WO2013021826A1 - Polymerizable liquid crystal composition, and method for producing optically anisotropic body - Google Patents

Polymerizable liquid crystal composition, and method for producing optically anisotropic body Download PDF

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Publication number
WO2013021826A1
WO2013021826A1 PCT/JP2012/068953 JP2012068953W WO2013021826A1 WO 2013021826 A1 WO2013021826 A1 WO 2013021826A1 JP 2012068953 W JP2012068953 W JP 2012068953W WO 2013021826 A1 WO2013021826 A1 WO 2013021826A1
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liquid crystal
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polymerizable liquid
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PCT/JP2012/068953
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French (fr)
Japanese (ja)
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長谷部　浩史
桑名　康弘
小谷　邦彦
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Dic株式会社
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Priority to JP2013527955A priority Critical patent/JP5522313B2/en
Publication of WO2013021826A1 publication Critical patent/WO2013021826A1/en

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    • C—CHEMISTRY; METALLURGY
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    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
    • C09K19/2007—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups
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    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/14—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain
    • C09K19/18—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain the chain containing carbon-to-carbon triple bonds, e.g. tolans
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    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
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    • C09K19/2007—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups
    • C09K19/2014—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers 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-
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    • C09K19/3441—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom
    • C09K19/3483—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom the heterocyclic ring being a non-aromatic ring
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
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    • C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
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    • C09K2019/0448—Liquid 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
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    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
    • C09K2019/121—Compounds containing phenylene-1,4-diyl (-Ph-)
    • C09K2019/122—Ph-Ph
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    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
    • C09K2019/121—Compounds containing phenylene-1,4-diyl (-Ph-)
    • C09K2019/123—Ph-Ph-Ph
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    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/14—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain
    • C09K19/18—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain the chain containing carbon-to-carbon triple bonds, e.g. tolans
    • C09K2019/181—Ph-C≡C-Ph
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    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/14—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain
    • C09K19/18—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain the chain containing carbon-to-carbon triple bonds, e.g. tolans
    • C09K2019/183—Ph-Ph-C≡C-Ph
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    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/14—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain
    • C09K19/18—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain the chain containing carbon-to-carbon triple bonds, e.g. tolans
    • C09K2019/188—Ph-C≡C-Ph-C≡C-Ph
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    • C09K2019/2035—Ph-COO-Ph
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    • C09K2019/2042—Ph-Ph-COO-Ph
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    • C09K2019/2078—Ph-COO-Ph-COO-Ph

Definitions

  • the present invention relates to an optical anisotropic body useful as a liquid crystal device, a display, an optical component, a colorant, a security marking, and a laser emission member, and a method for producing the same.
  • optically anisotropic bodies obtained by ultraviolet curing in a state in which a polymerizable liquid crystal material is aligned. Since such an optical anisotropic body is mainly used for polarization control applications such as a retardation film, it is required to control light scattering of the optical anisotropic body as small as possible. This is because if the light scattering is large, a part of the polarization state is lost, and the polarization state control becomes incomplete.
  • the optical anisotropic body since the light scattering increases as the thickness of the optical anisotropic body increases, the influence is serious particularly in the optical anisotropic body having a thickness of 2 ⁇ m or more.
  • Examples of the optical anisotropic body that requires a thickness of 2 ⁇ m or more include an optical low-pass filter and a reflective polarizing plate using a cholesteric liquid crystal (Patent Document 1).
  • Patent Document 1 there has been no means for effectively suppressing light scattering in such an optical film.
  • the problem to be solved by the present invention is a polymerizable liquid crystal composition that suppresses light scattering of an optical anisotropic body obtained by curing active energy rays in an aligned state of the polymerizable liquid crystal material, and an optical heterogeneity using the same.
  • the object is to provide means for suppressing light scattering of a rectangular parallelepiped.
  • polymer impurities having a molecular weight of about 5,000 or more and oligomer impurities having a molecular weight of about 2 to 4 in the polymerizable liquid crystal composition induce light scattering, and the size that induces light scattering has a large molecular weight. I found that it grows.
  • the magnitude of the influence of tri- and tetrameric impurities causing light scattering is about 5.3 times that of dimeric impurities. That is, the inventors have found that the light scattering magnitude when the tri- and tetrameric impurities are 100 ppm is almost equal to the light scattering magnitude when the dimer impurity is 530 ppm. In addition, the inventors have also found that oligomer impurities having a cyano group are about 47 times larger in the influence of causing light scattering than oligomer impurities not having a cyano group.
  • the present invention relates to the oligomer impurity in the polymerizable liquid crystal composition having a concentration of a cyano group-containing tri- to tetramer impurity a (ppm) and a concentration of a cyano group-containing dimer impurity b (ppm).
  • 3-4 amounts of the oligomer impurities in the polymerizable liquid crystal composition having a cyano group The concentration of the body impurity is a (ppm), the concentration of the dimer impurity having a cyano group is b (ppm), the concentration of the trimer to tetramer impurity having no cyano group is c (ppm), and the cyano group is present.
  • the concentration of the dimer impurities not to be used is d (ppm) and the thickness of the obtained optical anisotropic body is e ( ⁇ m)
  • the formula (I) x [(a + 0.19b) +0.0215 (c + 0.19d)] / e (I)
  • the production method is characterized in that the polymerizable liquid crystal composition controlled so that the x value represented by the formula is 150 or less is used.
  • the polymerizable liquid crystal composition and the method for producing an optical anisotropic body of the present invention since light scattering is reduced, depolarization is suppressed, and an optical anisotropic body having good polarization control performance can be obtained. .
  • the concentration of oligomer impurities in the polymerizable liquid crystal composition can be measured with a GPC (gel permeation chromatograph) apparatus.
  • the concentration of the cyano group-containing trimer to tetramer impurity is a (ppm)
  • the concentration of the cyano group-containing dimer impurity is b (ppm)
  • the concentration of the tri- to tetramer impurity having a cyano group is a (ppm)
  • the concentration of the dimer impurity having a cyano group is b (ppm)
  • no cyano group is contained.
  • the concentration of tetramer impurities is c (ppm)
  • the concentration of dimer impurities not having a cyano group is d (ppm)
  • the thickness of the optical anisotropic body obtained by curing the polymerizable liquid crystal composition is e.
  • the formula (I) x [(a + 0.19b) +0.0215 (c + 0.19d)] / e (I) It is preferable to manage so that the x value represented by the formula is 150 or less, more preferably 110 or less, and particularly preferably 80 or less. However, if these Xa values and x values are to be managed to be unnecessarily low, the purification cost and time in the production of the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition will be increased. It is necessary to adjust the control value.
  • the concentration of the oligomeric impurities can be determined by using a sufficient amount of a polymerization inhibitor in the synthesis of the polymerizable liquid crystal compound to be used. It can be effectively reduced by the activated carbon treatment.
  • the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition can be applied to either a rod shape or a disk shape.
  • the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition can be used without particular limitation as long as it is recognized as a polymerizable liquid crystal compound in this technical field.
  • a compound having only one polymerizable functional group in the molecule is preferable because it is easy to produce a compound containing a low temperature around room temperature as the liquid crystal temperature range of the composition.
  • Examples of such compounds include, for example, Handbook of Liquid Crystals (D. Demus, JW Goodby, GW Gray, HW Spies, V. Vill, edited by Wiley-VCH, 1998). , Quarterly Chemical Review No.
  • a rod-like polymerizable liquid crystal compound having a polymerizable functional group such as a vinyl group, an acryloyl group or a (meth) acryloyl group, or a maleimide as described in JP-A Nos. 2004-2373 and 2004-99446 Examples thereof include a rod-like polymerizable liquid crystal compound having a group.
  • Examples of the polymerizable functional group include a vinyl group, an acryloyl group, a (meth) acryloyl group, and a maleimide group. From the viewpoint of productivity, an acryloyl group and a (meth) acryloyl group are preferable.
  • liquid crystal compound having only one polymerizable functional group is preferably a compound represented by the following general formula (a).
  • Z 3 represents a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group having 1 to 20 carbon atoms
  • Z 4 represents a hydrogen atom or a methyl group
  • W 3 represents a single bond, —O—, -COO- or -OCO-
  • v represents an integer of 0 to 18
  • u represents 0 or 1
  • D E and F are each independently a 1,4-phenylene group or a non-adjacent CH group.
  • R represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxyl group, or a carbamoyl group.
  • a cyano group, a nitro group, and a halogen atom and when these groups are alkyl groups having 1 to 6 carbon atoms or alkoxy groups having 1 to 6 carbon atoms, they are all unsubstituted, When these groups are a carboxyl group or a carbamoyl group, the terminal hydrogen atom may be unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms.
  • R preferably represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a cyano group. Since the compound having a cyano group as R is greatly affected by oligomer impurities, its concentration control is important.
  • liquid crystal compounds can be used alone or in combination of two or more.
  • the content of the compound represented by the general formula (a) is preferably 5% to 70%, more preferably 7% to 60%, and particularly preferably 9% to 50%.
  • a liquid crystal compound having two polymerizable functional groups is useful from the viewpoint of ensuring the mechanical strength of a film obtained by curing.
  • examples of such compounds having two polymerizable functional groups include, for example, Handbook of Liquid Crystals (D. Demus, JW Goodby, GW Gray, HW Spiss, V. Vill, edited by Wiley. -Published by VCH, 1998), Quarterly Chemical Review No. 22, Liquid Crystal Chemistry (edited by the Chemical Society of Japan, 1994), or Japanese Patent Laid-Open Nos.
  • 1,4-phenylene group 1,4-cyclohex A rod-like polymerizable liquid crystal compound having a rigid site called mesogen in which a plurality of structures such as a len group are connected, and a polymerizable functional group such as a vinyl group, an acryloyl group, and a (meth) acryloyl group, or JP-A-2004-2373, A rod-like polymerizable liquid crystal compound having a maleimide group as described in JP-A-2004-99446 And the like.
  • Examples of the polymerizable functional group include a vinyl group, an acryloyl group, a (meth) acryloyl group, and a maleimide group. From the viewpoint of productivity, an acryloyl group and a (meth) acryloyl group are preferable.
  • liquid crystal compound having two polymerizable functional groups is preferably a compound represented by the following general formula (b).
  • Z 5 and Z 6 each independently represent a hydrogen atom or a methyl group
  • G, H and I each independently represent a 1,4-phenylene group and a non-adjacent CH group substituted with nitrogen.
  • a 1,4-phenylene group present in the formula may be substituted with one or more alkyl groups, alkoxy groups, alkanoyl groups, cyano groups or halogen atoms having 1 to 7 carbon atoms;
  • W 1 and W 2 each independently represent a single bond, —O—, —COO— or —OCO—
  • Y 1 and Y 2 each independently represent a single bond, — COO-, -OCO-, -CH 2 CH
  • R represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxyl group, a carbamoyl group, cyano.
  • R is preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a cyano group.
  • liquid crystal compounds can be used alone or in combination of two or more.
  • the content of the compound represented by the general formula (b) is preferably 5% to 90%, more preferably 10% to * 80%, and particularly preferably 20% to 70%.
  • an additive may be contained depending on the purpose.
  • R 1 , R 2 , R 3 and R 4 each independently represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and one hydrocarbon atom in the hydrocarbon group
  • a compound having a repeating unit represented by the above-mentioned halogen atom may be used.
  • Examples of the compound represented by the general formula (II) include polyethylene, polypropylene, polyisobutylene, paraffin, liquid paraffin, chlorinated polypropylene, chlorinated paraffin, and chlorinated liquid paraffin.
  • the compound which has a repeating unit represented by these is mentioned.
  • structures represented by the formulas (II-a) to (II-e) are more preferable, and structures represented by the formulas (II-a) and (II-c) are particularly preferable.
  • a copolymer obtained by copolymerizing two or more compounds having a repeating unit represented by formulas (II-a) to (II-f) is also preferable.
  • the mass average molecular weight of the compound is too small, the effect of reducing the tilt angle is poor, and if it is too large, the orientation is not stable for a long time, so there is an optimum range.
  • it is preferably 200 to 1000000, more preferably 300 to 100,000, and particularly preferably 400 to 80000.
  • the compound is preferably contained in the polymerizable liquid crystal composition in an amount of 0.01 to 5% by mass, more preferably 0.05 to 2% by mass, and 0.1 to 1% by mass. Is particularly preferred.
  • a chiral compound is added so as to exhibit a cholesteric liquid crystal phase (chiral nematic liquid crystal phase).
  • a chiral compound preferably has one or more polymerizable functional groups. Examples of such compounds include JP-A-11-193287, JP-A-2001-158788, JP-T 2006-52669, JP-A-2007-269639, JP-A-2007-269640, 2009.
  • -84178 which contains chiral saccharides such as isosorbide, isomannite, glucoside, and the like, and a rigid site such as 1,4-phenylene group and 1,4-cyclohexylene group, and a vinyl group
  • a polymerizable chiral compound having a polymerizable functional group such as an acryloyl group, a (meth) acryloyl group, or a maleimide group, a polymerizable chiral compound comprising a terpenoid derivative as described in JP-A-8-239666, NATURE VOL35, pages 467-469 (November 30, 1995) Issue), NATURE VOL392, pages 476-479 (issued on April 2, 1998), or the like, or a polymerizable chiral compound comprising a mesogenic group and a spacer having a chiral moiety, or JP-T-2004-504285.
  • a polymerizable chiral compound containing a binaphthyl group as described in JP-A-2007-248945 a polymerizable chiral compound containing a binaphthyl group as described in JP-A-2007-248945.
  • a chiral compound having a large helical twisting power (HTP) is preferable because the polymerizable liquid crystal composition of the present invention can be easily produced.
  • chiral compound used in the polymerizable liquid crystal composition include the following liquid crystal compounds.
  • n and n each independently represent an integer of 1 to 10
  • R represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxyl group, a carbamoyl group, cyano.
  • these groups are an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, they are all unsubstituted, or one or two
  • these groups are a carboxyl group or a carbamoyl group, the terminal hydrogen atom may be unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms.
  • These chiral compounds can be used alone or in combination of two or more.
  • a polymerization initiator may be added to the polymerizable liquid crystal composition.
  • a polymerization initiator a well-known usual thing can be used as a photoinitiator used when performing by an active energy ray.
  • 2-hydroxy-2-methyl-1-phenylpropan-1-one (“Darocur 1173” manufactured by Merck)
  • 1-hydroxycyclohexyl phenyl ketone (“Irgacure 184” manufactured by Ciba Specialty Chemicals)
  • 1- ( 4-Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one (“Darocur 1116” manufactured by Merck & Co.)
  • 2-methyl-1-[(methylthio) phenyl] -2-morpholinopropane-1 “Irgacure 907” manufactured by Ciba Specialty Chemicals).
  • Benzylmethylketal (“Irgacure 651” manufactured by Ciba Specialty Chemicals) 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone (“Irgacure 369” manufactured by Ciba Specialty Chemicals) ), 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) butan-1-one (“Irgacure 379” manufactured by Ciba Specialty Chemicals), 2 , 2-Dimethoxy-1,2-diphenylethane-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Darocur TPO), 2,4,6-trimethylbenzoyl-diphenyl-phosphine Oxide (“Irgaku” manufactured by Ciba Specialty Chemicals) 819 "), 1,2-octanedione, 1- [4- (phenylthio)
  • the content of the photopolymerization initiator is preferably 1 to 10% by mass, particularly preferably 2 to 7% by mass. These can be used alone or in combination of two or more.
  • thermal polymerization initiator examples include methyl acetoacetate peroxide, cumene hydroperoxide, benzoyl peroxide, bis (4-t-butylcyclohexyl) peroxydicarbonate, t-butylperoxybenzoate, and methyl ethyl ketone peroxide.
  • Oxide 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, p-pentahydroperoxide, t-butylhydroperoxide, dicumyl peroxide, isobutyl peroxide, di (3- Methyl-3-methoxybutyl) peroxydicarbonate, organic peroxides such as 1,1-bis (t-butylperoxy) cyclohexane, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-Dimethylvaleronitrile ), Azonitrile compounds such as 2,2′-azobis (2-methyl-N-phenylpropion-amidin) dihydrochloride, 2,2′azobis ⁇ 2-methyl-N- [1,1-bis An azoamide compound such as (hydroxymethyl) -2-hydroxyethyl] propionamide ⁇ , an alkylazo compound such as 2,2′azobis (2,4,4-trimethylpentan
  • a polymerization inhibitor to the polymerizable liquid crystal composition.
  • the polymerization inhibitor include phenol compounds, quinone compounds, amine compounds, thioether compounds, nitroso compounds, and the like.
  • phenolic compounds include p-methoxyphenol, cresol, t-butylcatechol, 3.5-di-t-butyl-4-hydroxytoluene, 2.2'-methylenebis (4-methyl-6-t-butylphenol) 2.2′-methylenebis (4-ethyl-6-tert-butylphenol), 4.4′-thiobis (3-methyl-6-tert-butylphenol), 4-methoxy-1-naphthol, 4,4′- Dialkoxy-2,2′-bi-1-naphthol, and the like.
  • quinone compounds include hydroquinone, methylhydroquinone, tert-butylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, tert-butyl-p-benzoquinone, 2,5-diphenylbenzoquinone, 2-hydroxy-1,4-naphthoquinone 1,4-naphthoquinone, 2,3-dichloro-1,4-naphthoquinone, anthraquinone, diphenoquinone and the like.
  • amine compounds include p-phenylenediamine, 4-aminodiphenylamine, N.I.
  • N'-diphenyl-p-phenylenediamine Ni-propyl-N'-phenyl-p-phenylenediamine, N- (1.3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N.I. N′-di-2-naphthyl-p-phenylenediamine, diphenylamine, N-phenyl- ⁇ -naphthylamine, 4.4′-dicumyl-diphenylamine, 4.4′-dioctyl-diphenylamine and the like.
  • thioether compounds include phenothiazine and distearyl thiodipropionate.
  • nitroso compounds include N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, N-nitrosodinaphthylamine, p-nitrosophenol, nitrosobenzene, p-nitrosodiphenylamine, ⁇ -nitroso- ⁇ -naphthol, and the like, N, N-dimethyl p-nitrosoaniline, p-nitrosodiphenylamine, p-nitronedimethylamine, p-nitrone-N, N-diethylamine, N-nitrosoethanolamine, N-nitrosodi-n-butylamine, N-nitroso-N-n-butyl- 4-butanolamine, N-nitroso-diisopropanolamine, N-nitroso-N-ethyl-4-butanolamine, 5-nitroso-8-hydroxyquinoline, N-nitrosomorpholine, N-nitro
  • surfactants that can be included include alkyl carboxylates, alkyl phosphates, alkyl sulfonates, fluoroalkyl carboxylates, fluoroalkyl phosphates, fluoroalkyl sulfonates, polyoxyethylene derivatives, fluoro Examples thereof include alkylethylene oxide derivatives, polyethylene glycol derivatives, alkylammonium salts, fluoroalkylammonium salts, silicone derivatives and the like, and 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
  • the preferred addition amount of the surfactant varies depending on components other than the surfactant contained in the polymerizable liquid crystal composition, the use temperature, etc., but is contained in the polymerizable liquid crystal composition in an amount of 0.01 to 1% by mass.
  • the content is preferably 0.02 to 0.5% by mass, more preferably 0.03 to 0.1% by mass. When the content is lower than 0.01% by mass, it is difficult to obtain the effect of reducing film thickness unevenness.
  • the total content of the horizontal alignment additive having a repeating unit represented by the general formula (I) and the content of the surfactant is preferably 0.02 to 0.5% by mass, and 0.05 to 0
  • the content is more preferably 4% by mass, and particularly preferably 0.1 to 0.2% by mass.
  • the polymerizable liquid crystal composition may contain other additives such as thixotropic agents, surfactants, ultraviolet absorbers, infrared absorbers, antioxidants, surface treatment agents, and the like. Can be added to such an extent that it does not significantly decrease.
  • the optical anisotropic body of the present invention can be produced by forming a polymerizable liquid crystal composition with controlled oligomer purity on a substrate by a method such as coating, and then curing.
  • the base material used for the optical anisotropic body of the present invention is a base material usually used for a liquid crystal device, a display, an optical component or an optical film, and when dried after application of the polymerizable liquid crystal composition of the present invention, or
  • the material is not particularly limited as long as it is a material having heat resistance capable of withstanding heating at the time of manufacturing a liquid crystal device.
  • 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 is an organic material
  • cellulose derivatives, polyolefins, polyesters, polyolefins, polycarbonates, polyacrylates, polyarylates, polyether sulfones, polyimides, polyphenylene sulfides, polyphenylene ethers, nylons, polystyrenes, and the like can be given.
  • 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 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 substrate surface by a method such as vapor deposition, or in order to add an 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 substrate is usually subjected to an alignment treatment or an alignment film so that the polymerizable liquid crystal composition is aligned when the polymerizable liquid crystal composition of the present invention is applied and dried.
  • 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.
  • Applicable methods such as applicator method, bar coating method, spin coating method, gravure printing method, flexographic printing method, ink jet method, die coating method, cap coating method, dipping, etc. are known as methods for applying the polymerizable liquid crystal material to the substrate. Conventional methods can be performed. It is preferable to apply a polymerizable liquid crystal composition diluted with a solvent.
  • the solvent to be used may be any solvent that does not dissolve the substrate or the alignment film formed on the substrate when applied on the substrate.
  • a solvent that favorably dissolves the polymerizable cholesteric liquid crystal composition of the present invention is preferable.
  • 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, and cyclohexanone.
  • 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, and cyclohexanone.
  • Ketone solvents such as tetrahydrofuran, ether solvents such as tetrahydrofuran, 1,2-dimethoxyethane, anisole, amide solvents such as N, N-dimethylformamide, N-methyl-2-pyrrolidone, propylene glycol monomethyl ether acetate, diethylene glycol Examples include monomethyl ether acetate, ⁇ -butyrolactone, chlorobenzene and the like. These can be used alone or in combination of two or more.
  • the ratio of the solvent is not particularly limited as long as the polymerizable liquid crystal composition used in the present invention is usually applied by coating, so long as the applied state is not significantly impaired, but the solid content of the polymerizable liquid crystal composition and the solvent
  • the ratio is preferably 0.1: 99.9 to 80:20, and more preferably 1:99 to 60:40 in view of coating properties.
  • the polymerization operation of the polymerizable liquid crystal composition of the present invention is preferably performed by generally irradiating active energy rays in a state of being oriented in a desired state after removing the solvent in the polymerizable liquid crystal composition by drying or the like.
  • active energy rays include ultraviolet rays and electron beams. From the simplicity of the apparatus, it is preferable to use ultraviolet rays as the active energy ray.
  • ultraviolet 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 liquid crystal 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 intensity of the ultraviolet light is preferably 1 ⁇ 100mW / cm 2, more preferably 2 ⁇ 50mW / cm 2, particularly preferably 5 ⁇ 30mW / cm 2.
  • the optical anisotropic body can be heat-treated.
  • the heating temperature is preferably within a range not exceeding the glass transition point of the base material when an organic material is used as the base material.
  • Example 1 15.18% polymerizable liquid crystal compound represented by formula (A-1), 6.50% polymerizable liquid crystal compound represented by formula (A-2), 23.85% polymerizable liquid crystal compound represented by formula (B-1) 32.52% of a polymerizable liquid crystal compound represented by the formula (B-2), 7.01% of a polymerizable chiral compound represented by the formula (C-1), 8.67% of a polymerizable liquid crystal compound represented by the formula (D-1) %, Liquid crystal compound represented by formula (E-1) 3.25%, photopolymerization initiator represented by formula (F-1) 2.17%, photopolymerization initiator represented by formula (F-2) 0.44 parts Then, 0.44 part of p-methoxyphenol (E-1) was mixed to obtain a polymerizable cholesteric liquid crystal composition (1).
  • the oligomer impurities contained in this polymerizable cholesteric liquid crystal composition were analyzed using GPC and NMR. As a result, the total of ternary tetramer impurities (I-1) and (I-2) having a cyano group was 182 ppm, The total amount of dimer impurities (I-3) and (I-4) having a cyano group is 1182 ppm, and the total amount of tri to tetramer impurities (I-5) to (I-8) having no cyano group is The total amount of dimer impurities (I-9) to (I-12) having no cyano group was 4385 ppm. The Xa value calculated from the formula (Ia) in this polymerizable cholesteric liquid crystal composition (1) was 434.
  • R 1 and R 2 represents a hydrogen atom, the other represents the formula (I-1b), and m1 represents 3 or 4)
  • R 3 and R 4 represents a hydrogen atom, the other represents the formula (I-2b), and m2 represents 3 or 4)
  • one of R 9 and R 10 represents a hydrogen atom, the other represents the formula (I-5b), and m3 represents 3 or 4)
  • R 11 and R 12 represents a hydrogen atom, the other represents the formula (I-6b), and m4 represents 3 or 4)
  • R 13 and R 14 represents a hydrogen atom, the other represents the formula (I-7b), and m5 represents 3 or 4)
  • R 15 and R 16 represents a hydrogen atom, the other represents the formula (I-8b), and m6 represents 3 or 4)
  • the polymerizable cholesteric liquid crystal composition (A) of the present invention was prepared by adding 0.10% of polypropylene having a weight average molecular weight of 1650 as a horizontal alignment additive to the prepared polymerizable cholesteric liquid crystal composition (1).
  • 30% toluene and 30% cyclohexanone were added to prepare a solution of the polymerizable liquid crystal composition (1 ′).
  • the polyimide solution for alignment film was applied to a glass substrate having a thickness of 0.7 mm using a spin coating method, dried at 100 ° C. for 10 minutes, and then baked at 200 ° C. for 60 minutes to obtain a coating film. .
  • the obtained coating film was rubbed to obtain a cholesteric reflective film substrate of the present invention.
  • the rubbing treatment was performed using a commercially available rubbing apparatus.
  • a solution of the polymerizable liquid crystal composition (1 ′) was applied to the rubbed substrate by a spin coating method and dried at 65 ° C. for 3 minutes.
  • the obtained coating film was placed on a hot plate at 60 ° C., and a 15 mW / cm 2 high-pressure mercury lamp adjusted so that ultraviolet light (UV light) of only around 365 nm was obtained with a bandpass filter. Irradiated with UV light for 10 seconds at intensity.
  • the bandpass filter was removed, and the optical anisotropic body (cholesteric reflective film) of the present invention was obtained by irradiating with UV light at an intensity of 70 mW / cm 2 for 20 seconds.
  • the film thickness of the obtained cholesteric reflective film was 5.5 ⁇ m. Moreover, it was 4.6% when the haze of the film was measured.
  • the x value calculated from formula (I) was 79.
  • Example 1 In Example 1, the experiment was performed in the same manner as in Example 1 except that the polymerizable liquid crystal compound was replaced with a compound of a lot having a different purification method. The results are shown in Table 1.
  • Example 1 (Comparative Examples 1 to 7)
  • the experiment was performed in the same manner as in Example 1 except that the polymerizable liquid crystal compound was replaced with a compound of a lot having a different purification method.
  • the results are shown in Table 1.
  • the polymerizable liquid crystal composition of the present invention having an Xa value of 825 or less has a haze of an optical anisotropic body obtained by using this of 10% or less, and can suppress light scattering.
  • the optical anisotropic body obtained by the method of the present invention having an x value of 150 or less has a haze of 10% or less, and light scattering is suppressed.

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Abstract

The present invention provides a polymerizable liquid crystal composition characterized in that a value Xa represented by formula (Ia): Xa = (a+0.19b) + 0.0215(c+0.19d) is adjusted to 825 or less, wherein a (ppm) represents the concentration of a 3- to 4-mer impurity each having a cyano group, b (ppm) represents the concentration of a dimer impurity having a cyano group, c (ppm) represents the concentration of a 3- to 4-mer impurity having no ciano group, and d (ppm) represents the concentration of a dimer impurity having no cyano group, among oligomer impurities in the polymerizable liquid crystal composition. According to this polymerizable liquid crystal composition, light scattering can be reduced and consequently depolarization can be inhibited. Therefore, an optically anisotropic body having good polarization control performance can be produced.

Description

重合性液晶組成物、及び光学異方体の製造方法Polymerizable liquid crystal composition and method for producing optical anisotropic body
　本発明は、液晶デバイス、ディスプレイ、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として有用な、光学異方体とその製造方法に関する。 The present invention relates to an optical anisotropic body useful as a liquid crystal device, a display, an optical component, a colorant, a security marking, and a laser emission member, and a method for producing the same.
　重合性液晶材料を配向させた状態で紫外線硬化させて得られる光学異方体について多くの検討がなされている。このような光学異方体は主に、位相差フィルムなどの偏光制御用途に使用されることが多いので、光学異方体の光散乱はできる限り小さく制御することが求められている。光散乱が大きいと偏光状態が一部失われ、偏光状態制御が不完全なものになってしまうからである。 Many studies have been made on optically anisotropic bodies obtained by ultraviolet curing in a state in which a polymerizable liquid crystal material is aligned. Since such an optical anisotropic body is mainly used for polarization control applications such as a retardation film, it is required to control light scattering of the optical anisotropic body as small as possible. This is because if the light scattering is large, a part of the polarization state is lost, and the polarization state control becomes incomplete.
　また、光散乱は光学異方体の厚みが増すほど大きくなるため、特に2μｍ以上の厚みを有する光学異方体において、その影響は深刻であった。2μm以上の厚みを必要な光学異方体としては、例えば、光学的ローパスフィルターやコレステリック液晶を用いた反射型偏光板（特許文献１）などを挙げることができる。しかし、このような光学フィルムにおいて、光散乱を効果的に抑制する手段は無かった。 In addition, since the light scattering increases as the thickness of the optical anisotropic body increases, the influence is serious particularly in the optical anisotropic body having a thickness of 2 μm or more. Examples of the optical anisotropic body that requires a thickness of 2 μm or more include an optical low-pass filter and a reflective polarizing plate using a cholesteric liquid crystal (Patent Document 1). However, there has been no means for effectively suppressing light scattering in such an optical film.
特許第３５９２３８３号公報Japanese Patent No. 3592383 特許第３８２８１５８号公報Japanese Patent No. 3828158
　本発明が解決しようとする課題は、重合性液晶材料を配向させた状態において活性エネルギー線硬化させて得られる光学異方体の光散乱を抑制する重合性液晶組成物及びそれを用いた光学異方体の光散乱抑制手段を提供することにある。 The problem to be solved by the present invention is a polymerizable liquid crystal composition that suppresses light scattering of an optical anisotropic body obtained by curing active energy rays in an aligned state of the polymerizable liquid crystal material, and an optical heterogeneity using the same. The object is to provide means for suppressing light scattering of a rectangular parallelepiped.
　鋭意検討した結果、重合性液晶組成物中の分子量が約5000以上のポリマー不純物や2～4量体程度のオリゴマー不純物が、光散乱を誘起すること、光散乱を誘起する大きさは分子量が大きいほど大きくなることを見出した。 As a result of intensive studies, polymer impurities having a molecular weight of about 5,000 or more and oligomer impurities having a molecular weight of about 2 to 4 in the polymerizable liquid crystal composition induce light scattering, and the size that induces light scattering has a large molecular weight. I found that it grows.
　また、カラムクロマトグラフィー、活性炭吸着、分子蒸留によって、これらの不純物は除去可能であること、またオリゴマー不純物より、ポリマー不純物の方が除去がはるかに容易であることも見出した。したがって、オリゴマー不純物の濃度を一定以下に管理すれば、ポリマー濃度による光散乱への影響は無視できる状態になる。重合性液晶組成物を硬化させて得られる光学異方体の光散乱を低減するためには、光散乱を誘起するポリマーとオリゴマー不純物を管理しなければならないが、この管理についてはオリゴマー濃度で代表させて管理すれば良いことも見出した。 It was also found that these impurities can be removed by column chromatography, activated carbon adsorption, and molecular distillation, and that polymer impurities are much easier to remove than oligomer impurities. Therefore, if the oligomer impurity concentration is controlled below a certain level, the influence of the polymer concentration on light scattering can be ignored. In order to reduce the light scattering of the optical anisotropic body obtained by curing the polymerizable liquid crystal composition, it is necessary to manage the polymer and oligomer impurities that induce light scattering. This management is represented by the oligomer concentration. I also found out that I should manage it.
　さらに、3～4量体不純物が光散乱を引き起こす影響の大きさは、2量体不純物のおよそ5.3倍であることを見出した。つまり、3～4量体不純物を100ppm含有している場合の光散乱の大きさと、2量体不純物を530ppm含有している場合の光散乱の大きさがほぼ等しいことを見出した。また、シアノ基を有するオリゴマー不純物は、シアノ基を持たないオリゴマー不純物と比較して、光散乱を引き起こす影響の大きさがおよそ47倍大きいことも見出した。 Furthermore, it has been found that the magnitude of the influence of tri- and tetrameric impurities causing light scattering is about 5.3 times that of dimeric impurities. That is, the inventors have found that the light scattering magnitude when the tri- and tetrameric impurities are 100 ppm is almost equal to the light scattering magnitude when the dimer impurity is 530 ppm. In addition, the inventors have also found that oligomer impurities having a cyano group are about 47 times larger in the influence of causing light scattering than oligomer impurities not having a cyano group.
　即ち、本発明は、重合性液晶組成物中におけるオリゴマー不純物のうち、シアノ基を有する3～4量体不純物の濃度をa(ppm)、シアノ基を有する2量体不純物の濃度をb(ppm)、シアノ基を有さない3～4量体不純物の濃度をc(ppm)、シアノ基を有さない2量体不純物の濃度をd(ppm)としたとき、式（Ｉａ）
　Xa=(a+0.19b)+0.0215(c+0.19d)   (Ia)
で表されるXa値が、825以下になるように制御することを特徴とした重合性液晶組成物を提供する。併せて、重合性液晶組成物を配向させた状態において活性エネルギー線硬化させて光学異方体を製造する方法において、重合性液晶組成物中におけるオリゴマー不純物のうち、シアノ基を有する3～4量体不純物の濃度をa(ppm)、シアノ基を有する2量体不純物の濃度をb(ppm)、シアノ基を有さない3～4量体不純物の濃度をc(ppm)、シアノ基を有さない2量体不純物の濃度をd(ppm)、得られる光学異方体の厚みをe（μｍ）としたとき、式（Ｉ）
　x=[(a+0.19b)+0.0215(c+0.19d)]/e   (I)
で表されるx値が、150以下になるように制御した重合性液晶組成物を使用することを特徴とする製造方法を提供する。 That is, the present invention relates to the oligomer impurity in the polymerizable liquid crystal composition having a concentration of a cyano group-containing tri- to tetramer impurity a (ppm) and a concentration of a cyano group-containing dimer impurity b (ppm). ), When the concentration of the 3-4 tetramer impurity having no cyano group is c (ppm) and the concentration of the dimer impurity having no cyano group is d (ppm), the formula (Ia)
Xa = (a + 0.19b) +0.0215 (c + 0.19d) (Ia)
The polymerizable liquid crystal composition is characterized in that the Xa value represented by is controlled to be 825 or less. In addition, in the method for producing an optical anisotropic body by curing the active energy ray in an aligned state of the polymerizable liquid crystal composition, 3-4 amounts of the oligomer impurities in the polymerizable liquid crystal composition having a cyano group The concentration of the body impurity is a (ppm), the concentration of the dimer impurity having a cyano group is b (ppm), the concentration of the trimer to tetramer impurity having no cyano group is c (ppm), and the cyano group is present. When the concentration of the dimer impurities not to be used is d (ppm) and the thickness of the obtained optical anisotropic body is e (μm), the formula (I)
x = [(a + 0.19b) +0.0215 (c + 0.19d)] / e (I)
The production method is characterized in that the polymerizable liquid crystal composition controlled so that the x value represented by the formula is 150 or less is used.
　本発明の重合性液晶組成物及び光学異方体の製造方法によれば、光散乱が低減されるため、偏光解消が抑制され、良好な偏光制御性能を有する光学異方体を得ることができる。 According to the polymerizable liquid crystal composition and the method for producing an optical anisotropic body of the present invention, since light scattering is reduced, depolarization is suppressed, and an optical anisotropic body having good polarization control performance can be obtained. .
　重合性液晶組成物中のオリゴマー不純物の濃度は、ＧＰＣ（ゲルパーミエーションクロマトグラフ）装置で測定することができる。 The concentration of oligomer impurities in the polymerizable liquid crystal composition can be measured with a GPC (gel permeation chromatograph) apparatus.
　重合性液晶組成物中におけるシアノ基を有する3～4量体不純物の濃度をa(ppm)、シアノ基を有する2量体不純物の濃度をb(ppm)、シアノ基を有さない3～4量体不純物の濃度をc(ppm)、シアノ基を有さない2量体不純物の濃度をd(ppm)としたとき、式（Ｉａ）
　Xa=(a+0.19b)+0.0215(c+0.19d)   (Ia)
で表されるXa値が、825以下に管理するのが好ましく、605以下が更に好ましく、440以下が特に好ましい。 In the polymerizable liquid crystal composition, the concentration of the cyano group-containing trimer to tetramer impurity is a (ppm), the concentration of the cyano group-containing dimer impurity is b (ppm), and the cyano group-free 3-4 When the concentration of the monomer impurity is c (ppm) and the concentration of the dimer impurity not having a cyano group is d (ppm), the formula (Ia)
Xa = (a + 0.19b) +0.0215 (c + 0.19d) (Ia)
Is preferably controlled to be 825 or less, more preferably 605 or less, and particularly preferably 440 or less.
　更に、重合性液晶組成物中におけるシアノ基を有する3～4量体不純物の濃度をa(ppm)、シアノ基を有する2量体不純物の濃度をb(ppm)、シアノ基を有さない3～4量体不純物の濃度をc(ppm)、シアノ基を有さない2量体不純物の濃度をd(ppm)、重合性液晶組成物を硬化させて得られる光学異方体の厚みをe（μｍ）としたとき、式（Ｉ）
　x=[(a+0.19b)+0.0215(c+0.19d)]/e   (I)
で表されるx値が、150以下になるように管理するのが好ましく、110以下が更に好ましく、80以下が特に好ましい。しかし、いたずらにこれらXa値やx値を低く管理しようとすると重合性液晶組成物中に含有される重合性液晶化合物の製造における精製コストと時間を増大させてしまうことになるので目的に応じて管理値を調節する必要がある。オリゴマー不純物の濃度は、使用する重合性液晶化合物の合成の際に十分な量の重合禁止剤を併用することによって、また、得られた重合性液晶化合物をシリカゲルカラムクロマトグラフィー、アルミナカラムクロマトグラフィーや活性炭処理によって効果的に低減することができる。 Further, in the polymerizable liquid crystal composition, the concentration of the tri- to tetramer impurity having a cyano group is a (ppm), the concentration of the dimer impurity having a cyano group is b (ppm), and no cyano group is contained. The concentration of tetramer impurities is c (ppm), the concentration of dimer impurities not having a cyano group is d (ppm), and the thickness of the optical anisotropic body obtained by curing the polymerizable liquid crystal composition is e. (Μm), the formula (I)
x = [(a + 0.19b) +0.0215 (c + 0.19d)] / e (I)
It is preferable to manage so that the x value represented by the formula is 150 or less, more preferably 110 or less, and particularly preferably 80 or less. However, if these Xa values and x values are to be managed to be unnecessarily low, the purification cost and time in the production of the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition will be increased. It is necessary to adjust the control value. The concentration of the oligomeric impurities can be determined by using a sufficient amount of a polymerization inhibitor in the synthesis of the polymerizable liquid crystal compound to be used. It can be effectively reduced by the activated carbon treatment.
　重合性液晶組成物に含まれる重合性液晶化合物としては、棒状でも、円盤状のものどちらにでも適用可能である。 The polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition can be applied to either a rod shape or a disk shape.
　重合性液晶組成物に含まれる重合性液晶化合物としては、本技術分野で重合性液晶化合物として認識されるものであれば、特に制限無く使用することができる。この中でも分子内に重合性官能基を１つのみ有する化合物は、組成物の液晶温度範囲として室温前後の低温を含むものを作りやすく好ましい。このような化合物としては、例えば、Ｈａｎｄｂｏｏｋ　ｏｆ　Ｌｉｑｕｉｄ　Ｃｒｙｓｔａｌｓ（Ｄ．Ｄｅｍｕｓ，Ｊ．Ｗ．Ｇｏｏｄｂｙ，Ｇ．Ｗ．Ｇｒａｙ，Ｈ．Ｗ．Ｓｐｉｅｓｓ，Ｖ．Ｖｉｌｌ編集、Ｗｉｌｅｙ－ＶＣＨ社発行，１９９８年）、季刊化学総説Ｎｏ．２２、液晶の化学（日本化学会編，１９９４年）、あるいは、特開平７－２９４７３５号公報、特開平８－３１１１号公報、特開平８－２９６１８号公報、特開平１１－８００９０号公報、特開平１１－１１６５３８号公報、特開平１１－１４８０７９号公報、等に記載されているような、１，４－フェニレン基１，４－シクロヘキレン基等の構造が複数繋がったメソゲンと呼ばれる剛直な部位と、ビニル基、アクリロイル基、（メタ）アクリロイル基といった重合性官能基を有する棒状重合性液晶化合物、あるいは特開２００４－２３７３号公報、特開２００４－９９４４６号公報に記載されているようなマレイミド基を有する棒状重合性液晶化合物が挙げられる。 The polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition can be used without particular limitation as long as it is recognized as a polymerizable liquid crystal compound in this technical field. Among these, a compound having only one polymerizable functional group in the molecule is preferable because it is easy to produce a compound containing a low temperature around room temperature as the liquid crystal temperature range of the composition. Examples of such compounds include, for example, Handbook of Liquid Crystals (D. Demus, JW Goodby, GW Gray, HW Spies, V. Vill, edited by Wiley-VCH, 1998). , Quarterly Chemical Review No. 22, Liquid Crystal Chemistry (edited by the Chemical Society of Japan, 1994), or JP-A-7-294735, JP-A-8-3111, JP-A-8-29618, JP-A-11-80090, A rigid site called a mesogen in which a plurality of structures such as 1,4-phenylene group and 1,4-cyclohexylene group are connected as described in Kaihei 11-116538, JP-A-11-148079, etc. A rod-like polymerizable liquid crystal compound having a polymerizable functional group such as a vinyl group, an acryloyl group or a (meth) acryloyl group, or a maleimide as described in JP-A Nos. 2004-2373 and 2004-99446 Examples thereof include a rod-like polymerizable liquid crystal compound having a group.
　重合性官能基は、ビニル基、アクリロイル基、（メタ）アクリロイル基、マレイミド基等が上げられるが、生産性の観点から、アクリロイル基、（メタ）アクリロイル基が好ましい。 Examples of the polymerizable functional group include a vinyl group, an acryloyl group, a (meth) acryloyl group, and a maleimide group. From the viewpoint of productivity, an acryloyl group and a (meth) acryloyl group are preferable.
　重合性官能基を１つのみ有する液晶化合物は、具体的には以下の一般式（a）で表される化合物が好ましい。 Specifically, the liquid crystal compound having only one polymerizable functional group is preferably a compound represented by the following general formula (a).
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
（式中、Z3は水素原子、ハロゲン原子、シアノ基又は炭素原子数１～２０の炭化水素基を表し、Z4は水素原子又はメチル基を表し、W3は単結合、-O-、-COO-又は-OCO-を表し、vは０～１８の整数を表し、uは０又は１を表し、D、E及びFはそれぞれ独立的に、1,4－フェニレン基、隣接しないCH基が窒素で置換された1,4－フェニレン基、1,4－シクロヘキシレン基、１つ又は隣接しない２つのCH2基が酸素又は硫黄原子で置換された1,4－シクロヘキシレン基、1,4－シクロヘキセニレン基を表すが、式中に存在する1,4－フェニレン基は炭素原子数１～７のアルキル基、アルコキシ基、アルカノイル基、シアノ基又はハロゲン原子で一つ以上置換されていても良く、Y6及びY7はそれぞれ独立的に単結合、-CH2CH2-、-CH2O-、-OCH2-、-COO-、-OCO-、-C≡C-、-CH=CH-、-CF=CF-、-（CH2）4-、-CH2CH2CH2O-、-OCH2CH2CH2-、-CH=CHCH2CH2-、-CH2CH2CH=CH-、-CH=CHCOO-、-OCOCH=CH-、-CH2CH2COO-、-CH2CH2OCO-、-COO CH2CH2-、-OCOCH2CH2-、-CH=N-、-N=CH-、-N=N-又は-CH=N-N=CH-を表し、Y6及びY7の少なくとも一つは-CH=CH-、-CH=CHCOO-、-OCOCH=CH-、-CH=N-、-N=CH-、-N=N-、-CH=N-N=CH-を表し、
Y8は単結合、-O-、-COO-、-OCO-又は-CH=CHCOO-を表す。）
　一般式（a）で表される化合物は以下で示される化合物がより好ましい。 (In the formula, Z 3 represents a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group having 1 to 20 carbon atoms, Z 4 represents a hydrogen atom or a methyl group, W 3 represents a single bond, —O—, -COO- or -OCO-, v represents an integer of 0 to 18, u represents 0 or 1, D, E and F are each independently a 1,4-phenylene group or a non-adjacent CH group. 1,4-phenylene group substituted with nitrogen, 1,4-cyclohexylene group, 1,4-cyclohexylene group in which one or two non-adjacent CH 2 groups are substituted with oxygen or sulfur atoms, 1, Represents a 4-cyclohexenylene group, and the 1,4-phenylene group present in the formula is substituted by one or more alkyl groups, alkoxy groups, alkanoyl groups, cyano groups or halogen atoms having 1 to 7 carbon atoms. Y 6 and Y 7 are each independently a single bond, —CH 2 CH 2 —, —CH 2 O—, —OCH 2 —, —COO—, —OCO—, —C≡C—, — CH = CH-, -CF = CF -, - (CH 2) 4 -, - CH 2 CH 2 CH 2 O -, - OCH 2 CH 2 CH 2 -, - CH = CHCH 2 CH 2 -, - CH 2 CH 2 CH = CH -, - CH = CHCOO-, -OCOCH = CH-, -CH 2 CH 2 COO-, -CH 2 CH 2 OCO-, -COO CH 2 CH 2- , -OCOCH 2 CH 2- , -CH = N-, -N = CH-, -N = N- or -CH = NN = CH-, wherein at least one of Y 6 and Y 7 is -CH = CH-, -CH = CHCOO-, -OCOCH = CH-, -CH = N-, -N = CH-, -N = N-, -CH = NN = CH-
Y 8 represents a single bond, —O—, —COO—, —OCO— or —CH═CHCOO—. )
The compound represented by the general formula (a) is more preferably a compound represented by the following.
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
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
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000040
Figure JPOXMLDOC01-appb-C000040
Figure JPOXMLDOC01-appb-C000041
Figure JPOXMLDOC01-appb-C000041
Figure JPOXMLDOC01-appb-C000042
Figure JPOXMLDOC01-appb-C000042
Figure JPOXMLDOC01-appb-C000043
Figure JPOXMLDOC01-appb-C000043
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000046
Figure JPOXMLDOC01-appb-C000046
Figure JPOXMLDOC01-appb-C000047
Figure JPOXMLDOC01-appb-C000047
Figure JPOXMLDOC01-appb-C000048
Figure JPOXMLDOC01-appb-C000048
Figure JPOXMLDOC01-appb-C000049
Figure JPOXMLDOC01-appb-C000049
（式中、ｌ、ｍ及びｎはそれぞれ独立して１～１０の整数を表し、Ｒは水素原子、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、カルボキシル基、カルバモイル基、シアノ基、ニトロ基、ハロゲン原子を表すが、これらの基が炭素数１～６のアルキル基、あるいは炭素数１～６のアルコキシ基の場合、全部が未置換であるか、あるいは１つ又は２つ以上のハロゲン原子により置換されていてもよい。これらの基がカルボキシル基、カルバモイル基の場合、末端の水素原子が未置換であるか、あるいは炭素数１～１０のアルキル基で置換されていてもよい。）
　これらの式において、Ｒは水素原子、炭素数１～３のアルキル基、炭素数１～３のアルコキシ基、又はシアノ基を表すことが好ましい。Ｒとしてシアノ基を有する化合物は、オリゴマー不純物の影響が大きいので、その濃度管理は重要である。 (Wherein, l, m and n each independently represents an integer of 1 to 10; R represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxyl group, or a carbamoyl group. , A cyano group, a nitro group, and a halogen atom, and when these groups are alkyl groups having 1 to 6 carbon atoms or alkoxy groups having 1 to 6 carbon atoms, they are all unsubstituted, When these groups are a carboxyl group or a carbamoyl group, the terminal hydrogen atom may be unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms. May be.)
In these formulas, R preferably represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a cyano group. Since the compound having a cyano group as R is greatly affected by oligomer impurities, its concentration control is important.
　これらの液晶化合物は、単独で使用することもできるし、２種類以上混合して使用することもできる。 These liquid crystal compounds can be used alone or in combination of two or more.
　一般式（a）で表される化合物の含有量は、５％～７０％が好ましく、７％～６０％が好ましく、９％～５０％が特に好ましい。 The content of the compound represented by the general formula (a) is preferably 5% to 70%, more preferably 7% to 60%, and particularly preferably 9% to 50%.
　液晶組成物に含まれる重合性液晶化合物として、重合性官能基を２つ有する液晶化合物は、硬化させて得られるフィルムの機械的強度を確保する観点から有用である。このような重合性官能基を２つ有する化合物としては、例えば、Ｈａｎｄｂｏｏｋ　ｏｆ　Ｌｉｑｕｉｄ　Ｃｒｙｓｔａｌｓ（Ｄ．Ｄｅｍｕｓ，Ｊ．Ｗ．Ｇｏｏｄｂｙ，Ｇ．Ｗ．Ｇｒａｙ，Ｈ．Ｗ．Ｓｐｉｅｓｓ，Ｖ．Ｖｉｌｌ編集、Ｗｉｌｅｙ－ＶＣＨ社発行，１９９８年）、季刊化学総説Ｎｏ．２２、液晶の化学（日本化学会編，１９９４年）、あるいは、特開平４－２２７６８４号公報、特開平１１－８００９０号公報、特開平１１－１１６５３８号公報、特開平１１－１４８０７９号公報、特開２０００－１７８２３３号公報、特開２００２－３０８８３１号公報、特開２００２－１４５８３０号公報、特開２００４－１２５８４２号公報等に記載されているような、１，４－フェニレン基１，４－シクロヘキレン基等の構造が複数繋がったメソゲンと呼ばれる剛直な部位と、ビニル基、アクリロイル基、（メタ）アクリロイル基といった重合性官能基を有する棒状重合性液晶化合物、あるいは特開２００４－２３７３号公報、特開２００４－９９４４６号公報に記載されているようなマレイミド基を有する棒状重合性液晶化合物が挙げられる。 As a polymerizable liquid crystal compound contained in the liquid crystal composition, a liquid crystal compound having two polymerizable functional groups is useful from the viewpoint of ensuring the mechanical strength of a film obtained by curing. Examples of such compounds having two polymerizable functional groups include, for example, Handbook of Liquid Crystals (D. Demus, JW Goodby, GW Gray, HW Spiss, V. Vill, edited by Wiley. -Published by VCH, 1998), Quarterly Chemical Review No. 22, Liquid Crystal Chemistry (edited by the Chemical Society of Japan, 1994), or Japanese Patent Laid-Open Nos. 4-227684, 11-80090, 11-116538, 11-148079, As described in JP 2000-178233 A, JP 2002-308831 A, JP 2002-145830 A, JP 2004-125842 A, and the like, 1,4-phenylene group 1,4-cyclohex A rod-like polymerizable liquid crystal compound having a rigid site called mesogen in which a plurality of structures such as a len group are connected, and a polymerizable functional group such as a vinyl group, an acryloyl group, and a (meth) acryloyl group, or JP-A-2004-2373, A rod-like polymerizable liquid crystal compound having a maleimide group as described in JP-A-2004-99446 And the like.
　重合性官能基は、ビニル基、アクリロイル基、（メタ）アクリロイル基、マレイミド基等が上げられるが、生産性の観点から、アクリロイル基、（メタ）アクリロイル基が好ましい。 Examples of the polymerizable functional group include a vinyl group, an acryloyl group, a (meth) acryloyl group, and a maleimide group. From the viewpoint of productivity, an acryloyl group and a (meth) acryloyl group are preferable.
　重合性官能基を２つ有する液晶化合物は、具体的には以下の一般式（ｂ）で表される化合物が好ましい。 Specifically, the liquid crystal compound having two polymerizable functional groups is preferably a compound represented by the following general formula (b).
Figure JPOXMLDOC01-appb-C000050
Figure JPOXMLDOC01-appb-C000050
（式中、Z5、Z6はそれぞれ独立的に水素原子、又はメチル基を表し、G、H及びIはそれぞれ独立的に、1,4－フェニレン基、隣接しないCH基が窒素で置換された1,4－フェニレン基、1,4－シクロヘキシレン基、１つ又は隣接しない２つのCH2基が酸素又は硫黄原子で置換された1,4－シクロヘキシレン基、1,4－シクロヘキセニレン基を表すが、式中に存在する1,4－フェニレン基は炭素原子数１～７のアルキル基、アルコキシ基、アルカノイル基、シアノ基又はハロゲン原子で一つ以上置換されていても良く、mは０から３の整数を表し、W1及びW2はそれぞれ独立的に単結合、-O-、-COO-又は-OCO-を表し、Y1及びY2はそれぞれ独立的に単結合、-COO-、-OCO-、-CH2CH2COO-、-CH2CH2OCO-、-COO CH2CH2-、-OCOCH2CH2-、-CH=N-、-N=CH-、-N=N-、-CH=N-N=CH-又は単結合を表し、Y1及びY2のうち少なくとも一つは-CH=CH-、-CH=CHCOO-、-OCOCH=CH-、-CH=N-、-N=CH-、-N=N-、-CH=N-N=CH-を表しr及びsはそれぞれ独立的に２～１８の整数を表すが、式中に存在する1,4－フェニレン基は炭素原子数１～７のアルキル基、アルコキシ基、アルカノイル基、シアノ基、又はハロゲン原子で一つ以上置換されていても良い。）
　一般式（ｂ）で表される化合物は以下で示される化合物がより好ましい。 (Wherein Z 5 and Z 6 each independently represent a hydrogen atom or a methyl group, G, H and I each independently represent a 1,4-phenylene group and a non-adjacent CH group substituted with nitrogen. 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexylene group in which one or two non-adjacent CH 2 groups are substituted with oxygen or sulfur atoms, 1,4-cyclohexenylene A 1,4-phenylene group present in the formula may be substituted with one or more alkyl groups, alkoxy groups, alkanoyl groups, cyano groups or halogen atoms having 1 to 7 carbon atoms; Represents an integer of 0 to 3, W 1 and W 2 each independently represent a single bond, —O—, —COO— or —OCO—, Y 1 and Y 2 each independently represent a single bond, — COO-, -OCO-, -CH 2 CH 2 COO-, -CH 2 CH 2 OCO-, -COO CH 2 CH 2- , -OCOCH 2 CH 2- , -CH = N-, -N = CH-, -N = N -, - CH = NN = CH- or a single bond, Y 1 At least one of the fine Y 2 is -CH = CH -, - CH = CHCOO -, - OCOCH = CH -, - CH = N -, - N = CH -, - N = N -, - CH = NN = CH— and r and s each independently represent an integer of 2 to 18, and the 1,4-phenylene group present in the formula is an alkyl group having 1 to 7 carbon atoms, an alkoxy group, an alkanoyl group, a cyano group One or more groups or halogen atoms may be substituted.)
The compound represented by the general formula (b) is more preferably a compound represented by the following.
Figure JPOXMLDOC01-appb-C000051
Figure JPOXMLDOC01-appb-C000051
Figure JPOXMLDOC01-appb-C000052
Figure JPOXMLDOC01-appb-C000052
Figure JPOXMLDOC01-appb-C000053
Figure JPOXMLDOC01-appb-C000053
Figure JPOXMLDOC01-appb-C000054
Figure JPOXMLDOC01-appb-C000054
Figure JPOXMLDOC01-appb-C000055
Figure JPOXMLDOC01-appb-C000055
Figure JPOXMLDOC01-appb-C000056
Figure JPOXMLDOC01-appb-C000056
Figure JPOXMLDOC01-appb-C000057
Figure JPOXMLDOC01-appb-C000057
Figure JPOXMLDOC01-appb-C000058
Figure JPOXMLDOC01-appb-C000058
Figure JPOXMLDOC01-appb-C000059
Figure JPOXMLDOC01-appb-C000059
Figure JPOXMLDOC01-appb-C000060
Figure JPOXMLDOC01-appb-C000060
Figure JPOXMLDOC01-appb-C000061
Figure JPOXMLDOC01-appb-C000061
Figure JPOXMLDOC01-appb-C000062
Figure JPOXMLDOC01-appb-C000062
Figure JPOXMLDOC01-appb-C000063
Figure JPOXMLDOC01-appb-C000063
Figure JPOXMLDOC01-appb-C000064
Figure JPOXMLDOC01-appb-C000064
Figure JPOXMLDOC01-appb-C000065
Figure JPOXMLDOC01-appb-C000065
Figure JPOXMLDOC01-appb-C000066
Figure JPOXMLDOC01-appb-C000066
Figure JPOXMLDOC01-appb-C000067
Figure JPOXMLDOC01-appb-C000067
Figure JPOXMLDOC01-appb-C000068
Figure JPOXMLDOC01-appb-C000068
Figure JPOXMLDOC01-appb-C000069
Figure JPOXMLDOC01-appb-C000069
（式中、ｍ及びｎはそれぞれ独立して１～１０の整数を表し、Ｒは水素原子、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、カルボキシル基、カルバモイル基、シアノ基、ニトロ基又はハロゲン原子を表すが、これらの基が炭素数１～６のアルキル基、あるいは炭素数１～６のアルコキシ基の場合、全部が未置換であるか、又は１つ又は２つ以上のハロゲン原子により置換されていてもよい。これらの基がカルボキシル基、カルバモイル基の場合、末端の水素原子が未置換であるか、又は炭素数１～１０のアルキル基で置換されていてもよい。）
Ｒは水素原子、炭素数１～３のアルキル基、炭素数１～３のアルコキシ基又はシアノ基が好ましい。 (In the formula, m and n each independently represent an integer of 1 to 10, and R represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxyl group, a carbamoyl group, cyano. A group, a nitro group or a halogen atom, and when these groups are alkyl groups having 1 to 6 carbon atoms or alkoxy groups having 1 to 6 carbon atoms, they are all unsubstituted, or one or two When these groups are a carboxyl group or a carbamoyl group, the terminal hydrogen atom may be unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms. Good.)
R is preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a cyano group.
　これらの液晶化合物は、単独で使用することもできるし、２種類以上混合して使用することもできる。 These liquid crystal compounds can be used alone or in combination of two or more.
　一般式（ｂ）で表される化合物の含有量は、５％～９０％が好ましく、１０％～＊８０％が好ましく、２０％～７０％が特に好ましい。 The content of the compound represented by the general formula (b) is preferably 5% to 90%, more preferably 10% to * 80%, and particularly preferably 20% to 70%.
　重合液晶組成物中には、目的に応じて、添加剤を含有させても良い。特に、近年は重合性液晶組成物を基板に塗布等の手段によって基板上に坦持させ、配向してから活性エネルギー線照射によって光学異方体を製造することが多くなってきたことから、一枚の基板上に重合性液晶組成物の層を形成した状態で、所望の配向状態が得られるよう添加剤を調節することは重要である。 In the polymerization liquid crystal composition, an additive may be contained depending on the purpose. In particular, in recent years, it has become more common to produce an optical anisotropic body by irradiating active energy rays after the polymerizable liquid crystal composition is supported on the substrate by means such as coating, and aligned. It is important to adjust the additives so that a desired alignment state can be obtained in a state where a layer of the polymerizable liquid crystal composition is formed on a single substrate.
　ホモジニアス（水平一軸）配向させる場合、およびコレステリック液晶をプラナー（水平）配向させる場合には、重合性液晶組成物を水平配向させるための化合物を添加する必要がある。このような化合物としては一般式（II） In the case of homogeneous (horizontal uniaxial) alignment and cholesteric liquid crystal alignment in the planar (horizontal) direction, it is necessary to add a compound for horizontally aligning the polymerizable liquid crystal composition. Such compounds include general formula (II)
Figure JPOXMLDOC01-appb-C000070
Figure JPOXMLDOC01-appb-C000070
（式中、R1、R2、R3及びR4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、該炭化水素基中の水素原子は１つ以上のハロゲン原子で置換されていても良い。）で表される繰り返し単位を有する化合物をあげることができる。 (Wherein R 1 , R 2 , R 3 and R 4 each independently represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and one hydrocarbon atom in the hydrocarbon group) And a compound having a repeating unit represented by the above-mentioned halogen atom may be used.
　一般式（II）で表される化合物は、例えばポリエチレン、ポリプロピレン、ポリイソブチレン、パラフィン、流動パラフィン、塩素化ポリプロピレン、塩素化パラフィン、又は塩素化流動パラフィンが挙げられる。 Examples of the compound represented by the general formula (II) include polyethylene, polypropylene, polyisobutylene, paraffin, liquid paraffin, chlorinated polypropylene, chlorinated paraffin, and chlorinated liquid paraffin.
　これ以外にも、フッ素原子が導入された化合物はムラ抑制の観点からも有効である。 In addition to this, compounds introduced with fluorine atoms are also effective from the viewpoint of suppressing unevenness.
　一般式（II）で表される繰り返し単位を有する化合物のうち、好適な構造として、式（II-a）～式（II-f） Among the compounds having a repeating unit represented by the general formula (II), as a suitable structure, the formula (II-a) to the formula (II-f)
Figure JPOXMLDOC01-appb-C000071
Figure JPOXMLDOC01-appb-C000071
で表される繰り返し単位を有する化合物が挙げられる。中でも、式（II-a）～式（II-e）で表される構造がより好ましく、式（II-a）及び式（II-c）で表される構造が特に好ましい。又、式（II-a）～式（II-f）で表される繰り返し単位を有する化合物を２種以上共重合させた共重合体も好ましい。この場合、式（II-a）及び式（II-b）を有する共重合体、式（II-a）及び式（II-c）を有する共重合体、式（II-a）及び式（II-f）を有する共重合体、及び、式（II-a）、（II-b）及び式（II-f）を有する共重合体がより好ましく、式（II-a）及び式（II-b）を有する共重合体、及び、式（II-a）、（II-b）及び式（II-f）を有する共重合体が特に好ましい。 The compound which has a repeating unit represented by these is mentioned. Among these, structures represented by the formulas (II-a) to (II-e) are more preferable, and structures represented by the formulas (II-a) and (II-c) are particularly preferable. A copolymer obtained by copolymerizing two or more compounds having a repeating unit represented by formulas (II-a) to (II-f) is also preferable. In this case, a copolymer having the formula (II-a) and the formula (II-b), a copolymer having the formula (II-a) and the formula (II-c), the formula (II-a) and the formula ( More preferred are copolymers having the formula II-f) and copolymers having the formulas (II-a), (II-b) and (II-f). Particularly preferred are copolymers having -b) and copolymers having the formulas (II-a), (II-b) and (II-f).
　該化合物の質量平均分子量は、小さすぎるとチルト角を減じる効果が乏しくなり、大きすぎると配向が長時間安定しないため最適な範囲が存在する。具体的には、２００～１００００００であることが好ましく、３００～１０００００であることがさらに好ましく、４００～８００００であることが特に好ましい。 If the mass average molecular weight of the compound is too small, the effect of reducing the tilt angle is poor, and if it is too large, the orientation is not stable for a long time, so there is an optimum range. Specifically, it is preferably 200 to 1000000, more preferably 300 to 100,000, and particularly preferably 400 to 80000.
　又、該化合物を、重合性液晶組成物中に０．０１～５質量％含有することが好ましく、０．０５～２質量％含有することがより好ましく、０．１～1質量％含有することが特に好ましい。 The compound is preferably contained in the polymerizable liquid crystal composition in an amount of 0.01 to 5% by mass, more preferably 0.05 to 2% by mass, and 0.1 to 1% by mass. Is particularly preferred.
　らせん配向させる場合には、コレステリック液晶相（キラルネマチック液晶相）を呈するようにキラル化合物を添加する。このようなキラル化合物としては、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１１－１９３２８７号公報、特開２００１－１５８７８８号公報、特表２００６－５２６６９号公報、特開２００７－２６９６３９号公報、特開２００７－２６９６４０号公報、２００９－８４１７８号公報等に記載されているような、イソソルビド、イソマンニット、グルコシド等のキラルな糖類を含み、かつ、１，４－フェニレン基１，４－シクロヘキレン基等の剛直な部位と、ビニル基、アクリロイル基、（メタ）アクリロイル基、また、マレイミド基といった重合性官能基を有する重合性キラル化合物、特開平８－２３９６６６号公報に記載されているような、テルペノイド誘導体からなる重合性キラル化合物、ＮＡＴＵＲＥ　ＶＯＬ３５　４６７～４６９ページ（１９９５年１１月３０日発行）、ＮＡＴＵＲＥ　ＶＯＬ３９２　４７６～４７９ページ（１９９８年４月２日発行）等に記載されているような、メソゲン基とキラル部位を有するスペーサーからなる重合性キラル化合物、あるいは特表２００４－５０４２８５号公報、特開２００７－２４８９４５号公報に記載されているような、ビナフチル基を含む重合性キラル化合物が挙げられる。中でも、らせんねじれ力（ＨＴＰ）の大きなキラル化合物は、本発明の重合性液晶組成物が作りやすく好ましい。 In the case of helical alignment, a chiral compound is added so as to exhibit a cholesteric liquid crystal phase (chiral nematic liquid crystal phase). Such a chiral compound preferably has one or more polymerizable functional groups. Examples of such compounds include JP-A-11-193287, JP-A-2001-158788, JP-T 2006-52669, JP-A-2007-269639, JP-A-2007-269640, 2009. -84178, which contains chiral saccharides such as isosorbide, isomannite, glucoside, and the like, and a rigid site such as 1,4-phenylene group and 1,4-cyclohexylene group, and a vinyl group A polymerizable chiral compound having a polymerizable functional group such as an acryloyl group, a (meth) acryloyl group, or a maleimide group, a polymerizable chiral compound comprising a terpenoid derivative as described in JP-A-8-239666, NATURE VOL35, pages 467-469 (November 30, 1995) Issue), NATURE VOL392, pages 476-479 (issued on April 2, 1998), or the like, or a polymerizable chiral compound comprising a mesogenic group and a spacer having a chiral moiety, or JP-T-2004-504285. And a polymerizable chiral compound containing a binaphthyl group as described in JP-A-2007-248945. Among them, a chiral compound having a large helical twisting power (HTP) is preferable because the polymerizable liquid crystal composition of the present invention can be easily produced.
　重合性液晶組成物で用いられる、キラル化合物は、具体的には以下に示されるような液晶化合物が例示される。 Specific examples of the chiral compound used in the polymerizable liquid crystal composition include the following liquid crystal compounds.
Figure JPOXMLDOC01-appb-C000072
Figure JPOXMLDOC01-appb-C000072
Figure JPOXMLDOC01-appb-C000073
Figure JPOXMLDOC01-appb-C000073
Figure JPOXMLDOC01-appb-C000074
Figure JPOXMLDOC01-appb-C000074
Figure JPOXMLDOC01-appb-C000075
Figure JPOXMLDOC01-appb-C000075
Figure JPOXMLDOC01-appb-C000076
Figure JPOXMLDOC01-appb-C000076
Figure JPOXMLDOC01-appb-C000077
Figure JPOXMLDOC01-appb-C000077
Figure JPOXMLDOC01-appb-C000078
Figure JPOXMLDOC01-appb-C000078
Figure JPOXMLDOC01-appb-C000079
Figure JPOXMLDOC01-appb-C000079
Figure JPOXMLDOC01-appb-C000080
Figure JPOXMLDOC01-appb-C000080
Figure JPOXMLDOC01-appb-C000081
Figure JPOXMLDOC01-appb-C000081
Figure JPOXMLDOC01-appb-C000082
Figure JPOXMLDOC01-appb-C000082
Figure JPOXMLDOC01-appb-C000083
Figure JPOXMLDOC01-appb-C000083
Figure JPOXMLDOC01-appb-C000084
Figure JPOXMLDOC01-appb-C000084
Figure JPOXMLDOC01-appb-C000085
Figure JPOXMLDOC01-appb-C000085
Figure JPOXMLDOC01-appb-C000086
Figure JPOXMLDOC01-appb-C000086
Figure JPOXMLDOC01-appb-C000087
Figure JPOXMLDOC01-appb-C000087
Figure JPOXMLDOC01-appb-C000088
Figure JPOXMLDOC01-appb-C000088
Figure JPOXMLDOC01-appb-C000089
Figure JPOXMLDOC01-appb-C000089
Figure JPOXMLDOC01-appb-C000090
Figure JPOXMLDOC01-appb-C000090
Figure JPOXMLDOC01-appb-C000091
Figure JPOXMLDOC01-appb-C000091
Figure JPOXMLDOC01-appb-C000092
Figure JPOXMLDOC01-appb-C000092
Figure JPOXMLDOC01-appb-C000093
Figure JPOXMLDOC01-appb-C000093
Figure JPOXMLDOC01-appb-C000094
Figure JPOXMLDOC01-appb-C000094
Figure JPOXMLDOC01-appb-C000095
Figure JPOXMLDOC01-appb-C000095
（式中、ｍ及びｎはそれぞれ独立して１～１０の整数を表し、Ｒは水素原子、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、カルボキシル基、カルバモイル基、シアノ基、ニトロ基、ハロゲン原子を表すが、これらの基が炭素数１～６のアルキル基、あるいは炭素数１～６のアルコキシ基の場合、全部が未置換であるか、又は１つ又は２つ以上のハロゲン原子により置換されていてもよい。これらの基がカルボキシル基、カルバモイル基の場合、末端の水素原子が未置換であるか、又は炭素数１～１０のアルキル基で置換されていてもよい。）
　これらのキラル化合物は、単独で使用することもできるし、２種類以上混合して使用することもできる。 (In the formula, m and n each independently represent an integer of 1 to 10, and R represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxyl group, a carbamoyl group, cyano. Represents a group, a nitro group, or a halogen atom. When these groups are an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, they are all unsubstituted, or one or two When these groups are a carboxyl group or a carbamoyl group, the terminal hydrogen atom may be unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms. Good.)
These chiral compounds can be used alone or in combination of two or more.
　重合性液晶組成物に重合開始剤を添加しても良い。重合開始剤としては、活性エネルギー線によって行う場合に使用する光重合開始剤として公知慣用のものが使用できる。例えば２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン（メルク社製「ダロキュア１１７３」）、１－ヒドロキシシクロヘキシルフェニルケトン（チバ・スペシャルティ・ケミカルズ社製「イルガキュア１８４」）、１－（４－イソプロピルフェニル）－２－ヒドロキシ－２－メチルプロパン－１－オン（メルク社製「ダロキュア１１１６」）、２－メチル－１－［（メチルチオ）フェニル］－２－モリホリノプロパン－１（チバ・スペシャルティ・ケミカルズ社製「イルガキュア９０７」）。ベンジルメチルケタ－ル（チバ・スペシャルティ・ケミカルズ社製「イルガキュア６５１」）２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）－ブタノン（チバ・スペシャルティ・ケミカルズ社製「イルガキュア３６９」）、２－ジメチルアミノ－２－（４－メチルベンジル）－１－（４－モルフォリリン－４－イル－フェニル）ブタン－１－オン（チバ・スペシャルティ・ケミカルズ社製「イルガキュア３７９」）、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン、ビス（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキサイド（ダロキュアＴＰＯ）、２，４，６－トリメチルベンゾイル－ジフェニル－フォスフィンオキサイド（チバ・スペシャルティ・ケミカルズ社製「イルガキュア８１９」）、１，２－オクタンジオン，１－［４－（フェニルチオ）－，２－（Ｏ－ベンゾイルオキシム）］、エタノン（チバ・スペシャルティ・ケミカルズ社製「イルガキュアＯＸＥ０１」）、１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］－，１－（Ｏ－アセチルオキシム）（チバ・スペシャルティ・ケミカルズ社製「イルガキュアＯＸＥ０２」）。２，４－ジエチルチオキサントン（日本化薬社製「カヤキュアＤＥＴＸ」）とｐ－ジメチルアミノ安息香酸エチル（日本化薬社製「カヤキュアＥＰＡ」）との混合物、イソプロピルチオキサントン（ワ－ドプレキンソップ社製「カンタキュア－ＩＴＸ」）とｐ－ジメチルアミノ安息香酸エチルとの混合物、アシルフォスフィンオキシド（ＢＡＳＦ社製「ルシリンＴＰＯ」）、などが挙げられる。光重合開始剤の含有率１～１０質量が好ましく、２～７質量％が特に好ましい。これらは、単独で使用することもできるし、２種類以上混合して使用することもできる。 A polymerization initiator may be added to the polymerizable liquid crystal composition. As a polymerization initiator, a well-known usual thing can be used as a photoinitiator used when performing by an active energy ray. For example, 2-hydroxy-2-methyl-1-phenylpropan-1-one (“Darocur 1173” manufactured by Merck), 1-hydroxycyclohexyl phenyl ketone (“Irgacure 184” manufactured by Ciba Specialty Chemicals), 1- ( 4-Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one ("Darocur 1116" manufactured by Merck & Co.), 2-methyl-1-[(methylthio) phenyl] -2-morpholinopropane-1 ( “Irgacure 907” manufactured by Ciba Specialty Chemicals). Benzylmethylketal (“Irgacure 651” manufactured by Ciba Specialty Chemicals) 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone (“Irgacure 369” manufactured by Ciba Specialty Chemicals) ), 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) butan-1-one (“Irgacure 379” manufactured by Ciba Specialty Chemicals), 2 , 2-Dimethoxy-1,2-diphenylethane-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Darocur TPO), 2,4,6-trimethylbenzoyl-diphenyl-phosphine Oxide ("Irgaku" manufactured by Ciba Specialty Chemicals) 819 "), 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone (" Irgacure OXE01 "manufactured by Ciba Specialty Chemicals), 1- [9 -Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) ("Irgacure OXE02" manufactured by Ciba Specialty Chemicals). A mixture of 2,4-diethylthioxanthone (“Kayacure DETX” manufactured by Nippon Kayaku Co., Ltd.) and ethyl p-dimethylaminobenzoate (“Kayacure EPA” manufactured by Nippon Kayaku Co., Ltd.) -ITX ") and ethyl p-dimethylaminobenzoate, acylphosphine oxide (" Lucirin TPO "manufactured by BASF), and the like. The content of the photopolymerization initiator is preferably 1 to 10% by mass, particularly preferably 2 to 7% by mass. These can be used alone or in combination of two or more.
　また、熱重合開始剤を添加しても良い。熱重合開始剤としては、例えば、メチルアセトアセテイトパーオキサイド、キュメンハイドロパーオキサイド、ベンゾイルパーオキサイド、ビス（４－ｔ－ブチルシクロヘキシル）パ－オキシジカーボネイト、ｔ－ブチルパーオキシベンゾエイト、メチルエチルケトンパーオキサイド、１，１－ビス（ｔ－ヘキシルパ－オキシ）３，３，５－トリメチルシクロヘキサン、ｐ－ペンタハイドロパーオキサイド、ｔ－ブチルハイドロパーオキサイド、ジクミルパーオキサイド、イソブチルパーオキサイド、ジ（３－メチル－３－メトキシブチル）パーオキシジカーボネイト、１，１－ビス（ｔ－ブチルパーオキシ）シクロヘキサン等の有機過酸化物、２，２’－アゾビスイソブチロニトリル、２，２’－アゾビス（２，４－ジメチルバレロニトリル）等のアゾニトリル化合物、２，２’－アゾビス（２－メチル－Ｎ－フェニルプロピオン－アミヂン）ジハイドロクロライド等のアゾアミヂン化合物、２，２’アゾビス｛２－メチル－Ｎ－［１，１－ビス（ヒドロキシメチル）－２－ヒドロキシエチル］プロピオンアミド｝等のアゾアミド化合物、２，２’アゾビス（２，４，４－トリメチルペンタン）等のアルキルアゾ化合物等を使用することができる。熱重合開始剤の含有率１～１０質量が好ましく、２～６質量％が特に好ましい。これらは、単独で使用することもできるし、２種類以上混合して使用することもできる。 Further, a thermal polymerization initiator may be added. Examples of the thermal polymerization initiator include methyl acetoacetate peroxide, cumene hydroperoxide, benzoyl peroxide, bis (4-t-butylcyclohexyl) peroxydicarbonate, t-butylperoxybenzoate, and methyl ethyl ketone peroxide. Oxide, 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, p-pentahydroperoxide, t-butylhydroperoxide, dicumyl peroxide, isobutyl peroxide, di (3- Methyl-3-methoxybutyl) peroxydicarbonate, organic peroxides such as 1,1-bis (t-butylperoxy) cyclohexane, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-Dimethylvaleronitrile ), Azonitrile compounds such as 2,2′-azobis (2-methyl-N-phenylpropion-amidin) dihydrochloride, 2,2′azobis {2-methyl-N- [1,1-bis An azoamide compound such as (hydroxymethyl) -2-hydroxyethyl] propionamide}, an alkylazo compound such as 2,2′azobis (2,4,4-trimethylpentane), and the like can be used. The content of the thermal polymerization initiator is preferably 1 to 10% by mass, particularly preferably 2 to 6% by mass. These can be used alone or in combination of two or more.
　また、重合性液晶組成物に、重合禁止剤を添加することが好ましい。重合禁止剤としては、フェノール系化合物、キノン系化合物、アミン系化合物、チオエーテル系化合物、ニトロソ化合物、等が挙げられる。 In addition, it is preferable to add a polymerization inhibitor to the polymerizable liquid crystal composition. Examples of the polymerization inhibitor include phenol compounds, quinone compounds, amine compounds, thioether compounds, nitroso compounds, and the like.
　フェノール系化合物としては、ｐ－メトキシフェノール、クレゾール、ｔ－ブチルカテコール、３．５－ジ－ｔ－ブチル－４－ヒドロキシトルエン、２．２'－メチレンビス（４－メチル－６－ｔ－ブチルフェノール）、２．２'－メチレンビス（４－エチル－６－ｔ－ブチルフェノール）、４．４'－チオビス（３－メチル－６－ｔ－ブチルフェノール）、４－メトキシ－１－ナフトール、４，４’－ジアルコキシ－２，２’－ビ－１－ナフトール、等が挙げられる。
キノン系化合物としては、ヒドロキノン、メチルヒドロキノン、ｔｅｒｔ－ブチルヒドロキノン、ｐ－ベンゾキノン、メチル－ｐ－ベンゾキノン、ｔｅｒｔ－ブチル－ｐ－ベンゾキノン、２，５－ジフェニルベンゾキノン、２－ヒドロキシ－１，４－ナフトキノン、１，４－ナフトキノン、２，３－ジクロロ－１，４－ナフトキノン、アントラキノン、ジフェノキノン等が挙げられる。
アミン系化合物としては、ｐ－フェニレンジアミン、４－アミノジフェニルアミン、Ｎ．Ｎ'－ジフェニル－ｐ－フェニレンジアミン、Ｎ－ｉ－プロピル－Ｎ'－フェニル－ｐ－フェニレンジアミン、Ｎ－（１．３－ジメチルブチル）－Ｎ'－フェニル－ｐ－フェニレンジアミン、Ｎ．Ｎ'－ジ－２－ナフチル－ｐ－フェニレンジアミン、ジフェニルアミン、Ｎ－フェニル－β－ナフチルアミン、４．４'－ジクミル－ジフェニルアミン、４．４'－ジオクチル－ジフェニルアミン等が挙げられる。
チオエーテル系化合物としては、フェノチアジン、ジステアリルチオジプロピオネート等が挙げられる。
ニトロソ系化合物としては、Ｎ－ニトロソジフェニルアミン、Ｎ－ニトロソフェニルナフチルアミン、Ｎ－ニトロソジナフチルアミン、ｐ－ニトロソフェノール、ニトロソベンゼン、ｐ－ニトロソジフェニルアミン、α－ニトロソ－β－ナフトール等、Ｎ、Ｎ－ジメチルｐ－ニトロソアニリン、ｐ－ニトロソジフェニルアミン、ｐ－ニトロンジメチルアミン、ｐ－ニトロン－Ｎ、Ｎ－ジエチルアミン、Ｎ－ニトロソエタノールアミン、Ｎ－ニトロソジ－ｎ－ブチルアミン、Ｎ－ニトロソ－Ｎ　－ｎ－ブチル－４－ブタノールアミン、Ｎ－ニトロソ－ジイソプロパノールアミン、Ｎ－ニトロソ－Ｎ－エチル－４－ブタノールアミン、５－ニトロソ－８－ヒドロキシキノリン、Ｎ－ニトロソモルホリン、Ｎ－二トロソーＮ－フェニルヒドロキシルアミンアンモニウム塩、二トロソベンゼン、２，４．６－トリーｔｅｒｔ－ブチルニトロンベンゼン、Ｎ－ニトロソ－Ｎ－メチル－ｐ－トルエンスルホンアミド、Ｎ－ニトロソ－Ｎ－エチルウレタン、Ｎ－ニトロソ－Ｎ－ｎ－プロピルウレタン、１－ニトロソ－２－ナフトール、２－ニトロソー１－ナフトール、１－ニトロソ－２－ナフトール－３，６－スルホン酸ナトリウム、２－ニトロソ－１－ナフトール－４－スルホン酸ナトリウム、２－ニトロソ－５－メチルアミノフェノール塩酸塩、２－ニトロソ－５－メチルアミノフェノール塩酸塩等が挙げられる。 Examples of phenolic compounds include p-methoxyphenol, cresol, t-butylcatechol, 3.5-di-t-butyl-4-hydroxytoluene, 2.2'-methylenebis (4-methyl-6-t-butylphenol) 2.2′-methylenebis (4-ethyl-6-tert-butylphenol), 4.4′-thiobis (3-methyl-6-tert-butylphenol), 4-methoxy-1-naphthol, 4,4′- Dialkoxy-2,2′-bi-1-naphthol, and the like.
Examples of quinone compounds include hydroquinone, methylhydroquinone, tert-butylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, tert-butyl-p-benzoquinone, 2,5-diphenylbenzoquinone, 2-hydroxy-1,4-naphthoquinone 1,4-naphthoquinone, 2,3-dichloro-1,4-naphthoquinone, anthraquinone, diphenoquinone and the like.
Examples of amine compounds include p-phenylenediamine, 4-aminodiphenylamine, N.I. N'-diphenyl-p-phenylenediamine, Ni-propyl-N'-phenyl-p-phenylenediamine, N- (1.3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N.I. N′-di-2-naphthyl-p-phenylenediamine, diphenylamine, N-phenyl-β-naphthylamine, 4.4′-dicumyl-diphenylamine, 4.4′-dioctyl-diphenylamine and the like.
Examples of thioether compounds include phenothiazine and distearyl thiodipropionate.
Examples of nitroso compounds include N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, N-nitrosodinaphthylamine, p-nitrosophenol, nitrosobenzene, p-nitrosodiphenylamine, α-nitroso-β-naphthol, and the like, N, N-dimethyl p-nitrosoaniline, p-nitrosodiphenylamine, p-nitronedimethylamine, p-nitrone-N, N-diethylamine, N-nitrosoethanolamine, N-nitrosodi-n-butylamine, N-nitroso-N-n-butyl- 4-butanolamine, N-nitroso-diisopropanolamine, N-nitroso-N-ethyl-4-butanolamine, 5-nitroso-8-hydroxyquinoline, N-nitrosomorpholine, N-nitroso-N-phenylhydroxylamine Ammonium salt, ditrosobenzene, 2,4.6-tri-tert-butylnitronebenzene, N-nitroso-N-methyl-p-toluenesulfonamide, N-nitroso-N-ethylurethane, N-nitroso-N- n-propyl urethane, 1-nitroso-2-naphthol, 2-nitroso 1-naphthol, 1-nitroso-2-naphthol-3,6-sodium sulfonate, 2-nitroso-1-naphthol-4-sodium sulfonate, Examples include 2-nitroso-5-methylaminophenol hydrochloride and 2-nitroso-5-methylaminophenol hydrochloride.
　さらに重合性液晶組成物には、塗膜のレベリング性を確保する目的で界面活性剤を添加することが好ましい。含有することができる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をあげることができ、特に含フッ素界面活性剤、シリコーン誘導体が好ましい。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）等の例をあげることができる。界面活性剤の好ましい添加量は、重合性液晶組成物中に含有される界面活性剤以外の成分や、使用温度等によって異なるが、重合性液晶組成物中に０．０１～１質量％含有することが好ましく、０．０２～０．５質量％含有することがさらに好ましく、０．０３～０．１質量％含有することが特に好ましい。含有量が０．０１質量％より低いときは膜厚ムラ低減効果が得にくい。一般式（I）で表される繰り返し単位を有する水平配向添加剤の含有量と界面活性剤の含有量の合計が０．０２～０．５質量％であることが好ましく、０．０５～０．４質量％含有することがさらに好ましく、０．１～０．２質量％含有することが特に好ましい。 Furthermore, it is preferable to add a surfactant to the polymerizable liquid crystal composition for the purpose of ensuring the leveling property of the coating film. Surfactants that can be included include alkyl carboxylates, alkyl phosphates, alkyl sulfonates, fluoroalkyl carboxylates, fluoroalkyl phosphates, fluoroalkyl sulfonates, polyoxyethylene derivatives, fluoro Examples thereof include alkylethylene oxide derivatives, polyethylene glycol derivatives, alkylammonium salts, fluoroalkylammonium salts, silicone derivatives and the like, and fluorine-containing surfactants and silicone derivatives are particularly preferable. 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 -490, 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”, and “TEGO Rad2700” (above, manufactured by TEGO). The preferred addition amount of the surfactant varies depending on components other than the surfactant contained in the polymerizable liquid crystal composition, the use temperature, etc., but is contained in the polymerizable liquid crystal composition in an amount of 0.01 to 1% by mass. The content is preferably 0.02 to 0.5% by mass, more preferably 0.03 to 0.1% by mass. When the content is lower than 0.01% by mass, it is difficult to obtain the effect of reducing film thickness unevenness. The total content of the horizontal alignment additive having a repeating unit represented by the general formula (I) and the content of the surfactant is preferably 0.02 to 0.5% by mass, and 0.05 to 0 The content is more preferably 4% by mass, and particularly preferably 0.1 to 0.2% by mass.
　重合性液晶組成物には、目的に応じて他の添加剤、例えば、チキソ剤、界面活性剤、紫外線吸収剤、赤外線吸収剤、抗酸化剤、表面処理剤等の添加剤を液晶の配向能を著しく低下させない程度添加することができる。 Depending on the purpose, the polymerizable liquid crystal composition may contain other additives such as thixotropic agents, surfactants, ultraviolet absorbers, infrared absorbers, antioxidants, surface treatment agents, and the like. Can be added to such an extent that it does not significantly decrease.
　本発明の光学異方体は、オリゴマー純度を管理した重合性液晶組成物を基材に塗布等の方法によって製膜し、その後、硬化させることによって作製することができる。 The optical anisotropic body of the present invention can be produced by forming a polymerizable liquid crystal composition with controlled oligomer purity on a substrate by a method such as coating, and then curing.
　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。 The base material used for the optical anisotropic body of the present invention is a base material usually used for a liquid crystal device, a display, an optical component or an optical film, and when dried after application of the polymerizable liquid crystal composition of the present invention, or The material is not particularly limited as long as it is a material having heat resistance capable of withstanding heating at the time of manufacturing a liquid crystal device. 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, cellulose derivatives, polyolefins, polyesters, polyolefins, polycarbonates, polyacrylates, polyarylates, polyether sulfones, polyimides, polyphenylene sulfides, polyphenylene ethers, nylons, polystyrenes, and the like can be given. Of these, plastic substrates such as polyester, polystyrene, polyolefin, cellulose derivatives, polyarylate, and polycarbonate are preferable.
　重合性液晶組成物の塗布性や硬化によって得られる光学異方体の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。 In order to improve the adhesiveness of the optically anisotropic body obtained by applying and curing the polymerizable liquid crystal composition, 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 substrate surface by a method such as vapor deposition, or in order to add an 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ることが好ましい。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、ポリエーテルサルフォン、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。 Further, the substrate is usually subjected to an alignment treatment or an alignment film so that the polymerizable liquid crystal composition is aligned when the polymerizable liquid crystal composition of the present invention is applied and dried. It is preferable. 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.
　重合性液晶材料を基材に塗布するための法としては、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。溶剤で希釈した重合性液晶組成物を塗布することが好ましい。使用する溶剤は、基材上に塗布した際に基材、あるいは、基材上に形成されている配向膜を溶解させないものであれば良い。また、使用する溶剤としては本発明の重合性コレステリック液晶組成物を良好に溶解性させるものが好ましい。使用することができる溶剤としては、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。これらは、単独で使用することもできるし、２種類以上混合して使用することもできる。 Applicable methods such as applicator method, bar coating method, spin coating method, gravure printing method, flexographic printing method, ink jet method, die coating method, cap coating method, dipping, etc. are known as methods for applying the polymerizable liquid crystal material to the substrate. Conventional methods can be performed. It is preferable to apply a polymerizable liquid crystal composition diluted with a solvent. The solvent to be used may be any solvent that does not dissolve the substrate or the alignment film formed on the substrate when applied on the substrate. Moreover, as a solvent to be used, a solvent that favorably dissolves the polymerizable cholesteric liquid crystal composition of the present invention is preferable. Examples of solvents that can be used 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, and cyclohexanone. Ketone solvents such as tetrahydrofuran, ether solvents such as tetrahydrofuran, 1,2-dimethoxyethane, anisole, amide solvents such as N, N-dimethylformamide, N-methyl-2-pyrrolidone, propylene glycol monomethyl ether acetate, diethylene glycol Examples include monomethyl ether acetate, γ-butyrolactone, chlorobenzene and the like. These can be used alone or in combination of two or more.
　溶剤の比率は、本発明に用いられる重合性液晶組成物が通常塗布により行われることから、塗布した状態を著しく損なわない限りは特に制限はないが、重合性液晶組成物の固形分と溶剤の比率が０．１：９９．９～８０：２０が好ましく、塗布性を考慮すると、１：９９～６０：４０がさらに好ましい
　溶剤を使用した場合、60～100℃、さらに好ましくは80～90℃で加熱して溶剤を揮発させることが好ましい。加熱時間は5秒～3分が好ましい。 The ratio of the solvent is not particularly limited as long as the polymerizable liquid crystal composition used in the present invention is usually applied by coating, so long as the applied state is not significantly impaired, but the solid content of the polymerizable liquid crystal composition and the solvent The ratio is preferably 0.1: 99.9 to 80:20, and more preferably 1:99 to 60:40 in view of coating properties. When a solvent is used, 60 to 100 ° C., more preferably 80 to 90 ° C. It is preferable to evaporate the solvent by heating at The heating time is preferably 5 seconds to 3 minutes.
　本発明の重合性液晶組成物の重合操作については、重合性液晶組成物中の溶剤を乾燥等で除去した後、所望状態に配向した状態で一般に活性エネルギー線を照射することによって行うのが好ましい。活性エネルギー線としては紫外線、電子線を挙げることができる。装置の簡易さから、活性エネルギー線として紫外線を使用することが好ましい。重合を紫外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液晶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。紫外光の強度としては、1～100mW/cm2が好ましく、2～50mW/cm2が更に好ましく、5～30mW/cm2が特に好ましい。照射エネルギーとしては5～200mJ/cm2が好ましく、10～150mJ/cm2が更に好ましく、20～120ｍJ/cm2が特に好ましい。 The polymerization operation of the polymerizable liquid crystal composition of the present invention is preferably performed by generally irradiating active energy rays in a state of being oriented in a desired state after removing the solvent in the polymerizable liquid crystal composition by drying or the like. . Examples of active energy rays include ultraviolet rays and electron beams. From the simplicity of the apparatus, it is preferable to use ultraviolet rays as the active energy ray. When the polymerization is performed by ultraviolet 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 liquid crystal 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 intensity of the ultraviolet light is preferably 1 ~ 100mW / cm 2, more preferably 2 ~ 50mW / cm 2, particularly preferably 5 ~ 30mW / cm 2. Preferably 5 ~ 200mJ / cm 2 as irradiation energy, more preferably 10 ~ 150mJ / cm 2, particularly preferably 20 ~ 120mJ / cm 2.
　得られる光学異方体の耐溶剤特性や耐熱性の向上のために、光学異方体を加熱処理することもできる。その加熱温度は、基材として有機材料を使用する場合、基材のガラス転移点を越えない範囲での加熱が好ましい。 In order to improve the solvent resistance and heat resistance of the obtained optical anisotropic body, the optical anisotropic body can be heat-treated. The heating temperature is preferably within a range not exceeding the glass transition point of the base material when an organic material is used as the base material.
　以下に本発明を合成例、実施例、及び、比較例によって説明するが、もとより本発明はこれらに限定されるものではない。なお、特に断りのない限り、「％」は質量基準である。また、ヘイズの測定は、日本電色工業株式会社製のＮＤＨ-2000を用いて行った。 Hereinafter, the present invention will be described with reference to synthesis examples, examples, and comparative examples, but the present invention is not limited to these examples. Unless otherwise specified, “%” is based on mass. Moreover, the measurement of haze was performed using NDH-2000 by Nippon Denshoku Industries Co., Ltd.
（実施例１）
　式（Ａ－１）で表される重合性液晶化合物15.18%、式（Ａ－２）で表される重合性液晶化合物6.50%、式（Ｂ－１）で表される重合性液晶化合物23.85%、式（B－２）で表される重合性液晶化合物32.52%、式（Ｃ－１）で表される重合性キラル化合物7.01％、式（Ｄ－１）で表される重合性液晶化合物8.67％、式（Ｅ－１）で表される液晶化合物3.25％、式（Ｆ－１）で表される光重合開始剤2.17％、式（Ｆ－２）で表される光重合開始剤0.44部、ｐ－メトキシフェノール（Ｅ－１）0.44部を混合して重合性コレステリック液晶組成物（１）を得た。この重合性コレステリック液晶組成物中に含まれるオリゴマー不純物をGPC及びNMRを用いて解析したところ、シアノ基を有する3～4量体不純物（I－１）、（I－２）の合計が182ppm、シアノ基を有する2量体不純物（I－３）、（I－４）の合計が1182ppm、シアノ基を有さない3～4量体不純物（I－５）～（I－８）の総量が43ppm、シアノ基を有さない2量体不純物（I－９）～（I－１２）の総量が6385ppm、であった。
この重合性コレステリック液晶組成物（１）における式（Ia）から計算されるXa値は、434であった。 (Example 1)
15.18% polymerizable liquid crystal compound represented by formula (A-1), 6.50% polymerizable liquid crystal compound represented by formula (A-2), 23.85% polymerizable liquid crystal compound represented by formula (B-1) 32.52% of a polymerizable liquid crystal compound represented by the formula (B-2), 7.01% of a polymerizable chiral compound represented by the formula (C-1), 8.67% of a polymerizable liquid crystal compound represented by the formula (D-1) %, Liquid crystal compound represented by formula (E-1) 3.25%, photopolymerization initiator represented by formula (F-1) 2.17%, photopolymerization initiator represented by formula (F-2) 0.44 parts Then, 0.44 part of p-methoxyphenol (E-1) was mixed to obtain a polymerizable cholesteric liquid crystal composition (1). The oligomer impurities contained in this polymerizable cholesteric liquid crystal composition were analyzed using GPC and NMR. As a result, the total of ternary tetramer impurities (I-1) and (I-2) having a cyano group was 182 ppm, The total amount of dimer impurities (I-3) and (I-4) having a cyano group is 1182 ppm, and the total amount of tri to tetramer impurities (I-5) to (I-8) having no cyano group is The total amount of dimer impurities (I-9) to (I-12) having no cyano group was 4385 ppm.
The Xa value calculated from the formula (Ia) in this polymerizable cholesteric liquid crystal composition (1) was 434.
Figure JPOXMLDOC01-appb-C000096
Figure JPOXMLDOC01-appb-C000096
Figure JPOXMLDOC01-appb-C000097
Figure JPOXMLDOC01-appb-C000097
Figure JPOXMLDOC01-appb-C000098
Figure JPOXMLDOC01-appb-C000098
Figure JPOXMLDOC01-appb-C000099
Figure JPOXMLDOC01-appb-C000099
Figure JPOXMLDOC01-appb-C000100
Figure JPOXMLDOC01-appb-C000100
Figure JPOXMLDOC01-appb-C000101
Figure JPOXMLDOC01-appb-C000101
Figure JPOXMLDOC01-appb-C000102
Figure JPOXMLDOC01-appb-C000102
Figure JPOXMLDOC01-appb-C000103
Figure JPOXMLDOC01-appb-C000103
Figure JPOXMLDOC01-appb-C000104
Figure JPOXMLDOC01-appb-C000104
Figure JPOXMLDOC01-appb-C000105
Figure JPOXMLDOC01-appb-C000105
（式中、R1、R2のうち一方は水素原子、もう一方は、式（I-1b）を表し、m1は3または4を表す） (In the formula, one of R 1 and R 2 represents a hydrogen atom, the other represents the formula (I-1b), and m1 represents 3 or 4)
Figure JPOXMLDOC01-appb-C000106
Figure JPOXMLDOC01-appb-C000106
（*は結合点を表す） (* Represents the point of attachment)
Figure JPOXMLDOC01-appb-C000107
Figure JPOXMLDOC01-appb-C000107
（式中、R3、R4のうち一方は水素原子、もう一方は、式（I-2b）を表し、m2は3または4を表す） (In the formula, one of R 3 and R 4 represents a hydrogen atom, the other represents the formula (I-2b), and m2 represents 3 or 4)
Figure JPOXMLDOC01-appb-C000108
Figure JPOXMLDOC01-appb-C000108
（*は結合点を表す） (* Represents the point of attachment)
Figure JPOXMLDOC01-appb-C000109
Figure JPOXMLDOC01-appb-C000109
（式中、R5、R6のうち一方は水素原子、もう一方は、式（I-3b）を表す） (In the formula, one of R 5 and R 6 represents a hydrogen atom, and the other represents the formula (I-3b))
Figure JPOXMLDOC01-appb-C000110
Figure JPOXMLDOC01-appb-C000110
（*は結合点を表す） (* Represents the point of attachment)
Figure JPOXMLDOC01-appb-C000111
Figure JPOXMLDOC01-appb-C000111
（式中、R7、R8のうち一方は水素原子、もう一方は、式（I-4b）を表す） (In the formula, one of R 7 and R 8 represents a hydrogen atom, and the other represents the formula (I-4b))
Figure JPOXMLDOC01-appb-C000112
Figure JPOXMLDOC01-appb-C000112
（*は結合点を表す） (* Represents the point of attachment)
Figure JPOXMLDOC01-appb-C000113
Figure JPOXMLDOC01-appb-C000113
（式中、R9、R10のうち一方は水素原子、もう一方は、式（I-5b）を表し、m3は3または4を表す） (In the formula, one of R 9 and R 10 represents a hydrogen atom, the other represents the formula (I-5b), and m3 represents 3 or 4)
Figure JPOXMLDOC01-appb-C000114
Figure JPOXMLDOC01-appb-C000114
（*は結合点を表す） (* Represents the point of attachment)
Figure JPOXMLDOC01-appb-C000115
Figure JPOXMLDOC01-appb-C000115
（式中、R11、R12のうち一方は水素原子、もう一方は、式（I-6b）を表し、m4は3または4を表す） (In the formula, one of R 11 and R 12 represents a hydrogen atom, the other represents the formula (I-6b), and m4 represents 3 or 4)
Figure JPOXMLDOC01-appb-C000116
Figure JPOXMLDOC01-appb-C000116
（*は結合点を表す） (* Represents the point of attachment)
Figure JPOXMLDOC01-appb-C000117
Figure JPOXMLDOC01-appb-C000117
（式中、R13、R14のうち一方は水素原子、もう一方は、式（I-7b）を表し、m5は3または4を表す） (In the formula, one of R 13 and R 14 represents a hydrogen atom, the other represents the formula (I-7b), and m5 represents 3 or 4)
Figure JPOXMLDOC01-appb-C000118
Figure JPOXMLDOC01-appb-C000118
（*は結合点を表す） (* Represents the point of attachment)
Figure JPOXMLDOC01-appb-C000119
Figure JPOXMLDOC01-appb-C000119
（式中、R15、R16のうち一方は水素原子、もう一方は、式（I-8b）を表し、m6は3または4を表す） (In the formula, one of R 15 and R 16 represents a hydrogen atom, the other represents the formula (I-8b), and m6 represents 3 or 4)
Figure JPOXMLDOC01-appb-C000120
Figure JPOXMLDOC01-appb-C000120
（*は結合点を表す） (* Represents the point of attachment)
Figure JPOXMLDOC01-appb-C000121
Figure JPOXMLDOC01-appb-C000121
（式中、R17、R18のうち一方は水素原子、もう一方は、式（I-5b）を表す） (In the formula, one of R 17 and R 18 represents a hydrogen atom, and the other represents the formula (I-5b))
Figure JPOXMLDOC01-appb-C000122
Figure JPOXMLDOC01-appb-C000122
Figure JPOXMLDOC01-appb-C000123
Figure JPOXMLDOC01-appb-C000123
（式中、R19、R20のうち一方は水素原子、もう一方は、式（I-6b）を表す） (In the formula, one of R 19 and R 20 represents a hydrogen atom, and the other represents the formula (I-6b))
Figure JPOXMLDOC01-appb-C000124
Figure JPOXMLDOC01-appb-C000124
（*は結合点を表す） (* Represents the point of attachment)
Figure JPOXMLDOC01-appb-C000125
Figure JPOXMLDOC01-appb-C000125
（式中、R21、R22のうち一方は水素原子、もう一方は、式（I-7b）を表す） (In the formula, one of R 21 and R 22 represents a hydrogen atom, and the other represents the formula (I-7b))
Figure JPOXMLDOC01-appb-C000126
Figure JPOXMLDOC01-appb-C000126
（*は結合点を表す） (* Represents the point of attachment)
Figure JPOXMLDOC01-appb-C000127
Figure JPOXMLDOC01-appb-C000127
（式中、R23、R24のうち一方は水素原子、もう一方は、式（I-8b）を表す） (In the formula, one of R 23 and R 24 represents a hydrogen atom, and the other represents the formula (I-8b))
（*は結合点を表す）
　調製した重合性コレステリック液晶組成物（１）に、水平配向添加剤として質量平均分子量1650のポリプロピレンを0.10％添加して本発明の重合性コレステリック液晶組成物（Ａ）を調製した。この重合性コレステリック液晶組成物（１’）に、トルエン30％、シクロヘキサノン30％を加えて、重合性液晶組成物（１’）の溶液を調製した。 (* Represents the point of attachment)
The polymerizable cholesteric liquid crystal composition (A) of the present invention was prepared by adding 0.10% of polypropylene having a weight average molecular weight of 1650 as a horizontal alignment additive to the prepared polymerizable cholesteric liquid crystal composition (1). To this polymerizable cholesteric liquid crystal composition (1 ′), 30% toluene and 30% cyclohexanone were added to prepare a solution of the polymerizable liquid crystal composition (1 ′).
　次に配向膜用ポリイミド溶液を厚さ０．７ｍｍのガラス基材にスピンコート法を用いて塗布し、１００℃で１０分乾燥した後、２００℃で６０分焼成することにより塗膜を得た。得られた塗膜をラビング処理して、本発明のコレステリック反射フィルム用基材とした。ラビング処理は、市販のラビング装置を用いて行った。 Next, the polyimide solution for alignment film was applied to a glass substrate having a thickness of 0.7 mm using a spin coating method, dried at 100 ° C. for 10 minutes, and then baked at 200 ° C. for 60 minutes to obtain a coating film. . The obtained coating film was rubbed to obtain a cholesteric reflective film substrate of the present invention. The rubbing treatment was performed using a commercially available rubbing apparatus.
　次に、ラビングした基材に重合性液晶組成物（１’）の溶液をスピンコート法で塗布し、６５℃で３分乾燥した。得られた塗膜を６０℃のホットプレート上に置き、バンドパスフィルターで３６５ｎｍ付近のみの紫外光（ＵＶ光）が得られるように調整を行った高圧水銀ランプを用いて、１５ｍＷ／ｃｍ２の強度で１０秒間ＵＶ光を照射した。次にバンドパスフィルターを取り外し、７０ｍＷ／ｃｍ２の強度で２０秒間ＵＶ光を照射することで本発明の光学異方体（コレステリック反射フィルム）を得た。 Next, a solution of the polymerizable liquid crystal composition (1 ′) was applied to the rubbed substrate by a spin coating method and dried at 65 ° C. for 3 minutes. The obtained coating film was placed on a hot plate at 60 ° C., and a 15 mW / cm 2 high-pressure mercury lamp adjusted so that ultraviolet light (UV light) of only around 365 nm was obtained with a bandpass filter. Irradiated with UV light for 10 seconds at intensity. Next, the bandpass filter was removed, and the optical anisotropic body (cholesteric reflective film) of the present invention was obtained by irradiating with UV light at an intensity of 70 mW / cm 2 for 20 seconds.
　得られたコレステリック反射フィルムの膜厚は5.5μｍであった。また、フィルムのヘイズを測定したところ、4.6％であった。式（I）から計算されるx値は、79であった。 The film thickness of the obtained cholesteric reflective film was 5.5 μm. Moreover, it was 4.6% when the haze of the film was measured. The x value calculated from formula (I) was 79.
（実施例２～８）
　実施例１において、重合性液晶化合物として精製方法が異なるロットの化合物に代えた以外は、実施例１と同様にして実験を行った。結果を表１に示す。 (Examples 2 to 8)
In Example 1, the experiment was performed in the same manner as in Example 1 except that the polymerizable liquid crystal compound was replaced with a compound of a lot having a different purification method. The results are shown in Table 1.
（比較例１～７）
実施例１において、重合性液晶化合物として精製方法が異なるロットの化合物に代えた以外は、実施例１と同様にして実験を行った。結果を表１に示す。 (Comparative Examples 1 to 7)
In Example 1, the experiment was performed in the same manner as in Example 1 except that the polymerizable liquid crystal compound was replaced with a compound of a lot having a different purification method. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000129
Figure JPOXMLDOC01-appb-T000129
　以上の結果から、Xa値が825以下である本発明の重合性液晶組成物は、これを用いて得られた光学異方体のヘイズが10％以下であり、光散乱を抑制することができることがわかる。また、x値が150以下である本発明の方法で得られた光学異方体はヘイズが10％以下であり、光散乱が抑制されていることがわかる。 From the above results, the polymerizable liquid crystal composition of the present invention having an Xa value of 825 or less has a haze of an optical anisotropic body obtained by using this of 10% or less, and can suppress light scattering. I understand. In addition, it can be seen that the optical anisotropic body obtained by the method of the present invention having an x value of 150 or less has a haze of 10% or less, and light scattering is suppressed.

Claims (13)

  1. シアノ基を有する3～4量体不純物の濃度をa(ppm)、シアノ基を有する2量体不純物の濃度をb(ppm)、シアノ基を有さない3～4量体不純物の濃度をc(ppm)、シアノ基を有さない2量体不純物の濃度をd(ppm)としたとき、式（Ｉａ）
    　Xa=(a+0.19b)+0.0215(c+0.19d)   (Ia)
    で表されるXa値が、825以下である重合性液晶組成物。     The concentration of cyano group-containing tri- and tetrameric impurities is a (ppm), the concentration of dimer-containing impurities having a cyano group is b (ppm), and the concentration of cyano-group-free tri- and tetrameric impurities is c (ppm), when the concentration of the dimer impurity having no cyano group is d (ppm), the formula (Ia)
    Xa = (a + 0.19b) +0.0215 (c + 0.19d) (Ia)
    A polymerizable liquid crystal composition having an Xa value of 825 or less.
  2. 式（Ｉａ）で表されるXa値が、605以下である請求項１記載の重合性液晶組成物。 The polymerizable liquid crystal composition according to claim 1, wherein the Xa value represented by the formula (Ia) is 605 or less.
  3. 重合性液晶材料として、一般式（a）
    Figure JPOXMLDOC01-appb-C000001
     （式中、Z3は水素原子、ハロゲン原子、シアノ基又は炭素原子数１～２０の炭化水素基を表し、Z4は水素原子又はメチル基を表し、W3は単結合、-O-、-COO-又は-OCO-を表し、vは０～１８の整数を表し、uは０又は１を表し、D、E及びFはそれぞれ独立的に、1,4－フェニレン基、隣接しないCH基が窒素で置換された1,4－フェニレン基、1,4－シクロヘキシレン基、１つ又は隣接しない２つのCH2基が酸素又は硫黄原子で置換された1,4－シクロヘキシレン基、1,4－シクロヘキセニレン基を表すが、式中に存在する1,4－フェニレン基は炭素原子数１～７のアルキル基、アルコキシ基、アルカノイル基、シアノ基又はハロゲン原子で一つ以上置換されていても良く、Y6及びY7はそれぞれ独立的に単結合、-CH2CH2-、-CH2O-、-OCH2-、-COO-、-OCO-、-C≡C-、-CH=CH-、-CF=CF-、-（CH2）4-、-CH2CH2CH2O-、-OCH2CH2CH2-、-CH=CHCH2CH2-、-CH2CH2CH=CH-、-CH=CHCOO-、-OCOCH=CH-、-CH2CH2COO-、-CH2CH2OCO-、-COO CH2CH2-、-OCOCH2CH2-、-CH=N-、-N=CH-、-N=N-又は-CH=N-N=CH-を表し、Y6及びY7の少なくとも一つは-CH=CH-、-CH=CHCOO-、-OCOCH=CH-、-CH=N-、-N=CH-、-N=N-、-CH=N-N=CH-を表し、
    Y8は単結合、-O-、-COO-、-OCO-又は-CH=CHCOO-を表す。）で表される化合物、及び／又は一般式（ｂ）
    Figure JPOXMLDOC01-appb-C000002
     （式中、Z5、Z6はそれぞれ独立的に水素原子、又はメチル基を表し、G、H及びIはそれぞれ独立的に、1,4－フェニレン基、隣接しないCH基が窒素で置換された1,4－フェニレン基、1,4－シクロヘキシレン基、１つ又は隣接しない２つのCH2基が酸素又は硫黄原子で置換された1,4－シクロヘキシレン基、1,4－シクロヘキセニレン基を表すが、式中に存在する1,4－フェニレン基は炭素原子数１～７のアルキル基、アルコキシ基、アルカノイル基、シアノ基又はハロゲン原子で一つ以上置換されていても良く、mは０から３の整数を表し、W1及びW2はそれぞれ独立的に単結合、-O-、-COO-又は-OCO-を表し、Y1及びY2はそれぞれ独立的に単結合、-COO-、-OCO-、-CH2CH2COO-、-CH2CH2OCO-、-COO CH2CH2-、-OCOCH2CH2-、-CH=N-、-N=CH-、-N=N-、-CH=N-N=CH-又は単結合を表し、Y1及びY2のうち少なくとも一つは-CH=CH-、-CH=CHCOO-、-OCOCH=CH-、-CH=N-、-N=CH-、-N=N-、-CH=N-N=CH-を表しr及びsはそれぞれ独立的に２～１８の整数を表すが、式中に存在する1,4－フェニレン基は炭素原子数１～７のアルキル基、アルコキシ基、アルカノイル基、シアノ基、又はハロゲン原子で一つ以上置換されていても良い。）で表される化合物を含有する請求項１又は２記載の重合性液晶組成物。     As a polymerizable liquid crystal material, the general formula (a)
    Figure JPOXMLDOC01-appb-C000001
     (In the formula, Z 3 represents a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group having 1 to 20 carbon atoms, Z 4 represents a hydrogen atom or a methyl group, W 3 represents a single bond, —O—, -COO- or -OCO-, v represents an integer of 0 to 18, u represents 0 or 1, D, E and F are each independently a 1,4-phenylene group or a non-adjacent CH group. 1,4-phenylene group substituted with nitrogen, 1,4-cyclohexylene group, 1,4-cyclohexylene group in which one or two non-adjacent CH 2 groups are substituted with oxygen or sulfur atoms, 1, Represents a 4-cyclohexenylene group, and the 1,4-phenylene group present in the formula is substituted by one or more alkyl groups, alkoxy groups, alkanoyl groups, cyano groups or halogen atoms having 1 to 7 carbon atoms. Y 6 and Y 7 are each independently a single bond, —CH 2 CH 2 —, —CH 2 O—, —OCH 2 —, —COO—, —OCO—, —C≡C—, — CH = CH-, -CF = CF -, - (CH 2) 4 -, - CH 2 CH 2 CH 2 O -, - OCH 2 CH 2 CH 2 -, - CH = CHCH 2 CH 2 -, - CH 2 CH 2 CH = CH -, - CH = CHCOO-, -OCOCH = CH-, -CH 2 CH 2 COO-, -CH 2 CH 2 OCO-, -COO CH 2 CH 2- , -OCOCH 2 CH 2- , -CH = N-, -N = CH-, -N = N- or -CH = NN = CH-, wherein at least one of Y 6 and Y 7 is -CH = CH-, -CH = CHCOO-, -OCOCH = CH-, -CH = N-, -N = CH-, -N = N-, -CH = NN = CH-
    Y 8 represents a single bond, —O—, —COO—, —OCO— or —CH═CHCOO—. And / or the general formula (b)
    Figure JPOXMLDOC01-appb-C000002
     (Wherein Z 5 and Z 6 each independently represent a hydrogen atom or a methyl group, G, H and I each independently represent a 1,4-phenylene group and a non-adjacent CH group substituted with nitrogen. 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexylene group in which one or two non-adjacent CH 2 groups are substituted with oxygen or sulfur atoms, 1,4-cyclohexenylene A 1,4-phenylene group present in the formula may be substituted with one or more alkyl groups, alkoxy groups, alkanoyl groups, cyano groups or halogen atoms having 1 to 7 carbon atoms; Represents an integer of 0 to 3, W 1 and W 2 each independently represent a single bond, —O—, —COO— or —OCO—, Y 1 and Y 2 each independently represent a single bond, — COO-, -OCO-, -CH 2 CH 2 COO-, -CH 2 CH 2 OCO-, -COO CH 2 CH 2- , -OCOCH 2 CH 2- , -CH = N-, -N = CH-, -N = N -, - CH = NN = CH- or a single bond, Y 1 At least one of the fine Y 2 is -CH = CH -, - CH = CHCOO -, - OCOCH = CH -, - CH = N -, - N = CH -, - N = N -, - CH = NN = And CH and r and s each independently represent an integer of 2 to 18, and the 1,4-phenylene group present in the formula is an alkyl group having 1 to 7 carbon atoms, an alkoxy group, an alkanoyl group, cyano group The polymerizable liquid crystal composition according to claim 1, wherein the polymerizable liquid crystal composition comprises a compound represented by the formula:
  4. 一般式（a）においてZ3がシアノ基で表される化合物を含有する請求項３記載の重合性液晶組成物。 The polymerizable liquid crystal composition according to claim 3, which contains a compound represented by general formula (a) wherein Z 3 is a cyano group.
  5. 一般式（a）で表される化合物の含有量が5％～70％である請求項３又は４記載の重合性液晶組成物。 The polymerizable liquid crystal composition according to claim 3, wherein the content of the compound represented by the general formula (a) is 5% to 70%.
  6. 一般式（b）で表される化合物の含有量が5％～90％である請求項３又は４記載の重合性液晶組成物。 The polymerizable liquid crystal composition according to claim 3 or 4, wherein the content of the compound represented by the general formula (b) is 5% to 90%.
  7. 重合性液晶材料を配向させた状態において活性エネルギー線硬化させて光学異方体を製造する方法において、シアノ基を有する3～4量体不純物の濃度をa(ppm)、シアノ基を有する2量体不純物の濃度をb(ppm)、シアノ基を有さない3～4量体不純物の濃度をc(ppm)、シアノ基を有さない2量体不純物の濃度をd(ppm)、重合性液晶組成物を硬化させて得られる光学異方体の厚みをe（μｍ）としたとき、式（Ｉ）
    　x=[(a+0.19b)+0.0215(c+0.19d)]/e   (I)　　
    で表されるx値が、150以下になるように制御した重合性液晶組成物を使用することを特徴とする製造方法。     In a method for producing an optical anisotropic body by curing active energy rays in an aligned state of a polymerizable liquid crystal material, the concentration of a tri- to tetra-mer impurity having a cyano group is a (ppm), and a dimer having a cyano group Concentration of body impurity is b (ppm), concentration of tri to tetramer impurity without cyano group is c (ppm), concentration of dimer impurity without cyano group is d (ppm), polymerizability When the thickness of the optical anisotropic body obtained by curing the liquid crystal composition is e (μm), the formula (I)
    x = [(a + 0.19b) +0.0215 (c + 0.19d)] / e (I)
    A production method using a polymerizable liquid crystal composition in which an x value represented by the formula is controlled to be 150 or less.
  8. 式（Ｉ）で表されるx値が、110以下である請求項７記載の製造方法。 The production method according to claim 7, wherein the x value represented by formula (I) is 110 or less.
  9. 重合性液晶材料として、一般式（a）
    Figure JPOXMLDOC01-appb-C000003
     （式中、Z3は水素原子、ハロゲン原子、シアノ基又は炭素原子数１～２０の炭化水素基を表し、Z4は水素原子又はメチル基を表し、W3は単結合、-O-、-COO-又は-OCO-を表し、vは０～１８の整数を表し、uは０又は１を表し、D、E及びFはそれぞれ独立的に、1,4－フェニレン基、隣接しないCH基が窒素で置換された1,4－フェニレン基、1,4－シクロヘキシレン基、１つ又は隣接しない２つのCH2基が酸素又は硫黄原子で置換された1,4－シクロヘキシレン基、1,4－シクロヘキセニレン基を表すが、式中に存在する1,4－フェニレン基は炭素原子数１～７のアルキル基、アルコキシ基、アルカノイル基、シアノ基又はハロゲン原子で一つ以上置換されていても良く、Y6及びY7はそれぞれ独立的に単結合、-CH2CH2-、-CH2O-、-OCH2-、-COO-、-OCO-、-C≡C-、-CH=CH-、-CF=CF-、-（CH2）4-、-CH2CH2CH2O-、-OCH2CH2CH2-、-CH=CHCH2CH2-、-CH2CH2CH=CH-、-CH=CHCOO-、-OCOCH=CH-、-CH2CH2COO-、-CH2CH2OCO-、-COO CH2CH2-、-OCOCH2CH2-、-CH=N-、-N=CH-、-N=N-又は-CH=N-N=CH-を表し、Y6及びY7の少なくとも一つは-CH=CH-、-CH=CHCOO-、-OCOCH=CH-、-CH=N-、-N=CH-、-N=N-、-CH=N-N=CH-を表し、
    Y8は単結合、-O-、-COO-、-OCO-又は-CH=CHCOO-を表す。）で表される化合物、及び／又は一般式（ｂ）
    Figure JPOXMLDOC01-appb-C000004
     （式中、Z5、Z6はそれぞれ独立的に水素原子、又はメチル基を表し、G、H及びIはそれぞれ独立的に、1,4－フェニレン基、隣接しないCH基が窒素で置換された1,4－フェニレン基、1,4－シクロヘキシレン基、１つ又は隣接しない２つのCH2基が酸素又は硫黄原子で置換された1,4－シクロヘキシレン基、1,4－シクロヘキセニレン基を表すが、式中に存在する1,4－フェニレン基は炭素原子数１～７のアルキル基、アルコキシ基、アルカノイル基、シアノ基又はハロゲン原子で一つ以上置換されていても良く、mは０から３の整数を表し、W1及びW2はそれぞれ独立的に単結合、-O-、-COO-又は-OCO-を表し、Y1及びY2はそれぞれ独立的に単結合、-COO-、-OCO-、-CH2CH2COO-、-CH2CH2OCO-、-COO CH2CH2-、-OCOCH2CH2-、-CH=N-、-N=CH-、-N=N-、-CH=N-N=CH-又は単結合を表し、Y1及びY2のうち少なくとも一つは-CH=CH-、-CH=CHCOO-、-OCOCH=CH-、-CH=N-、-N=CH-、-N=N-、-CH=N-N=CH-を表しr及びsはそれぞれ独立的に２～１８の整数を表すが、式中に存在する1,4－フェニレン基は炭素原子数１～７のアルキル基、アルコキシ基、アルカノイル基、シアノ基、又はハロゲン原子で一つ以上置換されていても良い。）で表される化合物を含有する請求項７又は８記載の製造方法。     As a polymerizable liquid crystal material, the general formula (a)
    Figure JPOXMLDOC01-appb-C000003
     (In the formula, Z 3 represents a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group having 1 to 20 carbon atoms, Z 4 represents a hydrogen atom or a methyl group, W 3 represents a single bond, —O—, -COO- or -OCO-, v represents an integer of 0 to 18, u represents 0 or 1, D, E and F are each independently a 1,4-phenylene group or a non-adjacent CH group. 1,4-phenylene group substituted with nitrogen, 1,4-cyclohexylene group, 1,4-cyclohexylene group in which one or two non-adjacent CH 2 groups are substituted with oxygen or sulfur atoms, 1, Represents a 4-cyclohexenylene group, and the 1,4-phenylene group present in the formula is substituted by one or more alkyl groups, alkoxy groups, alkanoyl groups, cyano groups or halogen atoms having 1 to 7 carbon atoms. Y 6 and Y 7 are each independently a single bond, —CH 2 CH 2 —, —CH 2 O—, —OCH 2 —, —COO—, —OCO—, —C≡C—, — CH = CH-, -CF = CF -, - (CH 2) 4 -, - CH 2 CH 2 CH 2 O -, - OCH 2 CH 2 CH 2 -, - CH = CHCH 2 CH 2 -, - CH 2 CH 2 CH = CH -, - CH = CHCOO-, -OCOCH = CH-, -CH 2 CH 2 COO-, -CH 2 CH 2 OCO-, -COO CH 2 CH 2- , -OCOCH 2 CH 2- , -CH = N-, -N = CH-, -N = N- or -CH = NN = CH-, wherein at least one of Y 6 and Y 7 is -CH = CH-, -CH = CHCOO-, -OCOCH = CH-, -CH = N-, -N = CH-, -N = N-, -CH = NN = CH-
    Y 8 represents a single bond, —O—, —COO—, —OCO— or —CH═CHCOO—. And / or the general formula (b)
    Figure JPOXMLDOC01-appb-C000004
     (Wherein Z 5 and Z 6 each independently represent a hydrogen atom or a methyl group, G, H and I each independently represent a 1,4-phenylene group and a non-adjacent CH group substituted with nitrogen. 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexylene group in which one or two non-adjacent CH 2 groups are substituted with oxygen or sulfur atoms, 1,4-cyclohexenylene A 1,4-phenylene group present in the formula may be substituted with one or more alkyl groups, alkoxy groups, alkanoyl groups, cyano groups or halogen atoms having 1 to 7 carbon atoms; Represents an integer of 0 to 3, W 1 and W 2 each independently represent a single bond, —O—, —COO— or —OCO—, Y 1 and Y 2 each independently represent a single bond, — COO-, -OCO-, -CH 2 CH 2 COO-, -CH 2 CH 2 OCO-, -COO CH 2 CH 2- , -OCOCH 2 CH 2- , -CH = N-, -N = CH-, -N = N -, - CH = NN = CH- or a single bond, Y 1 At least one of the fine Y 2 is -CH = CH -, - CH = CHCOO -, - OCOCH = CH -, - CH = N -, - N = CH -, - N = N -, - CH = NN = And CH and r and s each independently represent an integer of 2 to 18, and the 1,4-phenylene group present in the formula is an alkyl group having 1 to 7 carbon atoms, an alkoxy group, an alkanoyl group, cyano group The manufacturing method of Claim 7 or 8 containing the compound represented by 1 or more by the group or the halogen atom.
  10. 一般式（a）においてZ3がシアノ基で表される化合物を含有する請求項９記載の製造方法。 The manufacturing method of Claim 9 containing the compound in which Z < 3 > is represented with a cyano group in General formula (a).
  11. 一般式（a）で表される化合物の含有量が5％～70％である請求項９又は１０記載の製造方法。 The production method according to claim 9 or 10, wherein the content of the compound represented by the general formula (a) is 5% to 70%.
  12. 一般式（b）で表される化合物の含有量が5％～90％である請求項９又は１０記載の製造方法。 The production method according to claim 9 or 10, wherein the content of the compound represented by the general formula (b) is 5% to 90%.
  13. 重合性液晶材料を配向させた状態において活性エネルギー線硬化させて光学異方体を製造する方法において、シアノ基を有する3～4量体不純物の濃度をa(ppm)、シアノ基を有する2量体不純物の濃度をb(ppm)、シアノ基を有さない3～4量体不純物の濃度をc(ppm)、シアノ基を有さない2量体不純物の濃度をd(ppm)、重合性液晶組成物を硬化させて得られる光学異方体の厚みをe（μｍ）としたとき、式（Ｉ）
    　x=[(a+0.19b)+0.0215(c+0.19d)]/e   (I)　　
    で表されるx値が、150以下になるように制御した重合性液晶組成物を使用する光学異方体。     In a method for producing an optical anisotropic body by curing active energy rays in an aligned state of a polymerizable liquid crystal material, the concentration of a tri- to tetra-mer impurity having a cyano group is a (ppm), and a dimer having a cyano group Concentration of body impurity is b (ppm), concentration of tri to tetramer impurity without cyano group is c (ppm), concentration of dimer impurity without cyano group is d (ppm), polymerizability When the thickness of the optical anisotropic body obtained by curing the liquid crystal composition is e (μm), the formula (I)
    x = [(a + 0.19b) +0.0215 (c + 0.19d)] / e (I)
    An optical anisotropic body using a polymerizable liquid crystal composition in which the x value represented by the formula is controlled to be 150 or less.
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