight of 100 or more.
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000032
(式中、R11、R12、R13及びR14はそれぞれ独立的に水素原子、ハロゲン原子又は炭素原子数1~20の炭化水素基を表し、該炭化水素基中の1つ以上の水素原子はハロゲン原子で置換されていても良い。)
 前記界面活性剤および前記一般式(3)で表される化合物は、空気界面での液晶化合物のチルト角を減じる効果を付与する。前記界面活性剤としては、アルキルカルボン酸塩、アルキルリン酸塩、アルキルスルホン酸塩、フルオロアルキルカルボン酸塩、フルオロアルキルリン酸塩、フルオロアルキルスルホン酸塩、ポリオキシエチレン誘導体、フルオロアルキルエチレンオキシド誘導体、ポリエチレングリコール誘導体、アルキルアンモニウム塩、フルオロアルキルアンモニウム塩類、シリコーン誘導体等が挙げられる。これらのうち、特に含フッ素界面活性剤及びシリコーン誘導体が好ましい。
(Wherein R 11 , R 12 , R 13 and R 14 each independently represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and one or more hydrogen atoms in the hydrocarbon group) The atom may be substituted with a halogen atom.)
The surfactant and the compound represented by the general formula (3) impart an effect of reducing the tilt angle of the liquid crystal compound at the air interface. Examples of the surfactant include alkyl carboxylates, alkyl phosphates, alkyl sulfonates, fluoroalkyl carboxylates, fluoroalkyl phosphates, fluoroalkyl sulfonates, polyoxyethylene derivatives, fluoroalkylethylene oxide derivatives, Examples include polyethylene glycol derivatives, alkyl ammonium salts, fluoroalkyl ammonium salts, silicone derivatives, and the like. Of these, fluorine-containing surfactants and silicone derivatives are particularly preferable.
更に具体的には「MEGAFAC F-110」、「MEGAFACF-113」、「MEGAFAC F-120」、「MEGAFAC F-812」、「MEGAFAC F-142D」、「MEGAFAC F-144D」、「MEGAFAC F-150」、「MEGAFAC F-171」、「MEGAFACF-173」、「MEGAFAC F-177」、「MEGAFAC F-183」、「MEGAFAC F-195」、「MEGAFAC F-824」、「MEGAFAC F-833」、「MEGAFAC F-114」、「MEGAFAC F-410」、「MEGAFAC F-493」、「MEGAFAC F-494」、「MEGAFAC F-443」、「MEGAFAC F-444」、「MEGAFAC F-445」、「MEGAFAC F-446」、「MEGAFAC F-470」、「MEGAFAC F-471」、「MEGAFAC F-474」、「MEGAFAC F-475」、「MEGAFAC F-477」、「MEGAFAC F-478」、「MEGAFAC F-479」、「MEGAFAC F-480SF」、「MEGAFAC F-482」、「MEGAFAC F-483」、「MEGAFAC F-484」、「MEGAFAC F-486」、「MEGAFAC F-487」、「MEGAFAC F-489」、「MEGAFAC F-172D」、「MEGAFAC F-178K」、「MEGAFAC F-178RM」、「MEGAFAC R-08」、「MEGAFAC R-30」、「MEGAFAC F-472SF」、「MEGAFAC BL-20」、「MEGAFAC R-61」、「MEGAFAC R-90」、「MEGAFAC ESM-1」、「MEGAFAC MCF-350SF」(以上、DIC株式会社製)、
「フタージェント100」、「フタージェント100C」、「フタージェント110」、「フタージェント150」、「フタージェント150CH」、「フタージェントA」、「フタージェント100A-K」、「フタージェント501」、「フタージェント300」、「フタージェント310」、「フタージェント320」、「フタージェント400SW」、「FTX-400P」、「フタージェント251」、「フタージェント215M」、「フタージェント212MH」、「フタージェント250」、「フタージェント222F」、「フタージェント212D」、「FTX-218」、「FTX-209F」、「FTX-213F」、「FTX-233F」、「フタージェント245F」、「FTX-208G」、「FTX-240G」、「FTX-206D」、「FTX-220D」、「FTX-230D」、「FTX-240D」、「FTX-207S」、「FTX-211S」、「FTX-220S」、「FTX-230S」、「FTX-750FM」、「FTX-730FM」、「FTX-730FL」、「FTX-710FS」、「FTX-710FM」、「FTX-710FL」、「FTX-750LL」、「FTX-730LS」、「FTX-730LM」、「FTX-730LL」、「FTX-710LL」(以上、ネオス社製)、
「BYK-300」、「BYK-302」、「BYK-306」、「BYK-307」、「BYK-310」、「BYK-315」、「BYK-320」、「BYK-322」、「BYK-323」、「BYK-325」、「BYK-330」、「BYK-331」、「BYK-333」、「BYK-337」、「BYK-340」、「BYK-344」、「BYK-370」、「BYK-375」、「BYK-377」、「BYK-350」、「BYK-352」、「BYK-354」、「BYK-355」、「BYK-356」、「BYK-358N」、「BYK-361N」、「BYK-357」、「BYK-390」、「BYK-392」、「BYK-UV3500」、「BYK-UV3510」、「BYK-UV3570」、「BYK-Silclean3700」(以上、ビックケミー・ジャパン社製)、
「TEGO Rad2100」、「TEGO Rad2200N」、「TEGO Rad2250」、「TEGO Rad2300」、「TEGO Rad2500」、「TEGO Rad2600」、「TEGO Rad2700」(以上、テゴ社製)等の例を挙げることができる。
More specifically, “MEGAFAC F-110”, “MEGAFACCF-113”, “MEGAFAC F-120”, “MEGAFAC F-812”, “MEGAFAC F-142D”, “MEGAFAC F-144D”, “MEGAFAC F-” 150 "," MEGAFAC F-171 "," MEGAFACF-173 "," MEGAFAC F-177 "," MEGAFAC F-183 "," MEGAFAC F-195 "," MEGAFAC F-824 "," MEGAFAC F-833 " , “MEGAFAC F-114”, “MEGAFAC F-410”, “MEGAFAC F-493”, “MEGAFAC F-494”, “MEGAFAC F-443”, “MEGAFAC F-444”, “MEGAFAC F-445”, "ME “GAFAC F-446”, “MEGAFAC F-470”, “MEGAFAC F-471”, “MEGAFAC F-474”, “MEGAFAC F-475”, “MEGAFAC F-477”, “MEGAFAC F-478”, “MEGAFAC” F-479, MEGAFAC F-480SF, MEGAFAC F-482, MEGAFAC F-484, MEGAFAC F-484, MEGAFAC F-486, MEGAFAC F-487, MEGAFAC F -489, MEGAFAC F-172D, MEGAFAC F-178K, MEGAFAC F-178RM, MEGAFAC R-08, MEGAFAC R-30, MEGAFAC F-472SF, MEGAFAC “BL-20”, “MEGAFAC R-61”, “MEGAFAC R-90”, “MEGAFAC ESM-1”, “MEGAFAC MCF-350SF” (manufactured by DIC Corporation),
“Furgent 100”, “Furgent 100C”, “Furgent 110”, “Furgent 150”, “Furgent 150CH”, “Furgent A”, “Furgent 100A-K”, “Furgent 501”, "Factent 300", "Factent 310", "Factent 320", "Factent 400SW", "FTX-400P", "Factent 251", "Factent 215M", "Factent 212MH", "Footer Gent 250, Fategent 222F, Fategent 212D, FTX-218, FTX-209F, FTX-213F, FTX-233F, Fate 245F, FTX-208G ”,“ FTX-240G ”,“ FT -206D "," FTX-220D "," FTX-230D "," FTX-240D "," FTX-207S "," FTX-211S "," FTX-220S "," FTX-230S "," FTX-750FM " ”,“ FTX-730FM ”,“ FTX-730FL ”,“ FTX-710FS ”,“ FTX-710FM ”,“ FTX-710FL ”,“ FTX-750LL ”,“ FTX-730LS ”,“ FTX-730LM ”, "FTX-730LL", "FTX-710LL" (above, manufactured by Neos),
“BYK-300”, “BYK-302”, “BYK-306”, “BYK-307”, “BYK-310”, “BYK-315”, “BYK-320”, “BYK-322”, “BYK” -323 "," BYK-325 "," BYK-330 "," BYK-331 "," BYK-333 "," BYK-337 "," BYK-340 "," BYK-344 "," BYK-370 " ”,“ BYK-375 ”,“ BYK-377 ”,“ BYK-350 ”,“ BYK-352 ”,“ BYK-354 ”,“ BYK-355 ”,“ BYK-356 ”,“ BYK-358N ”, “BYK-361N”, “BYK-357”, “BYK-390”, “BYK-392”, “BYK-UV3500”, “BYK-UV3510”, “BYK-UV3570”, “B K-Silclean3700 "(manufactured by BYK Japan KK),
Examples include “TEGO Rad2100”, “TEGO Rad2200N”, “TEGO Rad2250”, “TEGO Rad2300”, “TEGO Rad2500”, “TEGO Rad2600”, “TEGO Rad2700” (manufactured by TEGO).
 前記一般式(3)で表される化合物の重量平均分子量は200~100000であることが好ましく、300~10000であることがより好ましく、500~5000であることが更に好ましい。 The weight average molecular weight of the compound represented by the general formula (3) is preferably 200 to 100,000, more preferably 300 to 10,000, and further preferably 500 to 5,000.
 前記界面活性剤、及び前記一般式(3)で表される化合物は、それぞれ1種単独で使用してもよいし、2種以上を併用してもよい。また、前記界面活性剤と前記一般式(3)で表される化合物とを組み合わせて用いてもよい。 The surfactant and the compound represented by the general formula (3) may be used singly or in combination of two or more. Moreover, you may use combining the said surfactant and the compound represented by the said General formula (3).
 本実施形態の重合性液晶組成物の全重量に対する、前記界面活性剤及び前記一般式(3)で表される化合物の合計の含有量は、0.01~1重量%であることが好ましく、0.05~0.6重量%であることがより好ましい。 The total content of the surfactant and the compound represented by the general formula (3) with respect to the total weight of the polymerizable liquid crystal composition of the present embodiment is preferably 0.01 to 1% by weight, More preferably, it is 0.05 to 0.6% by weight.
<その他の成分>
 本実施形態の重合性液晶組成物には、その他の成分として、基材との密着性をより向上させるため、連鎖移動剤を添加することが好ましい。連鎖移動剤としては、チオール化合物が好ましく、モノチオール、ジチオール、トリチオール、テトラチオール化合物がより好ましく、トリチオール化合物が更により好ましい。具体的には下記一般式(5-1)~(5-12)で表される化合物が好ましい。
これらのチオール化合物の含有量としては、当該組成物の全重量に対して、0.5~5.0重量%であることが好ましく、1.0~3.0重量%であることがより好ましい。
<Other ingredients>
A chain transfer agent is preferably added to the polymerizable liquid crystal composition of the present embodiment as another component in order to further improve the adhesion to the substrate. The chain transfer agent is preferably a thiol compound, more preferably a monothiol, dithiol, trithiol, or tetrathiol compound, and even more preferably a trithiol compound. Specifically, compounds represented by the following general formulas (5-1) to (5-12) are preferable.
The content of these thiol compounds is preferably 0.5 to 5.0% by weight, more preferably 1.0 to 3.0% by weight, based on the total weight of the composition. .
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000034
(式中、R65は炭素原子数2~18のアルキル基を表し、該アルキル基は直鎖であっても分岐鎖であっても良く、該アルキル基中の1つ以上のメチレン基は酸素原子、及び硫黄原子が相互に直接結合しないものとして、酸素原子、硫黄原子、-CO-、-OCO-、-COO-、又は-CH=CH-で置換されていてもよく、R66は炭素原子数2~18のアルキレン基を表し、該アルキレン基中の1つ以上のメチレン基は酸素原子、及び硫黄原子が相互に直接結合しないものとして、酸素原子、硫黄原子、-CO-、-OCO-、-COO-、又は-CH=CH-で置換されていてもよい。) Wherein R 65 represents an alkyl group having 2 to 18 carbon atoms, and the alkyl group may be linear or branched, and one or more methylene groups in the alkyl group are oxygen atoms, and assuming that the sulfur atoms are not linked directly to one another, an oxygen atom, a sulfur atom, -CO -, - OCO -, - COO-, or -CH = CH- may be substituted by, R 66 is a carbon Represents an alkylene group having 2 to 18 atoms, and one or more methylene groups in the alkylene group are oxygen atoms, sulfur atoms, —CO—, —OCO on the assumption that an oxygen atom and a sulfur atom are not directly bonded to each other. It may be substituted with —, —COO—, or —CH═CH—.
 本実施形態の重合性液晶組成物には、保存安定性を高めるために、重合禁止剤、酸化防止剤等を添加することが好ましい。そのような化合物として、ヒドロキノン誘導体、ヒンダードフェノール系酸化防止剤等が挙げられる。より具体的には、p-メトキシフェノール、BASF社のIRGANOX1010、IRGANOX1035、IRGANOX1076、IRGANOX1098、IRGANOX1135、IRGANOX1330、IRGANOX1425、IRGANOX1520、IRGANOX1726、IRGANOX245、IRGANOX259、IRGANOX3114、IRGANOX3790、IRGANOX5057、IRGANOX565等々が挙げられる。 In the polymerizable liquid crystal composition of the present embodiment, it is preferable to add a polymerization inhibitor, an antioxidant or the like in order to improve storage stability. Examples of such compounds include hydroquinone derivatives and hindered phenol antioxidants. More specifically, p-methoxyphenol, IRGANOX1010, IRGANOX1035, IRGANOX1076, IRGANOX1098, IRGANOX1135, IRGANOX1325, IRGANOX1520, IRGANOX2457, IRGANOX3957, IRGANOX3590, IRGANOX3590, IRGANOX3590, IRGANOX3590
 上記重合禁止剤及び酸化防止剤の含有量としては、当該組成物の全重量に対して、0.01~1.0質量%であることが好ましく、0.05~0.2質量%であることがより好ましい。 The content of the polymerization inhibitor and the antioxidant is preferably 0.01 to 1.0% by mass, and 0.05 to 0.2% by mass with respect to the total weight of the composition. It is more preferable.
 更に、本実施形態の重合性液晶組成物の物性を調整するために、重合性でない液晶化合物、或いは、液晶性でない重合性化合物等も必要に応じて添加することも可能である。
これらの化合物の含有量としては、当該組成物の全重量に対して、20重量%以下が好ましく、10重量%以下がより好ましく、5重量%以下が更に好ましい。
Furthermore, in order to adjust the physical properties of the polymerizable liquid crystal composition of the present embodiment, a non-polymerizable liquid crystal compound, a non-liquid crystal polymerizable compound, or the like can be added as necessary.
The content of these compounds is preferably 20% by weight or less, more preferably 10% by weight or less, and still more preferably 5% by weight or less based on the total weight of the composition.
(光学異方体の製造方法)
(光学異方体)
 本発明の光学異方体は、基材、必要に応じて配向膜、及び、重合性組成物溶液の重合体を順次積層したものである。あるいは、基材、必要に応じて配向膜、及び、重合性組成物溶液の重合対を順次積層し、その上に必要に応じて配向膜、及び、前記又は前記と異なってもよい重合性組成物溶液を順次積層したものである。さらにその上に必要に応じて配向膜、及び、前記又は前記と異なってもよい重合性組成物溶液を順次積層することもできる。
 本発明の光学異方体に用いられる基材は、液晶デバイス、ディスプレイ、光学素子、光学部品、着色剤、セキュリティ用マーキング、レーザー発光用部材、及び、光学フィルムに通常使用する基材であって、本発明の重合性組成物溶液の塗布後の乾燥時における加熱に耐えうる耐熱性を有する材料であれば、特に制限はない。そのような基材としては、ガラス基材、金属基材、セラミックス基材やプラスチック基材等の有機材料が挙げられる。特に基材が有機材料の場合、セルロース誘導体、ポリオレフィン、ポリエステル、ポリオレフィン、ポリカーボネート、ポリアクリレート、ポリアリレート、ポリエーテルサルホン、ポリイミド、ポリフェニレンスルフィド、ポリフェニレンエーテル、ナイロン又はポリスチレン等が挙げられる。中でもポリエステル、ポリスチレン、ポリオレフィン、セルロース誘導体、ポリアリレート、ポリカーボネート等のプラスチック基材が好ましい。
 本発明の重合性組成物溶液の塗布性や接着性向上のために、これらの基材の表面処理を行っても良い。表面処理として、オゾン処理、プラズマ処理、コロナ処理、シランカップリング処理などが挙げられる。また、光の透過率や反射率を調節するために、基材表面に有機薄膜、無機酸化物薄膜や金属薄膜等を蒸着など方法によって設ける、あるいは、光学的な付加価値をつけるために、基材がピックアップレンズ、ロッドレンズ、光ディスク、位相差フィルム、光拡散フィルム、カラーフィルター、等であっても良い。中でも付加価値がより高くなるピックアップレンズ、位相差フィルム、光拡散フィルム、カラーフィルターは好ましい。
(Optical anisotropic body manufacturing method)
(Optical anisotropic)
The optical anisotropic body of the present invention is obtained by sequentially laminating a base material, an orientation film as necessary, and a polymer of a polymerizable composition solution. Alternatively, a base material, an orientation film as necessary, and a polymerization composition solution of a polymerizable composition solution are sequentially laminated, and an orientation film and a polymerizable composition that may be different from the above or above as necessary. A product solution is sequentially laminated. Furthermore, an alignment film and a polymerizable composition solution that may be different from the above or the above may be sequentially laminated thereon as necessary.
The base material used for the optical anisotropic body of the present invention is a base material usually used for liquid crystal devices, displays, optical elements, optical components, colorants, security markings, laser emission members, and optical films. The material is not particularly limited as long as it is a material having heat resistance capable of withstanding heating during drying after the application of the polymerizable composition solution of the present invention. Examples of such a substrate include organic materials such as a glass substrate, a metal substrate, a ceramic substrate, and a plastic substrate. In particular, when the substrate is an organic material, examples thereof include cellulose derivatives, polyolefins, polyesters, polyolefins, polycarbonates, polyacrylates, polyarylates, polyether sulfones, polyimides, polyphenylene sulfides, polyphenylene ethers, nylons, and polystyrenes. Of these, plastic substrates such as polyester, polystyrene, polyolefin, cellulose derivatives, polyarylate, and polycarbonate are preferable.
In order to improve the applicability and adhesion of the polymerizable composition solution of the present invention, surface treatment of these substrates may be performed. Examples of the surface treatment include ozone treatment, plasma treatment, corona treatment, silane coupling treatment, and the like. In addition, in order to adjust the light transmittance and reflectance, an organic thin film, an inorganic oxide thin film, a metal thin film, etc. are provided on the surface of the substrate by a method such as vapor deposition, or in order to add optical added value. The material may be a pickup lens, a rod lens, an optical disk, a retardation film, a light diffusion film, a color filter, or the like. Among these, a pickup lens, a retardation film, a light diffusion film, and a color filter that have higher added value are preferable.
 また、上記基材には、本発明の重合性組成物溶液を塗布乾燥した際に重合性組成物が配向するように、通常配向処理が施されている、あるいは配向膜が設けられていても良い。配向処理としては、延伸処理、ラビング処理、偏光紫外可視光照射処理、イオンビーム処理等が挙げられる。配向膜を用いる場合、配向膜は公知慣用のものが用いられる。そのような配向膜としては、ポリイミド、ポリシロキサン、ポリアミド、ポリビニルアルコール、ポリカーボネート、ポリスチレン、ポリフェニレンエーテル、ポリアリレート、ポリエチレンテレフタレート、ポリエーテルサルホン、エポキシ樹脂、エポキシアクリレート樹脂、アクリル樹脂、クマリン化合物、カルコン化合物、シンナメート化合物、フルギド化合物、アントラキノン化合物、アゾ化合物、アリールエテン化合物等の化合物が挙げられる。ラビングにより配向処理する化合物は、配向処理、もしくは配向処理の後に加熱工程を入れることで材料の結晶化が促進されるものが好ましい。ラビング以外の配向処理を行う化合物の中では光配向材料を用いることが好ましい。 Moreover, even if the said base material is normally orientated or the orientation film | membrane is provided so that polymeric composition may orientate when the polymeric composition solution of this invention is apply | coated and dried. good. Examples of the alignment treatment include stretching treatment, rubbing treatment, polarized ultraviolet visible light irradiation treatment, ion beam treatment, and the like. When the alignment film is used, a known and conventional alignment film is used. Such alignment films include polyimide, polysiloxane, polyamide, polyvinyl alcohol, polycarbonate, polystyrene, polyphenylene ether, polyarylate, polyethylene terephthalate, polyether sulfone, epoxy resin, epoxy acrylate resin, acrylic resin, coumarin compound, chalcone. Examples of the compound include compounds, cinnamate compounds, fulgide compounds, anthraquinone compounds, azo compounds, and arylethene compounds. The compound subjected to the alignment treatment by rubbing is preferably an alignment treatment or a compound in which crystallization of the material is promoted by inserting a heating step after the alignment treatment. Among the compounds that perform alignment treatment other than rubbing, it is preferable to use a photo-alignment material.
(塗布)
 本発明の光学異方体を得るための塗布法としては、アプリケーター法、バーコーティング法、スピンコーティング法、グラビア印刷法、フレキソ印刷法、インクジェット法、ダイコーティング法、キャップコーティング法、ディッピング等、公知慣用の方法を行うことができる。重合性組成物溶液を塗布後、乾燥させる。
(Application)
As an application method for obtaining the optical anisotropic body of the present invention, an applicator method, a bar coating method, a spin coating method, a gravure printing method, a flexographic printing method, an ink jet method, a die coating method, a cap coating method, dipping, etc. are known. Conventional methods can be performed. The polymerizable composition solution is applied and then dried.
(重合工程)
 乾燥した重合性組成物の重合処理は、該重合性組成物中の一般式(1)で表される重合性化合物がプレーナー配向した状態で一般に紫外線等の光照射、あるいは加熱によって行われる。重合を光照射で行う場合は、具体的には390nm以下の紫外光を照射することが好ましく、250~370nmの波長の光を照射することが最も好ましい。但し、390nm以下の紫外光により重合性組成物が分解などを引き起こす場合は、390nm以上の紫外光で重合処理を行ったほうが好ましい場合もある。この光は、拡散光で、かつ偏光していない光であることが好ましい。
(Polymerization process)
The polymerization treatment of the dried polymerizable composition is generally performed by irradiation with light such as ultraviolet rays or heating in a state where the polymerizable compound represented by the general formula (1) in the polymerizable composition is planarly aligned. When the polymerization is performed by light irradiation, specifically, it is preferable to irradiate ultraviolet light having a wavelength of 390 nm or less, and most preferable to irradiate light having a wavelength of 250 to 370 nm. However, when the polymerizable composition causes decomposition or the like due to ultraviolet light of 390 nm or less, it may be preferable to perform polymerization treatment with ultraviolet light of 390 nm or more. This light is preferably diffused light and unpolarized light.
(位相差膜)
 本発明の位相差膜は、本発明の光学異方体と同様にして作成される。重合性組成物中の一般式(1)で表される重合性化合物がプレーナー配向した状態で重合した場合は、基材に対して面内に複屈折性を有する位相差膜が得られる。前記位相差膜は、ホモジニアス液晶フィルムとして使用することができる。重合性組成物中の一般式(1)で表される重合性化合物、及び、重合性キラル化合物がプレーナー配向した状態で重合した場合は、基材に対して面外に複屈折性を有する位相差膜が得られる。重合性ディスコチック化合物を含む重合性組成物中の一般式(1)で表される重合性化合物がプレーナー配向した状態で重合した場合は、基材に対して面内にも面外にも複屈折性を有する位相差膜が得られる。
 また、基材が位相差を有する場合には、基材の有する複屈折性、及び、本発明の位相差膜の複屈折性を加算した複屈折性を有する位相差膜が得られる。前記位相差膜は、基材の有する複屈折性と位相差膜の有する複屈折性が基材の面内で同じ方向の場合もあれば、異なる方向の場合もある。液晶デバイス、ディスプレイ、光学素子、光学部品、着色剤、セキュリティ用マーキング、レーザー発光用部材、光学フィルム、及び、補償フィルム等の用途に応じて、用途に適した形で適用される。
(Retardation film)
The retardation film of the present invention is prepared in the same manner as the optical anisotropic body of the present invention. When the polymerizable compound represented by the general formula (1) in the polymerizable composition is polymerized in a planar alignment state, a retardation film having in-plane birefringence with respect to the substrate is obtained. The retardation film can be used as a homogeneous liquid crystal film. When the polymerizable compound represented by the general formula (1) in the polymerizable composition and the polymerizable chiral compound are polymerized in a planar alignment state, the birefringence is out of plane with respect to the substrate. A phase difference film is obtained. When the polymerizable compound represented by the general formula (1) in the polymerizable composition containing a polymerizable discotic compound is polymerized in a planar orientation state, it is compounded both in-plane and out-of-plane with respect to the substrate. A retardation film having refractive properties can be obtained.
When the substrate has a retardation, a retardation film having birefringence obtained by adding the birefringence of the substrate and the birefringence of the retardation film of the present invention can be obtained. In the retardation film, the birefringence of the base material and the birefringence of the retardation film may be in the same direction or different directions in the plane of the base material. The liquid crystal device, the display, the optical element, the optical component, the colorant, the marking for security, the member for laser emission, the optical film, and the compensation film are applied in a form suitable for the application.
(位相差パターニング膜)
 本発明の位相差パターニング膜は、本発明の光学異方体同様に、基材、配向膜、及び、重合性組成物溶液の重合体を順次積層したものであるが、重合工程において、部分的に異なる位相差が得られるようにパターニングされたものである。パターニングは、線状のパターニング、格子状のパターニング、円状のパターニング、多角形状のパターニング等、異なる方向の場合もある。液晶デバイス、ディスプレイ、光学素子、光学部品、着色剤、セキュリティ用マーキング、レーザー発光用部材、光学フィルム、及び、補償フィルム等の用途に応じて、適用される。
部分的に異なる位相差を得る方法としては、基材に配向膜を設け、配向処理する際に本発明の重合性組成物溶液を塗布乾燥した際に重合性組成物がパターニング配向するように処理する。そのような配向処理は、微細ラビング処理、フォトマスクを介しての偏光紫外可視光照射処理、微細形状加工処理等が挙げられる。配向膜は、公知慣用のものが用いられる。そのような配向膜としては、ポリイミド、ポリシロキサン、ポリアミド、ポリビニルアルコール、ポリカーボネート、ポリスチレン、ポリフェニレンエーテル、ポリアリレート、ポリエチレンテレフタレート、ポリエーテルサルホン、エポキシ樹脂、エポキシアクリレート樹脂、アクリル樹脂、クマリン化合物、カルコン化合物、シンナメート化合物、フルギド化合物、アントラキノン化合物、アゾ化合物、アリールエテン化合物等の化合物が挙げられる。微細ラビングにより配向処理する化合物は、配向処理、もしくは配向処理の後に加熱工程を入れることで材料の結晶化が促進されるものが好ましい。ラビング以外の配向処理を行う化合物の中では光配向材料を用いることが好ましい。
(Phase difference patterning film)
The retardation patterning film of the present invention is obtained by sequentially laminating a base material, an alignment film, and a polymer of a polymerizable composition solution in the same manner as the optical anisotropic body of the present invention. Are patterned so as to obtain different phase differences. The patterning may be in different directions, such as linear patterning, lattice patterning, circular patterning, polygonal patterning, and the like. The liquid crystal device, display, optical element, optical component, colorant, security marking, laser emission member, optical film, compensation film, and the like are used.
As a method of obtaining a partially different phase difference, an alignment film is provided on the substrate, and the polymerizable composition solution of the present invention is applied and dried during the alignment treatment so that the polymerizable composition is patterned and aligned. To do. Examples of such an alignment treatment include a fine rubbing treatment, a polarized ultraviolet visible light irradiation treatment through a photomask, and a fine shape processing treatment. As the alignment film, known and conventional ones are used. Such alignment films include polyimide, polysiloxane, polyamide, polyvinyl alcohol, polycarbonate, polystyrene, polyphenylene ether, polyarylate, polyethylene terephthalate, polyether sulfone, epoxy resin, epoxy acrylate resin, acrylic resin, coumarin compound, chalcone. Examples of the compound include compounds, cinnamate compounds, fulgide compounds, anthraquinone compounds, azo compounds, and arylethene compounds. The compound subjected to the alignment treatment by fine rubbing is preferably an alignment treatment or a compound in which crystallization of the material is promoted by adding a heating step after the alignment treatment. Among the compounds that perform alignment treatment other than rubbing, it is preferable to use a photo-alignment material.
(ホモジニアス配向)
一方、重合性液晶化合物を適宜選択し、界面活性剤、又は一般式(3)で表される繰り返し単位を有する重量平均分子量が100以上である化合物の量を調整することで、ホモジニアス配向を達成することができる。
(Homogeneous orientation)
On the other hand, homogeneous alignment is achieved by appropriately selecting a polymerizable liquid crystal compound and adjusting the amount of the surfactant or the compound having a repeating unit represented by the general formula (3) and having a weight average molecular weight of 100 or more. can do.
 次に、実施例により本発明をさらに詳細に説明するが、本発明はこれらの例によって限定されるものではない。なお、特に断りのない限り、「部」及び「%」は質量基準である。 Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, “part” and “%” are based on mass.
 以下の表に示す割合で各化合物を混合したUCL組成物を調製した。UCL組成物30重量部と、各溶剤70重量部とを混合したUCL溶液に、さらに各添加剤を加えて、各実施例および比較例のサンプル溶液を調製した。 A UCL composition was prepared by mixing each compound at the ratio shown in the following table. Each additive was further added to the UCL solution in which 30 parts by weight of the UCL composition and 70 parts by weight of each solvent were mixed to prepare sample solutions for the examples and comparative examples.
<2官能化合物> <Bifunctional compound>
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000036
<単官能化合物> <Monofunctional compound>
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-T000039
Figure JPOXMLDOC01-appb-T000039
Figure JPOXMLDOC01-appb-T000040
Figure JPOXMLDOC01-appb-T000040
Figure JPOXMLDOC01-appb-T000041
Figure JPOXMLDOC01-appb-T000041
Figure JPOXMLDOC01-appb-T000042
Figure JPOXMLDOC01-appb-T000042
Figure JPOXMLDOC01-appb-T000043
Figure JPOXMLDOC01-appb-T000043
Figure JPOXMLDOC01-appb-T000044
Figure JPOXMLDOC01-appb-T000044
Figure JPOXMLDOC01-appb-T000045
Figure JPOXMLDOC01-appb-T000045
Figure JPOXMLDOC01-appb-T000046
Figure JPOXMLDOC01-appb-T000046
Figure JPOXMLDOC01-appb-T000047
Figure JPOXMLDOC01-appb-T000047
Figure JPOXMLDOC01-appb-T000048
Figure JPOXMLDOC01-appb-T000048
Figure JPOXMLDOC01-appb-T000049
Figure JPOXMLDOC01-appb-T000049
 各表のサンプル溶液に使用した溶剤および添加剤は以下の通りである。
MEK・・・メチルエチルケトン
PGMEA・・・プロピレングリコール1-モノメチルエーテル2-アセタート
NMP・・・N-メチルピロリドン
MIBK・・・メチルイソブチルケトン
MEHQ・・・p-メトキシフェノール
 Irg907・・・イルガキュア907
 N535・・・フッ素ゴム:TECNOFLON N535
The solvents and additives used for the sample solutions in each table are as follows.
MEK ... Methyl ethyl ketone PGMEA ... Propylene glycol 1-monomethyl ether 2-acetate NMP ... N-methylpyrrolidone MIBK ... Methyl isobutyl ketone MEHQ ... p-methoxyphenol Irg907 ... Irgacure 907
N535 ... Fluoro rubber: TECNOFLON N535
 <光配向膜の作製> <Production of photo-alignment film>
Figure JPOXMLDOC01-appb-C000050
Figure JPOXMLDOC01-appb-C000050
上記式(A)で表される化合物0.5重量部を2-(2-エトキシエトキシ)エタノール49.5重量部に溶解させた後、2-ブトキシエタノール49重量部を加えて、光配向膜用組成物Aの溶液を得た。この溶液を0.45μmのメンブランフィルターでろ過し、光配向膜用組成物(A-1)を得た。 After dissolving 0.5 parts by weight of the compound represented by the above formula (A) in 49.5 parts by weight of 2- (2-ethoxyethoxy) ethanol, 49 parts by weight of 2-butoxyethanol is added to form a photo-alignment film. A solution of composition A was obtained. This solution was filtered through a 0.45 μm membrane filter to obtain a composition (A-1) for photo-alignment films.
 光配向膜用組成物(A-1)をバーコーターで基材である80μmのトリアセチルセルロース誘導体からなるフィルム上に塗布し、80℃で2分間乾燥した。このときの乾燥膜厚は15nmであった。次に超高圧水銀ランプに波長カットフィルター、バンドパスフィルター、及び、偏光フィルターを介して、波長365nm付近の可視紫外光(照射強度:20mW/cm)の直線偏光の平行光を、基材に対して垂直方向から照射し、光配向膜を得た。照射量は100mJ/cmであった。 The composition for photo-alignment film (A-1) was applied onto a film made of an 80 μm triacetyl cellulose derivative as a base material with a bar coater and dried at 80 ° C. for 2 minutes. The dry film thickness at this time was 15 nm. Next, the ultra-high pressure mercury lamp is passed through a wavelength cut filter, a band-pass filter, and a polarizing filter, and visible ultraviolet light having a wavelength of around 365 nm (irradiation intensity: 20 mW / cm 2 ) is applied to the substrate as linearly polarized parallel light. On the other hand, the photo-alignment film was obtained by irradiating from the vertical direction. The irradiation amount was 100 mJ / cm 2 .
 <位相差膜の作製>
作製した光配向膜上に、実施例又は比較例のUCLサンプル溶液を塗布し、80℃で2分乾燥し、室温で1分冷却後、UV照射して、目的の位相差膜を作製した。
<Production of retardation film>
The UCL sample solution of the example or the comparative example was applied on the prepared photo-alignment film, dried at 80 ° C. for 2 minutes, cooled at room temperature for 1 minute, and then irradiated with UV to prepare a target retardation film.
<位相差膜の評価>
作製した位相差膜を公知の偏光フィルムを用いて目視観察した。各実施例及び比較例の位相差膜について観察し、その結果が良好であった場合を「○」、不良であった場合を「×」として、表1~10に評価結果を示した。
<Evaluation of retardation film>
The prepared retardation film was visually observed using a known polarizing film. The retardation films of the examples and comparative examples were observed, and the evaluation results are shown in Tables 1 to 10, where “◯” indicates that the result was good and “×” indicates that the result was poor.
<保存安定性の評価>
実施例又は比較例のUCLサンプル溶液を恒温槽内(0℃、10℃又は20℃)に保管し、3日後の析出の有無を目視で確認した。
3日後に析出が生じていなかった場合を「○」、析出が生じていた場合を「×」として、表1~11に評価結果を示した。
<Evaluation of storage stability>
The UCL sample solution of the example or the comparative example was stored in a constant temperature bath (0 ° C., 10 ° C. or 20 ° C.), and the presence or absence of precipitation after 3 days was visually confirmed.
The evaluation results are shown in Tables 1 to 11, where “○” indicates that no precipitation occurred after 3 days and “×” indicates that precipitation occurred.
 以上で説明した各実施形態における各構成及びそれらの組み合わせ等は一例であり、本発明の趣旨を逸脱しない範囲で、構成の付加、省略、置換、およびその他の変更が可能である。また、本発明は各実施形態によって限定されることはなく、請求項(クレーム)の範囲によってのみ限定される。 The configurations and combinations thereof in the embodiments described above are merely examples, and additions, omissions, substitutions, and other changes can be made without departing from the spirit of the present invention. Further, the present invention is not limited by each embodiment, and is limited only by the scope of the claims.
 本発明に係る重合性液晶組成物は、液晶ディスプレイの分野に広く適用可能である。 The polymerizable liquid crystal composition according to the present invention is widely applicable in the field of liquid crystal displays.

Claims (8)

  1.  一般式(I)
    Figure JPOXMLDOC01-appb-C000001
    (式中、P及びPは反応性官能基を表し、MGはメソゲン基又はメソゲン性支持基を表し、2つのmは1~6の同一の数値を表す。)で表される重合性化合物を2種以上と有機溶媒を含み、当該重合性化合物のうち、任意の2種の重合性化合物のmをそれぞれSAとSBとした場合に|SA-SB|=1又は2であり、かつ、SA+SB≦10を満たすことを特徴とする重合性液晶組成物。
    Formula (I)
    Figure JPOXMLDOC01-appb-C000001
    (Wherein P 1 and P 2 represent a reactive functional group, MG represents a mesogenic group or a mesogenic supporting group, and two m represent the same numerical value of 1 to 6). When two or more compounds and an organic solvent are included, and m of any two polymerizable compounds among the polymerizable compounds is SA and SB, respectively, | SA−SB | = 1 or 2; A polymerizable liquid crystal composition satisfying SA + SB ≦ 10.
  2. MGが一般式(II-b)
    Figure JPOXMLDOC01-appb-C000002
     (式中、A1、A2及びA3はそれぞれ独立的に、1,4-フェニレン基、1,4-シクロヘキシレン基、1,4-シクロヘキセニル基、テトラヒドロピラン-2,5-ジイル基、1,3-ジオキサン-2,5-ジイル基、テトラヒドロチオピラン-2,5-ジイル基、1,4-ビシクロ(2,2,2)オクチレン基、デカヒドロナフタレン-2,6-ジイル基、ピリジン-2,5-ジイル基、ピリミジン-2,5-ジイル基、ピラジン-2,5-ジイル基、1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基、2,6-ナフチレン基、フェナントレン-2,7-ジイル基、9,10-ジヒドロフェナントレン-2,7-ジイル基、1,2,3,4,4a,9,10a-オクタヒドロフェナントレン2,7-ジイル基又はフルオレン2,7-ジイル基を表し、該1,4-フェニレン基、1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基、2,6-ナフチレン基、フェナントレン-2,7-ジイル基、9,10-ジヒドロフェナントレン-2,7-ジイル基、1,2,3,4,4a,9,10a-オクタヒドロフェナントレン2,7-ジイル基及びフルオレン2,7-ジイル基に結合する1つ以上の水素原子は、F、Cl、CF、OCF、シアノ基、炭素原子数1~8のアルキル基、アルコキシ基、アルカノイル基、アルカノイルオキシ基、炭素原子数2~8のアルケニル基、アルケニルオキシ基、アルケノイル基又はアルケノイルオキシ基により置換されていても良く、
    Z0及びZ3は、-COO-、-OCO-、-CH=CH-、-C≡C-、-CH=CHCOO-、-OCOCH=CH-、-CONH-、-NHCO-、-O-、-S-、-NH-、-N(CH)-、-CO-、-OCOO-、-SCO-、-COS-又は単結合を表し、
    Z1及びZ2はそれぞれ独立して、-COO-、-OCO-、-CHCH―、-OCH-、-CHO-、-CH=CH-、-C≡C-、-CH=CHCOO-、-OCOCH=CH-、-CHCHCOO-、-CHCHOCO-、-COOCHCH-、-OCOCHCH-、-CONH-、-NHCO-、-O-、-S-、-NH-、-N(CH)-、-CO-、-OCOO-、-SCO-、-COS-又は単結合を表し、
    は0、1又は2を表し、nbが2でありZ1が複数存在する場合それらは同一であっても異なっていてもよく、A2が複数存在する場合それらは同一であっても異なっていてもよい。)で表される構造を表す、請求項1記載の重合性液晶組成物。
    MG is represented by the general formula (II-b)
    Figure JPOXMLDOC01-appb-C000002
    (In the formula, A1, A2 and A3 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, 1, 3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2,6-diyl group, pyridine- 2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, Phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a, 9,10a-octahydrophenanthrene 2,7-diyl group or fluorene 2, Represents a 7-diyl group, the 1,4-phenylene group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9 , 10-Dihydrophenanthrene-2,7- Yl group, 1,2,3,4,4a, 9,10a- 1 or more hydrogen atoms bonded to octahydrophenanthrene 2,7-diyl group and fluorene 2,7-diyl group, F, Cl, CF 3 , OCF 3 , a cyano group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkanoyl group, an alkanoyloxy group, an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group, an alkenoyl group or an alkenoyloxy group May be replaced,
    Z0 and Z3 are —COO—, —OCO—, —CH═CH—, —C≡C—, —CH═CHCOO—, —OCOCH═CH—, —CONH—, —NHCO—, —O—, — S—, —NH—, —N (CH 3 ) —, —CO—, —OCOO—, —SCO—, —COS— or a single bond,
    Z1 and Z2 are each independently —COO—, —OCO—, —CH 2 CH 2 —, —OCH 2 —, —CH 2 O—, —CH═CH—, —C≡C—, —CH═ CHCOO—, —OCOCH═CH—, —CH 2 CH 2 COO—, —CH 2 CH 2 OCO—, —COOCH 2 CH 2 —, —OCOCH 2 CH 2 —, —CONH—, —NHCO—, —O— , -S-, -NH-, -N (CH 3 )-, -CO-, -OCOO-, -SCO-, -COS- or a single bond,
    n b is 0, 1 or 2, if nb is located at 2 Z1 there are a plurality of them may be the same or different and if A2 there is more than one they have be the same or different May be. The polymerizable liquid crystal composition according to claim 1, which represents a structure represented by:
  3. 又はPが一般式(II-c)、一般式(II-d)及び一般式(II-e)
    Figure JPOXMLDOC01-appb-C000003
    (式中、R21、R22、R23、R31、R32、R33、R41、R42及びR43はそれぞれ独立的に水素原子、ハロゲン原子又は炭素原子数1~5のアルキル基を表し、nは0又は1を表す。)で表される置換基からなる群より選ばれる置換基を表す、請求項1又は請求項2記載の重合性液晶組成物。
    P 1 or P 2 is represented by the general formula (II-c), general formula (II-d) and general formula (II-e).
    Figure JPOXMLDOC01-appb-C000003
    Wherein R 21 , R 22 , R 23 , R 31 , R 32 , R 33 , R 41 , R 42 and R 43 are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 5 carbon atoms. The polymerizable liquid crystal composition according to claim 1, wherein n represents a substituent selected from the group consisting of substituents represented by:
  4. 一般式(X)で表される化合物を含有する、請求項1~3いずれか一項記載の重合性液晶組成物。
    Figure JPOXMLDOC01-appb-C000004
    (一般式(X)中、PXは反応性官能基を表し、mXは1~8の整数を表し、MGはメソゲン基又はメソゲン性支持基を表し、Rは水素原子、ハロゲン原子、シアノ基又は炭素原子数1~25のアルキル基を表すが、該アルキル基に結合する1つ以上の水素原子はハロゲン原子又はCNにより置換されていても良く、この基中に存在する1つのCH基又は隣接していない2つ以上のCH基はそれぞれ相互に独立して、酸素原子同士、硫黄原子同士及び酸素原子と硫黄原子とが相互に直接結合しない形で、-O-、-S-、-NH-、-N(CH)-、-CO-、-COO-、-OCO-、-OCOO-、-SCO-、-COS-、-CH=CH-、又は-C≡C-により置き換えられていても良い(ただし、Rが前記反応性官能基である場合を除く)。)
    The polymerizable liquid crystal composition according to any one of claims 1 to 3, comprising a compound represented by the general formula (X).
    Figure JPOXMLDOC01-appb-C000004
    (In the general formula (X), P X represents a reactive functional group, m X represents an integer of 1 to 8, MG represents a mesogenic group or a mesogenic supporting group, R 1 represents a hydrogen atom, a halogen atom, A cyano group or an alkyl group having 1 to 25 carbon atoms, wherein one or more hydrogen atoms bonded to the alkyl group may be substituted with a halogen atom or CN, and one CH present in the group; Two groups or two or more CH 2 groups that are not adjacent to each other are independently of each other in a form in which oxygen atoms, sulfur atoms, and oxygen atoms and sulfur atoms are not directly bonded to each other. S—, —NH—, —N (CH 3 ) —, —CO—, —COO—, —OCO—, —OCOO—, —SCO—, —COS—, —CH═CH—, or —C≡C. -(Wherein R 1 is the reactive functional group) Except when it is a group).)
  5. 重合性ディスコチック液晶化合物を含む請求項1~4のいずれか1項記載の重合性液晶組成物。 The polymerizable liquid crystal composition according to any one of claims 1 to 4, comprising a polymerizable discotic liquid crystal compound.
  6.  請求項1~5いずれか一項記載の重合性液晶組成物を用いてなる位相差膜。 A retardation film comprising the polymerizable liquid crystal composition according to any one of claims 1 to 5.
  7.  請求項1~5いずれか一項記載の重合性液晶組成物を用いてなる位相差パターニング膜。 A retardation patterning film comprising the polymerizable liquid crystal composition according to any one of claims 1 to 5.
  8.  請求項1~5いずれか一項記載の重合性液晶組成物を用いてなるホモジニアス配向液晶フィルム。 A homogeneously aligned liquid crystal film comprising the polymerizable liquid crystal composition according to any one of claims 1 to 5.
PCT/JP2014/063698 2013-05-29 2014-05-23 Polymerisable liquid crystal composition, phase difference film, phase difference patterning film, and homogeneously aligned liquid crystal film WO2014192657A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2014557905A JPWO2014192657A1 (en) 2013-05-29 2014-05-23 Polymerizable liquid crystal composition, retardation film, retardation patterning film, and homogeneous alignment liquid crystal film

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013-113353 2013-05-29
JP2013113353 2013-05-29

Publications (1)

Publication Number Publication Date
WO2014192657A1 true WO2014192657A1 (en) 2014-12-04

Family

ID=51988690

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/063698 WO2014192657A1 (en) 2013-05-29 2014-05-23 Polymerisable liquid crystal composition, phase difference film, phase difference patterning film, and homogeneously aligned liquid crystal film

Country Status (3)

Country Link
JP (1) JPWO2014192657A1 (en)
TW (1) TW201510186A (en)
WO (1) WO2014192657A1 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017199512A1 (en) * 2016-05-18 2017-11-23 Jnc株式会社 Low molecular polar compound for homogeneously aligning liquid crystal medium, and liquid crystal medium containing same
WO2017199513A1 (en) * 2016-05-18 2017-11-23 Jnc株式会社 Low molecular polar compound for homogeneously aligning liquid crystal medium, and liquid crystal medium containing same
WO2018003514A1 (en) * 2016-06-28 2018-01-04 Dic株式会社 Polymerizable liquid crystal composition
US10787608B2 (en) 2016-05-18 2020-09-29 Jnc Corporation Liquid crystal display device including liquid crystal medium containing low molecular weight polar compound for homogeneously aligning liquid crystal medium
CN113260909A (en) * 2018-12-27 2021-08-13 日产化学株式会社 Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013014538A (en) * 2011-07-04 2013-01-24 Dic Corp Polymerizable liquid crystal compound
WO2013021826A1 (en) * 2011-08-08 2013-02-14 Dic株式会社 Polymerizable liquid crystal composition, and method for producing optically anisotropic body

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2395201B (en) * 2002-09-24 2006-10-04 Merck Patent Gmbh Broadband reflective film
JP4569189B2 (en) * 2003-06-23 2010-10-27 チッソ株式会社 Liquid crystal compound, liquid crystal composition and polymer thereof
JP4846724B2 (en) * 2004-09-06 2011-12-28 メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング Polymerizable liquid crystal material
JP5162985B2 (en) * 2006-09-21 2013-03-13 Jnc株式会社 Trifunctional compound, composition and polymer thereof
JP5545518B2 (en) * 2009-09-30 2014-07-09 Dic株式会社 Polymerizable biphenyl compound
JP5685806B2 (en) * 2009-10-08 2015-03-18 Dic株式会社 Polymerizable liquid crystal composition

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013014538A (en) * 2011-07-04 2013-01-24 Dic Corp Polymerizable liquid crystal compound
WO2013021826A1 (en) * 2011-08-08 2013-02-14 Dic株式会社 Polymerizable liquid crystal composition, and method for producing optically anisotropic body

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017199512A1 (en) * 2016-05-18 2017-11-23 Jnc株式会社 Low molecular polar compound for homogeneously aligning liquid crystal medium, and liquid crystal medium containing same
WO2017199513A1 (en) * 2016-05-18 2017-11-23 Jnc株式会社 Low molecular polar compound for homogeneously aligning liquid crystal medium, and liquid crystal medium containing same
JPWO2017199512A1 (en) * 2016-05-18 2019-01-24 Jnc株式会社 Low molecular polar compound for homogeneously aligning liquid crystal medium, and liquid crystal medium containing the same
JPWO2017199513A1 (en) * 2016-05-18 2019-01-24 Jnc株式会社 Low molecular polar compound for homogeneously aligning liquid crystal medium, and liquid crystal medium containing the same
US10787608B2 (en) 2016-05-18 2020-09-29 Jnc Corporation Liquid crystal display device including liquid crystal medium containing low molecular weight polar compound for homogeneously aligning liquid crystal medium
US10865344B2 (en) 2016-05-18 2020-12-15 Jnc Corporation Low molecular weight polar compound for homogeneously aligning liquid crystal medium, and liquid crystal medium containing same
WO2018003514A1 (en) * 2016-06-28 2018-01-04 Dic株式会社 Polymerizable liquid crystal composition
JP6414367B2 (en) * 2016-06-28 2018-10-31 Dic株式会社 Polymerizable liquid crystal composition
JPWO2018003514A1 (en) * 2016-06-28 2018-12-27 Dic株式会社 Polymerizable liquid crystal composition
CN109415632A (en) * 2016-06-28 2019-03-01 Dic株式会社 Polymerizable liquid crystal compound
CN113260909A (en) * 2018-12-27 2021-08-13 日产化学株式会社 Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element

Also Published As

Publication number Publication date
TW201510186A (en) 2015-03-16
JPWO2014192657A1 (en) 2017-02-23

Similar Documents

Publication Publication Date Title
JP5880994B1 (en) Polymerizable liquid crystal composition and optical anisotropic body, retardation film and retardation patterning film produced using the composition
JP5725325B2 (en) Polymerizable liquid crystal composition
JP5748031B2 (en) Polymerizable composition solution and optical anisotropic body using the same
JP5387807B1 (en) Polymerizable liquid crystal composition and thin film using the same
JP5885049B2 (en) Method for producing polymerizable liquid crystal composition
JPWO2018047806A1 (en) Polymerizable liquid crystal composition, and optical film using the same
JP2018203945A (en) Polymerizable liquid crystal composition and optical anisotropic body using the same
WO2014192657A1 (en) Polymerisable liquid crystal composition, phase difference film, phase difference patterning film, and homogeneously aligned liquid crystal film
JP2011026384A (en) Polymerizable liquid crystal composition
WO2016043087A1 (en) Polymerizable composition and film using same
JP2011042703A (en) Polymerizable liquid crystal composition
JP6296135B2 (en) Polymerizable composition and film using the same
JP5685806B2 (en) Polymerizable liquid crystal composition
JP6209864B2 (en) Polymerizable liquid crystal composition, retardation film, retardation patterning film, and homogeneous alignment liquid crystal film
JP6288536B2 (en) Polymerizable composition and optical anisotropic body using the same
JP6341401B2 (en) Polymerizable composition solution and optical anisotropic body using the same
JP2011002556A (en) Method of manufacturing biaxial retardation film
JP2013035938A (en) Polymerizable cholesteric liquid crystal composition and cholesteric reflective film using the same
JPWO2019124090A1 (en) Phase difference film, elliptical polarizing plate and display device using it

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2014557905

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: 14804060

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: 14804060

Country of ref document: EP

Kind code of ref document: A1