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WO2018151070A1 - Corps optiquement anisotrope - Google Patents

Corps optiquement anisotrope Download PDF

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Publication number
WO2018151070A1
WO2018151070A1 PCT/JP2018/004800 JP2018004800W WO2018151070A1 WO 2018151070 A1 WO2018151070 A1 WO 2018151070A1 JP 2018004800 W JP2018004800 W JP 2018004800W WO 2018151070 A1 WO2018151070 A1 WO 2018151070A1
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group
oco
liquid crystal
coo
carbon atoms
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PCT/JP2018/004800
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Japanese (ja)
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美花 高崎
桑名　康弘
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Dic株式会社
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Priority to JP2018568514A priority Critical patent/JPWO2018151070A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/38—Polymers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13363—Birefringent elements, e.g. for optical compensation

Definitions

  • the present invention relates to an optical anisotropic member used for optical compensation and viewing angle compensation of a liquid crystal display, an optical anisotropic member used for an organic EL, etc., or an optical anisotropic member used for an optical element. , Retardation film, retardation patterning film, brightness enhancement film, antireflection film, thermal barrier film, laminate having a protective layer on the optical anisotropic body, and optical anisotropic body, retardation film, phase difference patterning
  • the present invention relates to a liquid crystal display device, an image display device, an optical element, and a printed matter having a film, a brightness enhancement film, an antireflection film, and a heat shielding film.
  • the polymerizable liquid crystal composition is useful as a component of an optical anisotropic body, and the optical anisotropic body is applied to various liquid crystal displays as, for example, a polarizing film and a retardation film.
  • the polarizing film and the retardation film are coated with a polymerizable liquid crystal composition on a substrate, dried with a solvent to form a coating film, and then heated or activated in a state where the polymerizable liquid crystal composition is aligned with an alignment film or the like. It is obtained by irradiating energy rays to cure the polymerizable liquid crystal composition.
  • the polymerizable liquid crystal composition is applied to a retardation film, a retardation patterning film, a brightness enhancement film, an antireflection film, a heat shielding film, or various optical elements such as a diffraction grating and a pickup lens, and an anti-counterfeit printed matter.
  • Patent Document 1 discloses that by using a liquid crystal compound having four or more rings such as a benzene ring and a cyclohexane ring, a retardation film having excellent heat resistance can be created in the baking treatment after the retardation film is formed. ing.
  • a firing step a transparent electrode sputtering step, and a re-baking step after the retardation film is formed, and the orientation of the retardation film is good even after the firing step and the sputtering step. It is required to be.
  • Patent Document 1 the orientation may be deteriorated depending on the polymerizable liquid crystal composition.
  • Patent Document 2 by adding a multi-branched compound such as a dendrimer to the polymerizable liquid crystal composition, the retardation unevenness is small, and the surface shape change of the retardation film is changed even after the firing process after the retardation film is formed.
  • a retardation film can be obtained in which cracks are not generated even in the sputtering step of the transparent electrode, which is a subsequent step of the firing step.
  • Patent Document 2 although a retardation film that does not generate cracks can be obtained, the transparency and retardation holding ratio of the retardation film after the firing process and the sputtering process are not disclosed, and there is room for further improvement. there were.
  • the problem to be solved by the present invention is to provide an optical anisotropic body that has good orientation and high transparency and retardation retention even after the firing process and sputtering process after the retardation film formation. is there.
  • another object is to provide a liquid crystal display device, an image display device, an optical element, and a printed matter having a retardation film, a retardation patterning film, a brightness enhancement film, an antireflection film, and a thermal barrier film.
  • the present invention has been conducted by paying attention to the amount of residual monomer contained in the optically anisotropic layer, and as a result, has come to provide the present invention.
  • the present invention relates to one or more polymerization initiators (I), one or two or more polymerizable liquid crystal compounds (II) having two or more polymerizable functional groups in the molecule, and optionalally, an optically anisotropic layer using a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound (II-1) having one or more kinds of one polymerizable functional group,
  • An optically anisotropic body in which the content of the polymerizable liquid crystal compound (II) contained in the rectangular layer and the polymerizable liquid crystal compound (II-1) optionally contained is 0.0001% by mass or more and 3% by mass or less.
  • the optical anisotropic body of the present invention is an optical anisotropic body that has good orientation after the firing step and sputtering step, and has high transparency and retardation retention, so it can be used for various optical materials such as optical films. Useful.
  • Polarizing layer (2) Adhesive layer (3) Light transmissive substrate (4) Color filter layer (5) Flattening layer (6) Alignment film for retardation film (7) Polymerizable liquid crystal composition was used.
  • Retardation film 1 (8) Retardation film 2 using polymerizable liquid crystal composition (9) Transparent electrode layer (10) Alignment film (11) Liquid crystal composition (12) Alignment film (13) Pixel electrode layer (14) Light transmissive substrate (15) Adhesive layer (16) Polarizing layer (17) Back Light
  • the “liquid crystal” of the polymerizable liquid crystal composition used when producing the optical anisotropic body is based on the polymerizable liquid crystal composition. It is intended to exhibit liquid crystallinity in a state where the organic solvent is removed after application to the material.
  • the “liquid crystal” of the polymerizable liquid crystal compound means a case where it is intended to show liquid crystal properties with only one type of polymerizable liquid crystal compound used, or a mixture with other liquid crystal compounds. It is intended to exhibit liquid crystal properties.
  • the polymerizable liquid crystal composition can be polymerized (formed into a film) by performing a polymerization treatment by irradiation with light such as ultraviolet rays, heating, or a combination thereof.
  • the polymerizable liquid crystal compound used in the present invention is not particularly limited as long as it is a compound that exhibits liquid crystallinity alone or in a composition with another compound and has at least one polymerizable functional group. Conventional ones can be used.
  • a rod-like polymerizable liquid crystal compound having a polymerizable functional group such as a vinyl group, an acrylic group or a (meth) acryl group, or a maleimide as described in JP-A Nos. 2004-2373 and 2004-99446
  • a rod-like polymerizable liquid crystal compound having a group examples thereof include a rod-like polymerizable liquid crystal compound having a group.
  • a rod-like liquid crystal compound having a polymerizable group is preferable because it can easily produce a liquid crystal having a temperature range around room temperature.
  • the optical anisotropic body of the present invention is produced using a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound (II) having two or more polymerizable functional groups in the molecule.
  • the polymerizable liquid crystal compound (II) having two or more polymerizable functional groups in the molecule is preferably a compound represented by the following general formula (II-A).
  • P 21 represents a polymerizable functional group
  • Sp 21 represents an alkylene group having 1 to 18 carbon atoms (the hydrogen atom in the alkylene group represents one or more halogen atoms, a CN group, or a polymerizable functional group). may be substituted by a group having, independently of each one CH 2 group or not adjoining two or more CH 2 groups existing in the alkylene group each other, -O -, - COO-, May be replaced by —OCO— or —OCO—O—).
  • X 21 represents —O—, —S—, —OCH 2 —, —CH 2 O—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, —SCH 2 —, —CH 2 S—, —CF 2 O—, —OCF 2 —, —CF 2 S—, —SCF 2 —, —CH ⁇ CH—COO—, —CH ⁇ CH—OCO—, —COO—CH ⁇ CH—, —OCO—CH ⁇ CH—, —COO—CH 2 CH 2 —, —OCO—CH 2 CH 2 —, —CH 2 CH 2 —COO—, —CH 2 CH 2 —OCO—, —COO—CH 2 CH 2 —, —OCO—CH 2 CH 2 —, —CH 2 CH 2 —COO—, —CH
  • P 22 represents a polymerizable functional group
  • Sp 22 represents the same as defined in Sp 21
  • X 22 represents that defined in X 21.
  • P 22 -Sp 22 and Sp 22 -X 22 do not include —O—O—, —O—NH—, —S—S— and —O—S— groups).
  • Q22 represents 0 or 1.
  • the mesogenic group represented by MG has the general formula (II-b)
  • B1, B2 and B3 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2, 5-diyl group, 1,3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2, 6-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3,4 Tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-d
  • P 23 represents a polymerizable functional group
  • Sp 23 represents the same as defined in Sp 21 above
  • X 23 represents —O—, —COO—, —OCO—, —OCH 2 —, —CH 2 O—, —CH 2 CH 2 OCO—, —COOCH 2 CH 2 —, —OCOCH 2 CH 2 —, or
  • a single bond is represented
  • q23 represents 0 or 1
  • q24 represents 0 or 1.
  • Z1 and Z2 are each independently —COO—, —OCO—, —CH 2 CH 2 —, —OCH 2 —, —CH 2 O—, —CH ⁇ CH—.
  • Sp 21 represents an alkylene group having 1 to 18 carbon atoms, and the hydrogen atom in the alkylene group is substituted with a group having a polymerizable functional group.
  • examples of the group having a polymerizable functional group include a group represented by the general formula (II-c).
  • P 21 , P 22 and P 23 are each independently represented by the following formula (P-2-1) To a substituent selected from a polymerizable group represented by the formula (P-2-20).
  • B1, B2 and B3 may each independently have the above-mentioned substituents, 1,4-phenylene group, 1,4-cyclohexylene group, 2,6 -Preferably represents a naphthylene group.
  • Sp 21 , Sp 22 and Sp 23 are each independently carbon from the viewpoint of enhancing storage stability. It is preferable that an alkylene group of atoms 1-14, each two or more CH 2 groups not one CH 2 group or adjacent existing in the alkylene group independently of one another, -O-, It may be replaced by —COO— or —OCO—. Further, Sp 21 , Sp 22 and Sp 23 each independently preferably represent an alkylene group having 1 to 12 carbon atoms, and are not adjacent to one CH 2 group present in the alkylene group. Two or more CH 2 groups may be replaced by —O—.
  • Z1 and Z2 are each independently —COO—, —OCO—, —CH 2 O—, —CH ⁇ CH—, —C ⁇ C—, —CH 2 CH 2. It preferably represents COO—, —CH 2 CH 2 OCO—, —COOCH 2 CH 2 —, —OCOCH 2 CH 2 —, —C ⁇ N—, —N ⁇ C—, or a single bond.
  • r1 preferably represents 0 or 1.
  • the optical anisotropic body of the present invention is produced using a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound (II) having two or more polymerizable functional groups in the molecule.
  • the product preferably contains a bifunctional polymerizable liquid crystal compound having two polymerizable functional groups in the molecule.
  • a compound represented by the following general formula (II-2) is preferable.
  • P 221 , X 211 , q221, X 222 , q222, and P 222 represent P 21 , X 21 in the general formula (II) or the general formula (II-a), respectively.
  • Sp 221 and Sp 222 each independently represent an alkylene group having 1 to 18 carbon atoms (the hydrogen atom in the alkylene group is one or more halogen atoms, or CN It may be substituted by a group, two or more of CH 2 groups, independently of one another each of the present in the radical is not one CH 2 group or adjacent, -O -, - COO -, - OCO -Or -OCO-O- may be substituted).
  • MG 2 represents a mesogenic group, and the mesogenic group includes the general formula (II-2-b)
  • B11, B21 and B31 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran- 2,5-diyl group, 1,3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene- 2,6-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3 4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group,
  • the hydrogen atom in the alkyl group may be substituted with one or more phenyl groups, each of two or more CH 2 groups not one CH 2 group or adjacent present in this group Independently of each other, —O—, —COO—, —OCO Or may be replaced by —OCO—O—), an alkoxy group having 1 to 8 carbon atoms, an alkanoyl group having 1 to 8 carbon atoms, an alkanoyloxy group having 1 to 8 carbon atoms, or the number of carbon atoms May have an alkoxycarbonyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group having 2 to 8 carbon atoms, and / or an alkenoyl group having 2 to 8 carbon atoms,
  • Z11 and Z21 are each independently —COO—, —OCO—, —CH 2 CH 2 —, —OCH 2 —, —CH
  • P 221 and P 222 are each independently from the above formulas (P-2-1), (P-2-2), (P— 2-7), (P-2-12), and (P-2-13) are preferable, and formulas (P-2-1) and (P-2-2) are more preferable.
  • Sp 221 and Sp 222 are preferably each independently an alkylene group having 1 to 14 carbon atoms from the viewpoint of enhancing storage stability.
  • One CH 2 group present or two or more non-adjacent CH 2 groups may each be independently replaced by —O—, —COO— or —OCO—.
  • each of Sp 221 and Sp 222 preferably independently represents an alkylene group having 1 to 12 carbon atoms, and one CH 2 group present in the alkylene group or two or more not adjacent to each other The CH 2 group may be replaced by —O—.
  • X 221 and X 222 each independently represent —O—, —OCH 2 —, —CH 2 O—, —CO—, —COO—, —OCO—, — O—CO—O—, —CH ⁇ CH—COO—, —CH ⁇ CH—OCO—, —COO—CH ⁇ CH—, —OCO—CH ⁇ CH—, —COO—CH 2 CH 2 —, —OCO -CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 - It preferably represents OCO—, —CH ⁇ CH—, —C ⁇ C— or a single bond, more preferably —O—, —COO—, —OCO— or a single bond (provided that P 221 —
  • B11, B21 and B31 each independently may have the above-described substituents such as 1,4-phenylene group, 1,4-cyclohexylene group, 2 , 6-naphthylene group, and Z11 and Z21 are each independently —COO—, —OCO—, —CH 2 CH 2 —, —OCH 2 —, —CH 2 O—, —CH ⁇ CH It is preferable to represent —, —C ⁇ C—, —C ⁇ N—, —N ⁇ C—, or a single bond, and r11 preferably represents 0 or 1.
  • Examples of the general formula (II-2) include compounds represented by the following general formulas (II-2-1) to (II-2-4), but are not limited to the following general formulas is not.
  • P 221 , Sp 221 , X 221 , q 221 , X 222 , Sp 222 , q 222 , and P 222 are respectively the above general formulas.
  • B111, B112, B113, B21, and B31 are the same as the definitions of B11 to B31 in the general formula (II-2-b).
  • Z111, Z112, Z113, and Z21 represent the same definitions as Z11 to Z21 in the general formula (II-2-b).
  • Preferred groups also represent the same definitions as Z11 to Z21, and may be the same or different.
  • the compounds represented by the general formulas (II-2-1) to (II-2-4) include the following general formulas (II-2-1-1) to (II-2-1-25): ) Is exemplified, but not limited thereto.
  • R d and R e each independently represent a hydrogen atom or a methyl group
  • the cyclic group includes one or more F, Cl, CF 3 , OCF 3 , CN groups, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and 1 to 8 alkanoyl groups, alkanoyloxy groups having 1 to 8 carbon atoms, alkoxycarbonyl groups having 1 to 8 carbon atoms, alkenyl groups having 2 to 8 carbon atoms, alkenyloxy groups having 2 to 8 carbon atoms, carbon atoms It may have an alkenoyl group having 2 to 8 carbon atoms and an alkenoyloxy group having 2 to 8 carbon atoms.
  • M1, m2, m3, and m4 each independently represent an integer of 0 to 8, and n1, n2, n3, and n4 each independently represent 0 or 1.
  • the compounds represented by the general formulas (II-2-1-1) to (II-2-1-25) are more specifically represented by the following general formulas (II-2-2-1) to The compound represented by (II-2-2-36) can be exemplified, but is not limited thereto.
  • the polymerizable liquid crystal compound having two polymerizable functional groups can be used singly or in combination of two or more, preferably 1 to 5 types, more preferably 2 to 5 types.
  • the total content of the liquid crystal compounds is such that the polymerizable liquid crystal compound (II), the polymerizable liquid crystal compound (II-1), and
  • the total content of the chiral compound (III) is preferably 20 to 100% by mass, more preferably 25 to 100% by mass, and particularly preferably 30 to 100% by mass.
  • the lower limit is preferably 40% by mass or more, and more preferably 50% by mass or more.
  • the optical anisotropic body of the present invention is produced using a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound (II) having two or more polymerizable functional groups in the molecule.
  • the product may contain a polyfunctional polymerizable liquid crystal compound having three or more polymerizable functional groups.
  • the polyfunctional polymerizable liquid crystal compound having three or more polymerizable functional groups it is preferable to use a compound having three polymerizable functional groups.
  • the following general formula (II-1) to Examples thereof include compounds represented by the general formula (II-3-2).
  • P 231 , X 231 , q231, X 232 , q232, P 232 , P 233 , X 233 , q234, q233, X 234 , Q236, q235, P 234 , X 235 , q238, q237, and P 235 are P 21 , X 21 in the general formula (II), general formula (II-a), and general formula (II-c), respectively.
  • Sp 231 , Sp 232 , Sp 233 , Sp 234 and Sp 235 are each independently an alkylene having 1 to 18 carbon atoms.
  • a hydrogen atom in the alkylene group may be substituted by one or more halogen atoms or a CN group, one CH 2 group present in the group or two or more non-adjacent Each independently of the CH 2 group may be replaced by —O—, —COO—, —OCO— or —OCO—O—.
  • j3 represents 0 or 1
  • MG 3 represents a mesogenic group, and the mesogenic group includes the general formula (II-3-b)
  • B11, B21 and B31 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran- 2,5-diyl group, 1,3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene- 2,6-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3 4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group,
  • the hydrogen atom in the alkyl group may be substituted with one or more phenyl groups, each of two or more CH 2 groups not one CH 2 group or adjacent present in this group Independently of each other, —O—, —COO—, —OCO Or may be replaced by —OCO—O—), an alkoxy group having 1 to 8 carbon atoms, an alkanoyl group having 1 to 8 carbon atoms, an alkanoyloxy group having 1 to 8 carbon atoms, or the number of carbon atoms May have an alkoxycarbonyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group having 2 to 8 carbon atoms, and / or an alkenoyl group having 2 to 8 carbon atoms,
  • Z11 and Z21 are each independently —COO—, —OCO—, —CH 2 CH 2 —, —OCH 2 —, —CH
  • Sp 231 , Sp 232 , Sp 233 , Sp 234 and Sp 235 are each independently from the viewpoint of enhancing storage stability.
  • , preferably represents an alkylene group having 1 to 14 carbon atoms, and each of the two or more CH 2 groups not one CH 2 group or adjacent existing in the alkylene group independently of one another, -O It may be replaced by-, -COO- or -OCO-.
  • Sp 231 , Sp 232 , Sp 233 , Sp 234 and Sp 235 each independently preferably represent an alkylene group having 1 to 12 carbon atoms, and one CH 2 present in the alkylene group. A group or two or more non-adjacent CH 2 groups may be replaced by —O—.
  • B11, B21 and B31 each independently may have the above-described substituents such as 1,4-phenylene group, 1,4-cyclohexylene group, 2 , 6-naphthylene group, and Z11 and Z21 are each independently —COO—, —OCO—, —CH 2 CH 2 —, —OCH 2 —, —CH 2 O—, —CH ⁇ CH It is preferable to represent —, —C ⁇ C—, —C ⁇ N—, —N ⁇ C—, or a single bond, and r11 preferably represents 0 or 1.
  • Examples of the compounds represented by the above general formula (II-3-1) to general formula (II-3-2) include the following general formulas (II-3-3-1) to (II-3-3-1-10) ), But is not limited to the following general formula.
  • P 231 to P 235 , Sp 231 to Sp 235 , X 231 to X 235 , q231 to q238, and MG 3 are Each represents the same definition as in general formula (II-3-1) to general formula (II-3-2).
  • B111, B112, B113, B21, and B31 are respectively B11 of the general formula (II-3-b), It represents the same as the definition of B21 and B31, and preferred groups also represent the same as the definitions of B11 to B31, and may be the same or different.
  • Z111, Z112, Z113, and Z21 are the same as Z11 and Z21 in the general formula (II-3-b), respectively. It represents the same as the definition, and preferred groups also represent the same as the definitions of Z11 to Z21, and may be the same or different.
  • Examples of the compounds represented by the general formulas (II-3-3-1) to (II-3-3-10) include the following formulas (II-3-3-3-1) to (II-3): Although the compound represented by -3-3-3) is exemplified, the compound is not limited thereto.
  • R f , R g, and R h each independently represent a hydrogen atom or a methyl group
  • R i , R j, and R k are each independently a hydrogen atom, a halogen atom, or a carbon number of 1 to 6
  • m4 to m9 each independently represents an integer of 0 to 18, and n4 to n9 each independently represents 0 or 1.
  • the polyfunctional polymerizable liquid crystal compound having three or more polymerizable functional groups can be used alone or in combination of two or more.
  • the optical anisotropic body of the present invention is produced using a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound (II) having two or more polymerizable functional groups in the molecule.
  • the total content of the polyfunctional polymerizable liquid crystal compound having three or more polymerizable functional groups in the molecule is the polymerizable liquid crystal compound (II), polymerizable liquid crystal compound ( Of the total content of II-1) and chiral compound (III), it is preferably 0 to 80% by mass, more preferably 0 to 60% by mass, and particularly preferably 0 to 40% by mass. .
  • the lower limit is preferably 10% by mass or more, more preferably 20% by mass or more, and particularly preferably 30% by mass or more
  • the upper limit is preferably 50% by mass or less, more preferably 35% by mass or less, and particularly preferably 20% by mass or less.
  • the optical anisotropic body of the present invention is produced using a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound (II) having two or more polymerizable functional groups in the molecule.
  • the product may contain a monofunctional polymerizable liquid crystal compound having one polymerizable functional group in the molecule as an optional component.
  • a compound represented by the following general formula (II-1) is preferable.
  • P 211 represents a polymerizable functional group
  • X 211 represents —O—, —S—, —OCH 2 —, —CH 2 O—, —CO—, —COO—, —OCO—, —CO—S—, — S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, —SCH 2 —, —CH 2 S—, —CF 2 O—, —OCF 2 —, —CF 2 S—, —SCF 2 —, —CH ⁇ CH—COO—, —CH ⁇ CH—OCO—, —COO—CH ⁇ CH—, —OCO—CH ⁇ CH—, —COO—CH 2 CH 2 —, — OCO—CH 2 CH 2 —, —CH 2 CH 2 —COO—, —CH 2 CH 2 —OCO—, —COO—CH 2 CH 2 —, — OCO—CH 2 CH 2 —,
  • B11, B21 and B31 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran- 2,5-diyl group, 1,3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene- 2,6-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3 4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group,
  • the hydrogen atom in the alkyl group may be substituted with one or more phenyl groups, each of two or more CH 2 groups not one CH 2 group or adjacent present in this group Independently of each other, —O—, —COO—, —OCO Or may be replaced by —OCO—O—), an alkoxy group having 1 to 8 carbon atoms, an alkanoyl group having 1 to 8 carbon atoms, an alkanoyloxy group having 1 to 8 carbon atoms, or the number of carbon atoms May have an alkoxycarbonyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group having 2 to 8 carbon atoms, and / or an alkenoyl group having 2 to 8 carbon atoms,
  • Z11 and Z21 are each independently —COO—, —OCO—, —CH 2 CH 2 —, —OCH 2 —, —CH
  • Sp 211 is preferably each independently an alkylene group having 1 to 14 carbon atoms from the viewpoint of enhancing storage stability, and is present in the alkylene group.
  • Two CH 2 groups or two or more non-adjacent CH 2 groups may be each independently replaced by —O—, —COO— or —OCO—.
  • Sp 211 are each independently more preferably an alkylene group having 1 to 12 carbon atoms, not one CH 2 group or adjacent existing in the alkylene group two or more CH 2 The group may be replaced by -O-.
  • X 211 each independently represents —O—, —OCH 2 —, —CH 2 O—, —CO—, —COO—, —OCO—, —O—CO.
  • R 211 represents a hydrogen atom, a halogen atom, a cyano group, one —CH 2 —, or two or more non-adjacent —CH 2 —, each independently —O —, —CO—, —COO—, —OCO—, —O—CO—O—, —CH ⁇ CH—COO—, —CH ⁇ CH—OCO—, —COO—CH ⁇ CH—, —OCO—CH
  • R 211 represents a hydrogen atom, a halogen atom, a cyano group, one —CH 2 —, or two or more non-adjacent —CH 2 —, each independently —O—, —CO—, —COO.
  • one or more hydrogen atoms of the alkyl group or alkenyl group may be substituted with a halogen atom or a cyano group, and when a plurality of substituents are substituted, they may be the same or different. Also good.
  • Examples of the general formula (II-1) include compounds represented by the following general formulas (II-1-1) to (II-1-4), but are not limited to the following general formulas is not.
  • P 211 , Sp 211 , X 211 , and q 211 are the same as defined in the general formula (II-1).
  • B111, B112, B113, B21, and B31 are the same as the definitions of B11 to B31 in the general formula (II-1-b).
  • preferred groups also represent the same as defined for B11 to B31, and may be the same or different.
  • Z111, Z112, Z113, and Z21 represent the same definitions as Z11 to Z21 in the general formula (II-1-b).
  • R 211 represents a hydrogen atom, a halogen atom, a cyano group, one —CH 2 —, or two or more non-adjacent — CH 2 — is independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO.
  • the compounds represented by the general formulas (II-1-1) to (II-1-4) are represented by the following formulas (II-1-1-1) to (II-1-1-26).
  • the compounds represented are exemplified, but not limited thereto.
  • R c represents a hydrogen atom or a methyl group
  • m represents an integer of 0 to 18, n represents 0 or 1
  • R 211 represents the above general formulas (II-1-1) to (II- 1-4) is the same as defined above, except that R 211 represents a hydrogen atom, a halogen atom, a cyano group, one —CH 2 — is —O—, —CO—, —COO—, —OCO—, It preferably represents a linear alkyl group having 1 to 6 carbon atoms or a linear alkenyl group having 1 to 6 carbon atoms, which may be substituted by
  • the cyclic group includes one or more F, Cl, CF 3 , OCF 3 , CN groups, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and 1 to 8 alkanoyl groups, alkanoyloxy groups having 1 to 8 carbon atoms, alkoxycarbon
  • the compounds represented by the general formulas (II-1-1-1) to (II-1-1-26) are more specifically represented by the following general formulas (II-1-2-1) to The compound represented by (II-1-2-37) can be exemplified, but is not limited thereto.
  • the optical anisotropic body of the present invention is produced using a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound (II) having two or more polymerizable functional groups in the molecule.
  • the product may contain a monofunctional polymerizable liquid crystal compound having one polymerizable functional group in the molecule as an optional component, and the above general formula (II-1), general formula (II-1- 1) to the above general formula (II-1-4), the above general formula (II-1-1-1) to the general formula (II-1-1-26), or the general formula (II-1-2- 1) to the general formula (II-1-2-37), the total content of the monofunctional polymerizable liquid crystal compound having one polymerizable functional group in the molecule is Of the total content of the polymerizable liquid crystal compound (II), the polymerizable liquid crystal compound (II-1) and the chiral compound (III), 0 Preferably contains 30% by mass, more preferably contains 0 to 20 wt%, and particularly
  • the optical anisotropic body of the present invention is produced using a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound (II) having two or more polymerizable functional groups in the molecule.
  • the product contains a chiral compound (III) which may optionally exhibit liquid crystallinity or may be non-liquid crystalline.
  • the chiral compound used in the present invention preferably has one or more polymerizable functional groups.
  • the polymerizable 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, etc., and a rigid group 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.
  • the compounding amount of the polymerizable chiral compound needs to be appropriately adjusted depending on the helical induction force of the compound, but the polymerization contained in the polymerizable liquid crystal composition used when producing the optical anisotropic body of the present invention.
  • the total content of the polymerizable liquid crystal compound (II), the polymerizable liquid crystal compound (II-1) and the chiral compound (III) it is preferably 0 to 25% by mass, more preferably 0 to 20% by mass. It is preferably contained in an amount of 0 to 15% by mass.
  • Examples of the general formula of the chiral compound include general formulas (III-1) to (III-4), but are not limited to the following general formula.
  • Sp 3a and Sp 3b each independently represent an alkylene group having 0 to 18 carbon atoms, and the alkylene group is a carbon atom having one or more halogen atoms, a CN group, or a polymerizable functional group.
  • alkyl group having 1 to 8 may be substituted by an alkyl group having 1 to 8, two or more of CH 2 groups, independently of one another each of the present in the radical is not one CH 2 group or adjacent, each other oxygen atom -O-, -S-, -NH-, -N (CH 3 )-, -CO-, -COO-, -OCO-, -OCOO-, -SCO-, -COS- Or it may be replaced by -C ⁇ C- A1, A2, A3, A4 and A5 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, , 3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2
  • R 3a and R 3b are represented by the general formula (III-a)
  • P 3a represents a polymerizable functional group.
  • P 3a preferably represents a substituent selected from the polymerizable groups represented by the following formulas (P-1) to (P-20).
  • the formula (P-1) or the formulas (P-2), (P-7), (P-12), (P-13) ) are preferred, and formulas (P-1), (P-7), and (P-12) are more preferred.
  • chiral compound examples include compounds (III-5) to (III-46), but are not limited to the following compounds.
  • n and n each independently represent an integer of 1 to 18, R and R 1 to R 4 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms.
  • the optical anisotropic body of the present invention is produced using a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound (II) having two or more polymerizable functional groups in the molecule. It is preferable to use a mixture of a plurality of the polymerizable liquid crystal compounds in the product.
  • a polymerizable liquid crystal compound having one polymerizable functional group in the molecule and two or more polymerizable functional groups in the molecule.
  • the total amount of the polymerizable liquid crystal compound having a content of 60% by mass to 100% by mass of the total amount of the polymerizable liquid crystal compound (II), the polymerizable liquid crystal compound (II-1) and the chiral compound (III). It is particularly preferable that the content be 70% by mass to 100% by mass.
  • the polymerizable liquid crystal composition used for producing the optical anisotropic body of the present invention exhibits liquid crystallinity other than the polymerizable compound represented by the above general formula (II-A) and general formula (II-1).
  • a polymerizable discotic compound that may be non-liquid crystalline may be contained.
  • the polymerizable discotic compound used in the present invention preferably has at least one polymerizable functional group.
  • examples of such compounds include polymerizable compounds described in, for example, JP-A-7-281028, JP-A-7-287120, JP-A-7-333431, and JP-A-8-27284. Is mentioned.
  • the blending amount of the polymerizable discotic compound needs to be appropriately adjusted depending on the compound, but is preferably contained in an amount of 0 to 10% by mass in the polymerizable composition.
  • Examples of the general formula of the polymerizable discotic compound include general formulas (4-1) to (4-3), but are not limited to the following general formula.
  • Sp 4 represents an alkylene group having 0 to 18 carbon atoms, and the alkylene group is substituted with one or more halogen atoms, CN group, or an alkyl group having 1 to 8 carbon atoms having a polymerizable functional group.
  • a 4 represents 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, 1,3-dioxane-2,5-diyl group, tetrahydro Thiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2,6-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5 -Diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene- 2,7-diyl group, 9,10-dihydrophenanthrene-2,7-
  • One CH 2 group present or two or more non-adjacent CH 2 groups are each independently of each other in a form in which oxygen atoms are not directly bonded to each other, —O—, —S—, —NH—, May be replaced by —N (CH 3 ) —, —CO—, —COO—, —OCO—, —OCOO—, —SCO—, —COS— or —C ⁇ C—, Or R 4 represents the general formula (4-a)
  • P 4a represents a polymerizable functional group
  • Sp 3a represents the same meaning as Sp 1
  • P 4a preferably represents a substituent selected from the polymerizable groups represented by the following formulas (P-1) to (P-20).
  • the formula (P-1) or the formulas (P-2), (P-7), (P-12), (P-13) ) are preferred, and formulas (P-1), (P-7), and (P-12) are more preferred.
  • polymerizable discotic compound examples include compounds (4-4) to (4-8), but are not limited to the following compounds.
  • (Polymerization initiator) Photopolymerization initiator
  • the polymerizable liquid crystal composition used for producing the optical anisotropic body of the present invention preferably contains a photopolymerization initiator. It is preferable to contain at least one photopolymerization initiator.
  • the amount of the photopolymerization initiator used was 100 parts by mass of the total content of the polymerizable liquid crystal compound (II), the polymerizable liquid crystal compound (II-1) and the chiral compound (III) contained in the polymerizable liquid crystal composition.
  • the orientation state in the post-process after the retardation film formation (firing process, transparent electrode sputtering process, further calcining process) is good, transparency, An optical anisotropic body having a high phase difference retention can be obtained. If the usage-amount of a photoinitiator is 0.1 mass part or less, sclerosis
  • thermal polymerization initiator known and conventional ones can be used.
  • methyl acetoacetate peroxide cumene hydroperoxide, benzoyl peroxide, bis (4-t-butylcyclohexyl) peroxydicarbonate, t-butyl Peroxybenzoate, methyl ethyl ketone peroxide, 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, p-pentahydroperoxide, t-butylhydroperoxide, dicumyl peroxide, isobutyl Organic peroxides such as peroxide, di (3-methyl-3-methoxybutyl) peroxydicarbonate, 1,1-bis (t-butylperoxy) cyclohexane, 2,2′-azobisisobutyronitrile , 2,2'-azobis (2,4 Azonitrile compounds such as dimethylvaleronitrile), azoamidin compounds
  • the amount of the thermal polymerization initiator used was 100 parts by mass of the total content of the polymerizable liquid crystal compound (II), the polymerizable liquid crystal compound (II-1) and the chiral compound (III) contained in the polymerizable liquid crystal composition. In this case, it is preferable to add 0.1 to 7 parts by mass, more preferably 0.3 to 7 parts by mass, and particularly preferably 0.5 to 7 parts by mass. These can be used alone or in combination of two or more.
  • the polymerizable liquid crystal composition used when producing the optical anisotropic body of the present invention may be used in combination with a curing agent. Specific examples include aliphatic polyamines such as diethylenetriamine and triethylenetetramine, EH-235R-2 manufactured by ADEKA, and ketimine compounds such as jER Cure H3 and H30 manufactured by Mitsubishi Chemical.
  • the amount of the curing agent used is when the total content of the polymerizable liquid crystal compound (II), the polymerizable liquid crystal compound (II-1) and the chiral compound (III) contained in the polymerizable liquid crystal composition is 100 parts by mass. In addition, 0.01 to 20 parts by mass is preferable, 0.05 to 15 parts by mass is more preferable, and 0.1 to 10 parts by mass is particularly preferable. These can be used alone or in combination of two or more. (Organic solvent) An organic solvent may be added to the polymerizable liquid crystal composition used in producing the optical anisotropic body of the present invention.
  • an organic solvent in which the polymerizable liquid crystal compound exhibits good solubility is preferable, and an organic solvent having a low boiling point that can be dried at a temperature of 100 ° C. or lower is preferable.
  • an organic solvent having a boiling point of 135 ° C. or less is preferable, more preferably 125 ° C., and most preferably 115 ° C.
  • the organic solvent used in producing the optical anisotropic body of the present invention include aromatic hydrocarbons such as toluene, ester solvents such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate, methyl ethyl ketone, and methyl isobutyl.
  • ketone solvents such as ketone and cyclopentanone
  • ether solvents such as tetrahydrofuran and 1,2-dimethoxyethane
  • propylene glycol monomethyl ether acetate propylene glycol monomethyl ether acetate
  • diethylene glycol monomethyl ether acetate any one of ketone solvents, ether solvents, ester solvents and aromatic hydrocarbon solvents It is preferable to use the above from the viewpoint of solution stability.
  • the amount of residual solvent contained in the optically anisotropic layer is measured as follows. Specifically, first, the optical anisotropic body of the present invention is immersed in 1 ml of anisole for 24 hours.
  • An organic solvent other than anisole may be used as long as the organic solvent can obtain sufficient solubility of the polymerizable liquid crystal compound.
  • the anisole solution from which the residual solvent was extracted was analyzed using gas chromatography, and the residual solvent amount (ppm) of the optical anisotropic body was calculated.
  • the polymerizable liquid crystal composition used in producing the optical anisotropic body of the present invention can be applied to a substrate when it is made into a solution using an organic solvent.
  • the ratio of the organic solvent used in the polymerizable liquid crystal composition is not particularly limited as long as the applied state is not significantly impaired, but the total amount of the organic solvent contained in the polymerizable liquid crystal composition is 10 to 95% by mass. It is preferably 12 to 90% by mass, more preferably 15 to 85% by mass.
  • the heating temperature at the time of heating and stirring may be appropriately adjusted in consideration of the solubility of the composition to be used in the organic solvent, but is preferably 15 ° C. to 110 ° C., more preferably 15 ° C. to 105 ° C. from the viewpoint of productivity. 15 to 100 ° C. is more preferable, and 20 to 90 ° C. is particularly preferable.
  • a dispersion stirrer when adding the organic solvent, it is preferable to stir and mix with a dispersion stirrer.
  • the dispersion stirrer include a disperser having a stirring blade such as a disper, a propeller, and a turbine blade, a paint shaker, a planetary stirring device, a shaker, a stirrer, a shaker, or a rotary evaporator.
  • an ultrasonic irradiation apparatus can be used.
  • the number of rotations of stirring when the organic solvent is added is preferably adjusted as appropriate depending on the stirring device used.
  • the number of rotations of stirring is preferably 10 rpm to 1000 rpm, and 50 rpm More preferably, it is set to ⁇ 800 rpm, particularly preferably 150 rpm to 600 rpm.
  • 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-Nn-butyl- 4-butanolamine, N-nitroso-diisopropanolamine, N-nitroso-N-ethyl-4-butanolamine, 5-nitroso-8-hydroxyquinoline, N-nitrosomorpholine, N-nitros
  • the addition amount of the polymerization inhibitor used in the polymerizable liquid crystal composition used in producing the optical anisotropic body of the present invention is the polymerizable liquid crystal compound (II) and polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition.
  • the total content of (II-1) and chiral compound (III) is 100 parts by mass, it is preferably 0.01 to 1.0 part by mass, and 0.05 to 0.5 part by mass. Is more preferable.
  • the polymerizable liquid crystal composition used when producing the optical anisotropic body of the present invention is one kind of alignment control agent that further promotes the alignment in order to make the polymerizable liquid crystal compound horizontally or planarly aligned. You may contain above.
  • Alignment control agents that can be contained include alkyl carboxylates, alkyl phosphates, alkyl sulfonates, fluoroalkyl carboxylates, fluoroalkyl phosphates, fluoroalkyl sulfonates, polyoxyethylene derivatives, fluoro Examples include alkylethylene oxide derivatives, polyethylene glycol derivatives, alkylammonium salts, fluoroalkylammonium salts, and the like, and fluorine-containing surfactants are particularly preferable.
  • orientation control agent examples include compounds represented by the following general formulas (5-1) to (5-4), but the structure is not limited thereto.
  • R may be the same or different and each represents an alkoxy group having 1 to 30 carbon atoms which may be substituted with a fluorine atom.
  • m1, m2 and m3 each represents an integer of 1 or more. Represents.
  • Chain transfer agent The polymerizable liquid crystal composition used in producing the optical anisotropic body of the present invention preferably further includes a chain transfer agent in order to further improve the adhesion to the substrate when the optical anisotropic body is used.
  • chain transfer agent examples include aromatic hydrocarbons, halogenated hydrocarbons such as chloroform, carbon tetrachloride, carbon tetrabromide, and bromotrichloromethane, and thiol compounds such as monothiol, dithiol, trithiol, and tetrathiol.
  • aromatic hydrocarbons and thiol compounds are more preferable.
  • compounds represented by the following general formulas (8-1) to (8-12) are preferable.
  • R 65 represents an alkyl group having 2 to 18 carbon atoms, and the alkyl group may be linear or branched, and one or more methylene groups in the alkyl group are oxygen atoms.
  • a sulfur atom that is not directly bonded to each other may be substituted with an oxygen atom, a sulfur atom, —CO—, —OCO—, —COO—, or —CH ⁇ CH—
  • R 66 is a carbon atom Represents an alkylene group of 2 to 18, and one or more methylene groups in the alkylene group are oxygen atoms, sulfur atoms, —CO—, —OCO—, wherein oxygen atoms and sulfur atoms are not directly bonded to each other.
  • —COO—, or —CH ⁇ CH— may be substituted.
  • the amount of the chain transfer agent added is the polymerizable liquid crystal compound (II), polymerizable liquid crystal compound (II-1) and chiral compound (in the polymerizable liquid crystal composition used for producing the optical anisotropic body of the present invention).
  • the total content of III is 100 parts by mass, it is preferably 0.5 to 10 parts by mass, and more preferably 1.0 to 5.0 parts by mass.
  • additives such as polymerizable compounds that do not have liquid crystallinity, thixotropic agents, ultraviolet absorbers, infrared absorbers, antioxidants, surface treatment agents, etc., do not significantly reduce the alignment ability of liquid crystals. To the extent that can be added.
  • optical anisotropic body of the present invention is obtained by applying the polymerizable liquid crystal composition of the present invention on a substrate having an alignment function, and the liquid crystal molecules in the polymerizable liquid crystal composition of the present invention are nematic, smectic, It is obtained by aligning and polymerizing in a state in which a chiral nematic phase or a chiral smectic phase is retained.
  • the retardation film described later is one of the uses of the optical anisotropic body, and is included in the concept of the optical anisotropic body.
  • the optically anisotropic body of the present invention is a polymerizable liquid crystal compound (II) having one or more polymerization initiators (I), one or two or more polymerizable functional groups in one or more molecules. And, optionally, an optically anisotropic layer using a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound (II-1) having one or more kinds of one polymerizable functional group,
  • the content of the polymerizable liquid crystal compound (II) contained in the optically anisotropic layer and optionally the polymerizable liquid crystal compound (II-1) is 0.0001% by mass or more and 3% by mass or less.
  • the content of unreacted polymerizable liquid crystal compound (II) contained in the optically anisotropic layer and optionally contained unreacted polymerizable liquid crystal compound (II-1) is less than 0.0001% by mass.
  • the orientation and transparency in the firing step after forming the retardation film, the transparent electrode sputtering step, and the further firing step are deteriorated.
  • the content of the polymerizable liquid crystal compound (II) contained in the optically anisotropic layer and the unreacted polymerizable liquid crystal compound (II-1) optionally contained exceeds 3% by mass, the retardation film
  • the orientation, heat resistance, and retardation retention in the firing step after formation, the transparent electrode sputtering step, and the further firing step are deteriorated.
  • the content of the polymerizable liquid crystal compound (II) contained in the optically anisotropic layer and the polymerizable liquid crystal compound (II-1) optionally contained is 0.0001 mass% or more and 1 mass% or less. More preferably, it is 0.0001% by mass or more and 0.5% by mass or less.
  • a polymerizable liquid crystal composition is used. A method of heating the polymerizable liquid crystal composition when polymerizing by UV irradiation is exemplified.
  • the temperature during UV irradiation is preferably 50 ° C. to 60 ° C., more preferably 50 ° C. to 58 ° C., and most preferably 50 ° C. to 55 ° C.
  • the amount of residual monomer in the optical anisotropic body can be adjusted to 0.0001 to 3% by mass.
  • An optically anisotropic body having a good orientation state in the electrode sputtering step and further firing step, and high transparency and retardation retention can be obtained.
  • the amount of residual monomer contained in the optically anisotropic layer may be a known method, and an example is a measuring method using high performance liquid chromatography (HPLC).
  • the obtained optical anisotropic body of the present invention is immersed in acetone for 24 hours. After immersion, the acetone solution from which the residual monomer has been extracted is concentrated with an evaporator.
  • the solution may be an organic solvent other than acetone as long as sufficient solubility of the polymerizable liquid crystal compound can be obtained.
  • concentration by an evaporator the obtained residue is dissolved in 1 ml of tetrahydrofuran (THF).
  • HPLC high performance liquid chromatography
  • the amount of residual solvent contained in the optically anisotropic layer is preferably 2500 ppm or less. If the amount of residual solvent contained in the optically anisotropic layer exceeds 2500 ppm, the orientation and retardation retention ratio may deteriorate in the firing step after forming the optically anisotropic layer, the transparent electrode sputtering step, and the further firing step. is there. Further, the amount of residual solvent contained in the optically anisotropic layer is more preferably 1500 ppm or less. The amount of the residual solvent contained in the optically anisotropic layer can be adjusted to 2500 ppm or less by using the organic solvent having a boiling point of 135 ° C. or less.
  • the well-known method can be used for the amount of residual solvent contained in an optically anisotropic layer
  • the measuring method using gas chromatography (GC) is mentioned as an example. Measure as follows. First, specifically, the obtained optical anisotropic body of the present invention is immersed in 1 ml of anisole for 24 hours to obtain an anisole solution from which a residual solvent is extracted. The obtained anisole solution is analyzed by gas chromatography (GC), and the residual solvent amount (ppm) is calculated. (Retardation film) The retardation film of the present invention is produced in the same manner as the optical anisotropic body of the present invention. A liquid crystalline compound uniformly forms a continuous alignment state with respect to the substrate, and a retardation film is obtained.
  • the retardation film using the optical anisotropic body of the present invention is synonymous with the retardation layer and the retardation film.
  • Examples of the retardation film obtained by aligning and polymerizing the polymerizable liquid crystal composition of the present invention on a substrate by coating or the like include a positive A plate, a negative C plate, and a biaxial plate.
  • the positive A plate has a refractive index in the in-plane slow axis direction of the retardation film nx, a refractive index in the in-plane fast axis direction of the retardation film ny, and a refractive index in the thickness direction of the retardation film.
  • the refractive index in the in-plane slow axis direction of the retardation film is nx
  • the refractive index in the in-plane fast axis direction of the retardation film is ny
  • the refractive index in the thickness direction of the retardation film is nz.
  • the refractive index in the in-plane slow axis direction of the retardation film is nx
  • the refractive index in the in-plane fast axis direction of the retardation film is ny
  • the refractive index in the thickness direction of the retardation film is nz.
  • the retardation film has a relationship of “nx> ny> nz”.
  • the retardation film using the optical anisotropic body of the present invention is used for liquid crystal display devices, displays, optical elements, optical parts, colorants, security markings, laser emission members, optical films, compensation films, and the like. Accordingly, it is applied in a form suitable for the application. Moreover, an adhesive, an adhesive layer, an adhesive, an adhesive layer, a protective film, a polarizing film, or the like may be laminated. (Phase difference patterning film)
  • the retardation patterning film using the optical anisotropic body of the present invention is formed by sequentially laminating a base material, an alignment film, and a polymer of a polymerizable liquid crystal composition in the same manner as the optical anisotropic body of the present invention.
  • patterning is performed so as to obtain partially different phase differences. Patterning may be in different directions, such as lattice patterning, circular patterning, polygonal patterning, and the like.
  • the retardation patterning film of the present invention is applied depending on the use of a liquid crystal display device, a display, an optical element, an optical component, a colorant, a security marking, a laser emission member, an optical film, a compensation film, and the like. .
  • an alignment film is provided on a substrate, and the polymerizable liquid crystal composition is patterned and aligned when the polymerizable liquid crystal composition of the present invention is applied and dried during the alignment treatment.
  • an alignment treatment include a fine rubbing treatment, a polarized ultraviolet visible light irradiation treatment through a photomask, and a fine shape processing treatment.
  • the alignment film known and conventional ones are used.
  • Such alignment films include polyimide, polysiloxane, polyamide, polyvinyl alcohol, polycarbonate, polystyrene, polyphenylene ether, polyarylate, polyethylene terephthalate, polyether sulfone, epoxy resin, epoxy acrylate resin, acrylic resin, coumarin compound, chalcone.
  • the compound include compounds, cinnamate compounds, fulgide compounds, anthraquinone compounds, azo compounds, and arylethene compounds.
  • the compound subjected to the alignment treatment by fine rubbing is preferably an alignment treatment or a compound in which crystallization of the material is promoted by adding a heating step after the alignment treatment.
  • the brightness enhancement film using the optical anisotropic body of the present invention is produced in the same manner as the optical anisotropic body of the present invention.
  • a retardation film and a ⁇ / 4 wavelength plate obtained by curing the polymerizable liquid crystal composition with an adhesive layer or the like it can be used as the brightness enhancement film of the present invention.
  • the antireflection film using the optical anisotropic body of the present invention is produced in the same manner as the optical anisotropic body of the present invention.
  • a retardation film and a ⁇ / 4 wavelength plate obtained by curing the polymerizable liquid crystal composition with an adhesive layer or the like it can be used as the antireflection film of the present invention.
  • Image display devices such as organic EL have problems such as reflection of external light and reflection of the background. However, the above problem can be prevented by providing the antireflection film of the present invention.
  • Thermal barrier film The thermal barrier film using the optical anisotropic body of the present invention is produced in the same manner as the optical anisotropic body of the present invention.
  • the base material used for the optical anisotropic body of the present invention is a base material that is usually used for a liquid crystal display device, a display, an optical component or an optical film, and is dried at the time of coating after application of the polymerizable liquid crystal composition of the present invention There is no particular limitation as long as the material has heat resistance that can withstand heating.
  • Examples of such a substrate include organic materials such as a glass substrate, a metal substrate, a ceramic substrate, and a plastic substrate.
  • organic materials such as a glass substrate, a metal substrate, a ceramic substrate, and a plastic substrate.
  • examples thereof include cellulose derivatives, polyolefins, polyesters, polycarbonates, polyacrylates (acrylic resins), polyarylate, polyether sulfone, polyimide, polyphenylene sulfide, polyphenylene ether, nylon, and polystyrene.
  • plastic base materials such as polyester, polystyrene, polyacrylate, polyolefin, cellulose derivative, polyarylate, and polycarbonate are preferable, and base materials such as polyacrylate, polyolefin, and cellulose derivative are more preferable, and COP (cycloolefin polymer) is used as the polyolefin. It is particularly preferable to use TAC (triacetyl cellulose) as the cellulose derivative and PMMA (polymethyl methacrylate) as the polyacrylate.
  • TAC triacetyl cellulose
  • PMMA polymethyl methacrylate
  • As a shape of a base material you may have a curved surface other than a flat plate.
  • These base materials may have an electrode layer, an antireflection function, and a reflection function as needed.
  • 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 surface of the substrate by a method such as vapor deposition, or in order to add optical added value.
  • the material may be a pickup lens, a rod lens, an optical disk, a retardation film, a light diffusion film, a color filter, or the like.
  • 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 so that the polymerizable liquid crystal composition is aligned when the polymerizable liquid crystal composition used in producing the optical anisotropic body of the present invention is applied and dried.
  • an alignment film may be provided. Examples of the alignment treatment include stretching treatment, rubbing treatment, polarized ultraviolet visible light irradiation treatment, ion beam treatment, and the like.
  • 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.
  • 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.
  • Application methods for obtaining the optical anisotropic body of the present invention include applicator method, bar coating method, spin coating method, roll coating method, direct gravure coating method, reverse gravure coating method, flexo coating method, ink jet method, and die coating.
  • a publicly known method such as a method, a cap coating method, a dip coating method, or a slit coating method can be used. After applying the polymerizable liquid crystal composition, it is dried as necessary.
  • Polymerization method Regarding the polymerization operation of the polymerizable liquid crystal composition for obtaining the optical anisotropic body of the present invention, generally light such as ultraviolet rays is used in a state where the liquid crystal compound in the polymerizable liquid crystal composition is aligned horizontally or planarly with respect to the substrate. It is performed by irradiation or heating. When the polymerization is performed by light irradiation, specifically, irradiation with ultraviolet light of 390 nm or less is preferable, and irradiation with light having a wavelength of 250 to 370 nm is most preferable.
  • 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.
  • Examples of the method for polymerizing the polymerizable liquid crystal composition used in the production of the optical anisotropic body of the present invention include a method of irradiating active energy rays and a thermal polymerization method.
  • the method of irradiating active energy rays is preferable because the reaction proceeds, and among them, the method of irradiating light such as ultraviolet rays is preferable because the operation is simple.
  • a polymerizable liquid crystal composition usually has a liquid crystal phase within a range from a C (solid phase) -N (nematic) transition temperature (hereinafter abbreviated as a CN transition temperature) to a NI transition temperature in a temperature rising process. Indicates.
  • a C (solid phase) -N (nematic) transition temperature hereinafter abbreviated as a CN transition temperature
  • NI transition temperature a transition temperature rising process.
  • the temperature lowering process since the thermodynamically non-equilibrium state is obtained, there is a case where the liquid crystal state is not solidified even at a temperature below the CN transition temperature. This state is called a supercooled state.
  • the liquid crystal composition in a supercooled state is also included in the state in which the liquid crystal phase is retained.
  • irradiation with ultraviolet light of 390 nm or less is preferable, and irradiation with light having a wavelength of 250 to 370 nm is most preferable.
  • the polymerizable composition causes decomposition or the like due to ultraviolet light of 390 nm or less
  • This light is preferably diffused light and unpolarized light.
  • Ultraviolet irradiation intensity in the range of 0.05kW / m 2 ⁇ 10kW / m 2 is preferred.
  • the range of 0.2 kW / m 2 to 2 kW / m 2 is preferable.
  • the orientation state of the unpolymerized part is changed by applying an electric field, a magnetic field or temperature, and then the unpolymerized part is polymerized.
  • An optical anisotropic body having a plurality of regions having orientation directions can also be obtained.
  • the alignment was regulated in advance by applying an electric field, magnetic field or temperature to the unpolymerized polymerizable liquid crystal composition, and the state was maintained.
  • An optical anisotropic body having a plurality of regions having different orientation directions can also be obtained by irradiating light from above the mask and polymerizing it.
  • the optical anisotropic body obtained by polymerizing the polymerizable liquid crystal composition of the present invention can be peeled off from the substrate and used alone as an optical anisotropic body, or it can be used as an optical anisotropic body as it is without peeling off from the substrate. You can also In particular, since it is difficult to contaminate other members, it is useful when used as a laminated substrate or by being attached to another substrate.
  • the liquid crystal display device of the present invention is a display element in which a liquid crystal substance is sealed between light transmissive substrates such as glass.
  • the liquid crystal display device changes the polarization state of the light polarized by the polarizing plate placed on the back side of the liquid crystal cell by changing the molecular orientation of the liquid crystal material by electrical control from a display control device (not shown).
  • the image is displayed by controlling the amount of light transmitted through the polarizing plate arranged on the viewing side of the liquid crystal cell.
  • rod-shaped liquid crystal molecules having negative dielectric anisotropy are aligned.
  • the negative C plate of the retardation film of the present invention in order to widen the viewing angle by compensating the viewing angle dependence of the polarization axis orthogonality. Further, it is preferable to use a positive A plate in combination, and it is more preferable to stack a positive A plate and a negative C plate.
  • the positive A plate has an in-plane retardation value in the range of 30 to 500 nm at a wavelength of 550 nm. Are preferred.
  • the Nz coefficient is preferably in the range of 0.9 to 1.1.
  • the thickness direction retardation value at a wavelength of 550 nm is preferably in the range of 20 to 400 nm.
  • the refractive index anisotropy in the thickness direction is represented by a thickness direction retardation value Rth defined by the equation (2).
  • a thickness direction retardation value Rth an in-plane retardation value R 0 , a retardation value R 50 measured with a slow axis as an inclination axis and an inclination of 50 °, a film thickness d, and an average refractive index n 0 of the film are used.
  • nx, ny, and nz can be obtained by numerical calculation from the equation (1) and the following equations (4) to (7), and these can be substituted into the equation (2).
  • the Nz coefficient can be calculated from the equation (3). The same applies to other descriptions in the present specification.
  • R 0 (nx ⁇ ny) ⁇ d (1)
  • Rth [(nx + ny) / 2 ⁇ nz] ⁇ d (2)
  • Nz coefficient (nx ⁇ nz) / (nx ⁇ ny) (3)
  • R 50 (nx ⁇ ny ′) ⁇ d / cos ( ⁇ ) (4)
  • ny ′ ny ⁇ nz / [ny 2 ⁇ sin 2 ( ⁇ ) + nz 2 ⁇ cos 2 ( ⁇ )] 1/2 (7)
  • the numerical calculation shown here is automatically performed in the device, and the in-plane retardation value R0 , the thickness direction retardation value Rth, etc. are automatically displayed. There are many.
  • An example of such a measuring apparatus is RETS-100 (manufactured by Ot
  • the retardation film of the present invention is either a liquid crystal display device (out-cell type, FIG. 1) disposed outside the liquid crystal cell or a liquid crystal display device (in-cell type) where the retardation film is disposed inside the liquid crystal cell. It can also be applied to liquid crystal display devices. From the viewpoint of improving productivity by reducing the thickness, weight, and pasting process of the liquid crystal display device, it is better to use an in-cell type retardation film.
  • the “in-cell type retardation film” of the present invention has a retardation film on the inner side sandwiched between a pair of light-transmitting substrates, and is arranged inside the liquid crystal cell.
  • an optically anisotropic body polymerized with the polymerizable liquid crystal composition aligned is used for the retardation film.
  • the liquid crystal display device shown in FIGS. 2 and 3 is only one example of arrangement, and the position where the retardation film is provided is not limited thereto.
  • a retardation film may be provided at a desired position, such as between the electrode and the alignment film on the back side (FIGS. 10 and 11).
  • the liquid crystal display device of the present invention may have a color filter.
  • the color filter includes a black matrix and at least an RGB three-color pixel portion. Any method may be used for forming the color filter layer.
  • the liquid crystal display device of the present invention may have an alignment film for aligning the liquid crystal composition on the surface of the first substrate that contacts the liquid crystal composition on the second substrate.
  • the alignment film material is as described in the alignment treatment of the present invention.
  • a conductive metal oxide can be used as a material for the transparent electrode.
  • the metal oxide include indium oxide (In 2 O 3 ), tin oxide (SnO 2 ), and zinc oxide. (ZnO), indium tin oxide (In 2 O 3 —SnO 2 ), indium zinc oxide (In 2 O 3 —ZnO), niobium-doped titanium dioxide (Ti 1-x Nb x O 2 ), fluorine-doped tin oxide, graphene
  • nanoribbons or metal nanowires can be used, zinc oxide (ZnO), indium tin oxide (In 2 O 3 —SnO 2 ), or indium zinc oxide (In 2 O 3 —ZnO) is preferable.
  • a photo-etching method or a method using a mask can be used for patterning these transparent conductive films.
  • the liquid crystal display device of the invention may have a polarizing layer.
  • the polarizing layer is a member having a function of converting natural light into linearly polarized light.
  • the polarizing layer may be a film having a polarizing function.
  • a film obtained by stretching a polyvinyl alcohol film by adsorbing iodine or a dichroic dye a film obtained by stretching a polyvinyl alcohol film, and an iodine or dichroic dye.
  • substrate, and formed the polarizing layer, a wire grid polarizer, etc. are mentioned.
  • a material formed of a conductive material such as Al, Cu, Ag, Cu, Ni, Cr, and Si.
  • the polarizing layer may further include a film serving as a protective film, if necessary.
  • a film serving as a protective film examples include polyolefin films such as polyethylene, polypropylene and norbornene polymers, polyethylene terephthalate films, polymethacrylic acid ester films, polyacrylic acid ester films, and cellulose ester films.
  • an in-cell polarizing layer may be provided in which a polarizing layer is installed in the liquid crystal cell.
  • An example of the liquid crystal display device in this case is shown in FIGS.
  • the optical member having the polarizing layer described above may be provided with an adhesive layer for bonding with the liquid crystal cell.
  • An adhesive layer can also be provided for bonding with other members other than the liquid crystal cell.
  • the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer is not particularly limited. It can be selected and used.
  • the liquid crystal composition of the present invention includes cyanobiphenyl, phenylcyclohexyl, phenylbenzoate, cyclohexylbenzoate, azomethine, azobenzene, pyrimidine, dioxane, cyclohexylcyclohexane, stilbene, tolan, etc. There can be used a known and conventional one.
  • the image display device of the present invention can be used in various devices for image display.
  • Examples of the image display device include an organic EL display device, a plasma display display device, and the like, and there is no limitation on the application, type, and configuration of the image display device.
  • components such as a diffusion plate, an antireflection film, a protective film, a light diffusion plate, and a backlight can be arranged.
  • Optical element The optical anisotropic body of the present invention can also be used as an optical element. Examples of the optical element include a diffraction grating and a pickup lens, but the use, type, and configuration of the optical element are not limited.
  • the optically anisotropic body of the present invention can also be used as a printed matter. An example of the printed material is one printed to prevent counterfeiting, but there is no limitation on the application, type, and configuration of the printed material.
  • methylhydroquinone (MEHQ) D-1) as a polymerization inhibitor and the following compounds (E-1) to (E-3) as polymerization initiators with respect to 100 parts by mass of the total amount of the compounds represented by: Table 1 shows the following Megafac F-554 (F-1) as an orientation control agent, and cyclopentanone (G-1), toluene (G-2), and cyclohexanone (G-3) as organic solvents.
  • Each polymerizable liquid crystal composition was prepared using the ratio (parts by mass) shown in Table 4.
  • the following table shows specific compositions of the polymerizable liquid crystal compositions (1) to (23) and the comparative polymerizable liquid crystal compositions (24) to (36) of the present invention.
  • Example 1 (Residual monomer amount, residual solvent amount) ⁇ Preparation of optical anisotropic body for residual monomer amount and residual solvent amount evaluation> A polyimide alignment film material for a horizontal alignment film was applied on a light-transmitting substrate by spin coating, 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.
  • the rubbing treatment was performed using a commercially available rubbing apparatus.
  • the prepared polymerizable liquid crystal composition (1) was applied to the substrate obtained through the above steps at 700 rpm / 30 sec using a spin coater at room temperature and dried at 80 ° C. for 2 minutes. Then, after leaving at 25 ° C. for 2 minutes, use a high-pressure mercury lamp to set the irradiation amount to 3000 mJ / cm 2 and the irradiation temperature to 50 ° C. in a nitrogen atmosphere. Then, the optical anisotropic body of Example 1 was obtained by irradiating with UV light. The amount of residual monomer and the amount of residual solvent contained in the obtained optically anisotropic layer were evaluated.
  • the obtained optical anisotropic body was immersed in acetone for 24 hours to obtain an acetone solution in which residual monomers were extracted.
  • the obtained acetone solution was concentrated with an evaporator.
  • a solution obtained by dissolving the concentrated residue in 1 ml of tetrahydrofuran (THF) was analyzed by high performance liquid chromatography (HPLC), and the amount of residual monomer (mass%) of the optical anisotropic body was calculated.
  • residual solvent amount The obtained optical anisotropic body was immersed in 1 ml of anisole for 24 hours to obtain an anisole solution from which the remaining solvent was extracted.
  • the obtained anisole solution was analyzed by gas chromatography, and the residual solvent amount (ppm) was calculated.
  • the obtained optical anisotropic body was baked (230 ° C. for 30 minutes). After the firing treatment, ITO sputtering is performed on the obtained optical anisotropic body using a sputtering apparatus at 50 ° C.
  • the obtained optical anisotropic body was baked (230 ° C. for 30 minutes).
  • ITO sputtering was performed on the optical anisotropic body at 50 ° C. under a pressure of 3.7 ⁇ 10 ⁇ 1 Pa, an argon flow rate of 90 sccm, an oxygen gas flow rate of 4.7 sccm for 2 and a half minutes using a sputtering apparatus.
  • a 700 mm ITO film was formed on the optical anisotropic body.
  • the baking process 150 degreeC for 10 minutes
  • the phase difference was measured.
  • Optically anisotropic bodies were prepared using the polymerizable liquid crystal compositions (2) to (21) and (24) to (35), and their orientation, transparency and retardation retention were measured. The results are shown in the above table as Examples 2 to 21 and Comparative Examples 1 to 12, respectively.
  • the production methods of the optical anisotropic bodies of Examples 2 to 21 and Comparative Examples 1 to 12 are as follows.
  • the optically anisotropic body for evaluating the orientation of Example 2 was coated with a polyimide alignment film material for a horizontal alignment film on a light-transmitting substrate by spin coating, and the temperature was 100 ° C. And dried for 10 minutes, followed by baking at 200 ° C. for 60 minutes to obtain a coating film. The obtained coating film was rubbed. The rubbing treatment was performed using a commercially available rubbing apparatus. Each of the prepared polymerizable liquid crystal compositions was applied to the obtained base material at 700 rpm / 30 sec using a spin coater at room temperature, dried at 80 ° C. for 2 minutes, and then allowed to stand at 25 ° C. for 2 minutes.
  • the optical anisotropic bodies of Comparative Examples 5 to 6 for evaluation of orientation and the like were set at 25 ° C. and irradiated with UV light to obtain the optical anisotropic bodies of Examples and Comparative Examples.
  • the evaluation of the orientation, transparency, and retardation retention was performed by forming an ITO film on the optical anisotropic body under the same conditions as in Example 1.
  • the optical anisotropic body for evaluation of orientation, transparency, retardation retention, etc. is obtained by applying a polyimide alignment film material for a horizontal alignment film on a light-transmitting substrate by spin coating. After coating and drying at 100 ° C. for 10 minutes, a coating film was obtained by baking at 200 ° C. for 60 minutes. The obtained coating film was rubbed. The rubbing treatment was performed using a commercially available rubbing apparatus. Each of the prepared polymerizable liquid crystal compositions was applied to the obtained base material at 400 rpm / 30 sec using a spin coater at room temperature, dried at 80 ° C. for 2 minutes, and then allowed to stand at 25 ° C. for 2 minutes.
  • Example 8 Using a mercury lamp, in each nitrogen atmosphere, set the irradiation amount to 3000 mJ / cm 2 and the irradiation temperature to 50 ° C. and irradiate with UV light. An example optical anisotropic body was obtained.
  • the evaluation of the orientation, transparency, and retardation retention was performed by forming an ITO film on the optical anisotropic body under the same conditions as in Example 1.
  • the optical anisotropic body for evaluation of orientation in Example 8 has an irradiation temperature of 60 ° C.
  • the optical anisotropic body for evaluation of alignment in Comparative Examples 7 to 10 has a temperature of 75 ° C.
  • optical anisotropic bodies of Examples and Comparative Examples By setting and irradiating with UV light, optical anisotropic bodies of Examples and Comparative Examples were obtained.
  • the evaluation of the orientation, transparency, and retardation retention was performed by forming an ITO film on the optical anisotropic body under the same conditions as in Example 1.
  • the optically anisotropic bodies for evaluating the orientation of Examples 18 to 19 and Comparative Example 11 were prepared by adding a solution containing 3% by weight of a cinnamic acid polymer (H) (organic solvent cyclopentanone) on a light-transmitting substrate. It was applied by spin coating, dried at 80 ° C. for 2 minutes, and then allowed to stand at 25 ° C. for 2 minutes. Then, using a high-pressure mercury lamp, it was linearly polarized with visible ultraviolet light having a wavelength of about 313 nm through a polarizing filter. And the photo-alignment film was obtained by irradiating parallel light from the perpendicular direction with respect to a base material (irradiation amount: 100 mJ / cm ⁇ 2 >).
  • H cinnamic acid polymer
  • the cinnamic acid polymer (H) was prepared as follows. 1 part (10.0 mmol) of the compound (I) represented by the above structural formula was dissolved in 10 parts of ethyl methyl ketone, 0.01 part of azobisisobutyronitrile (AIBN) is added and heated under reflux for 2 days under a nitrogen atmosphere to obtain a solution, the solution is then added dropwise to 60 parts of methanol and the precipitated solid is filtered. The obtained solid was dissolved in 5 parts of THF, dropped into 120 parts of ice-cooled hexane, and the precipitated solid was filtered, and the obtained solid was dissolved in 5 parts of THF, and dropped into 120 parts of ice-cooled methanol, and stirred.
  • AIBN azobisisobutyronitrile
  • Example 2 The precipitated solid is filtered. The obtained solid is dissolved in THF and then vacuum-dried.
  • Each of the prepared polymerizable liquid crystal compositions was applied to the obtained base material at 700 rpm / 30 sec using a spin coater at room temperature, dried at 80 ° C. for 2 minutes, and then allowed to stand at 25 ° C. for 2 minutes. Using a mercury lamp, in each nitrogen atmosphere, set the irradiation amount to 3000 mJ / cm 2 and the irradiation temperature to 50 ° C. and irradiate with UV light.
  • the optical anisotropic bodies of Examples and Comparative Examples were obtained.
  • the evaluation of the orientation, transparency, and retardation retention was performed by forming an ITO film on the optical anisotropic body under the same conditions as in Example 1.
  • the optical anisotropic bodies for evaluation of orientation in Examples 20 to 21 were prepared by adding a solution containing 3% by weight of cinnamic acid polymer (H) on an optically transparent substrate (organic solvent cyclopenta Non-) is applied by spin coating, dried at 80 ° C. for 2 minutes, and then allowed to stand at 25 ° C. for 2 minutes. Then, a high-pressure mercury lamp is used, and a visible ultraviolet light having a wavelength of about 313 nm is passed through a polarizing filter. A photo-alignment film was obtained by irradiating linearly polarized light with parallel light from the direction perpendicular to the substrate (irradiation amount: 100 mJ / cm 2 ).
  • Each of the prepared polymerizable liquid crystal compositions was applied to the obtained base material at 400 rpm / 30 sec using a spin coater at room temperature, dried at 80 ° C. for 2 minutes, and then allowed to stand at 25 ° C. for 2 minutes.
  • a mercury lamp in each nitrogen atmosphere, set the irradiation amount to 3000 mJ / cm 2 and the irradiation temperature to 50 ° C. and irradiate with UV light.
  • the optical anisotropic bodies of Examples and Comparative Examples were obtained.
  • the evaluation of the orientation, transparency, and retardation retention was performed by forming an ITO film on the optical anisotropic body under the same conditions as in Example 1.
  • the optical anisotropic body of Comparative Example 12 was obtained by setting the optical anisotropic body for evaluating the orientation of Comparative Example 12 so that the temperature during irradiation was 75 ° C. and irradiating with UV light. .
  • the evaluation of the orientation, transparency, and retardation retention was performed by forming an ITO film on the optical anisotropic body under the same conditions as in Example 1.
  • Examples 22 to 23, Comparative Example 13 (VA mode liquid crystal display device)
  • Optically anisotropic bodies were prepared using the polymerizable liquid crystal compositions (22) to (23) and (36), and their orientation, transparency and retardation retention were measured. The results are shown in the above table as Examples 22 to 23 and Comparative Example 13, respectively.
  • the production methods of the optical anisotropic bodies of Examples 22 to 23 and Comparative Example 13 are as follows.
  • the optical anisotropic bodies for evaluating the orientation of Examples 22 to 23 were prepared by providing a color filter layer (4) and a planarizing layer (5) on a light-transmitting substrate (3), and then a cinnamic acid polymer ( A solution containing 3% by weight of H) (organic solvent cyclopentanone) was applied by spin coating, dried at 80 ° C. for 2 minutes, then allowed to stand at 25 ° C. for 2 minutes, and then a high-pressure mercury lamp was used.
  • a cinnamic acid polymer A solution containing 3% by weight of H) (organic solvent cyclopentanone) was applied by spin coating, dried at 80 ° C. for 2 minutes, then allowed to stand at 25 ° C. for 2 minutes, and then a high-pressure mercury lamp was used.
  • the obtained substrate was coated with the polymerizable liquid crystal composition (18) of Example 18 at 700 rpm / 30 sec using a spin coater at room temperature, dried at 80 ° C. for 2 minutes, and left at 25 ° C. for 2 minutes. Then, using a high-pressure mercury lamp, the first retardation film (7) was obtained by irradiating with UV light by setting the irradiation amount to 3000 mJ / cm 2 in a nitrogen atmosphere. . On the phase difference film 1, the prepared polymerizable liquid crystal compositions (22) to (23) shown in the above table were applied at room temperature at 400 rpm / 30 sec using a spin coater, dried at 80 ° C. for 2 minutes, and then After leaving at 25 ° C.
  • Example 2 For 2 minutes, use a high-pressure mercury lamp to set the irradiation amount to 3000 mJ / cm 2 in a nitrogen atmosphere and the irradiation temperature to 50 ° C. Then, UV light was irradiated to obtain a second retardation film (8). Evaluation of orientation, transparency, and retardation retention was performed by depositing an ITO film (9) on the second retardation film (8) under the same conditions as in Example 1. An ITO film (9), which is a transparent electrode layer, was deposited on the second retardation film (8), and then an alignment film (10) was formed. An ITO film (13) as a pixel electrode layer was attached to the light transmissive substrate (14), an alignment film (12) was formed, and then a weak rubbing treatment was performed. A TFT liquid crystal manufactured by DIC was injected into the liquid crystal layer (11) between the alignment film layers (10) and (12) to produce VA mode liquid crystal display devices of Examples 22 to 23 (FIG. 13).
  • An optical anisotropic body for evaluating the orientation of Comparative Example 13 was prepared by providing a color filter layer (4) and a planarizing layer (5) on a light-transmitting substrate (3), and then a cinnamic acid polymer (H).
  • a solution containing 3% by weight (organic solvent cyclopentanone) was applied by spin coating, dried at 80 ° C. for 2 minutes, and then allowed to stand at 25 ° C. for 2 minutes.
  • the photo-alignment film (6) is obtained by irradiating linearly polarized light of visible ultraviolet light having a wavelength of about 313 nm and parallel light from above in a direction perpendicular to the substrate (irradiation amount: 100 mJ / cm 2 ). It was.
  • the obtained substrate was coated with the polymerizable liquid crystal composition (18) of Example 18 at 700 rpm / 30 sec using a spin coater at room temperature, dried at 80 ° C. for 2 minutes, and left at 25 ° C. for 2 minutes. after using a high pressure mercury lamp, in a nitrogen atmosphere by irradiating UV light to set so that the amount of irradiation is 3000 mJ / cm 2, to obtain a first phase difference film (7) .
  • the adjusted polymerizable liquid crystal composition (36) shown in the above table was applied at room temperature at 400 rpm / 30 sec using a spin coater, dried at 80 ° C. for 2 minutes, and then at 25 ° C.
  • Example 1 After leaving for 2 minutes, use a high-pressure mercury lamp to set the irradiation amount to 3000 mJ / cm 2 in a nitrogen atmosphere and the irradiation temperature to 75 ° C. Irradiation was performed to obtain a second retardation film (8). Evaluation of orientation, transparency, and retardation retention was performed by depositing an ITO film (9) on the second retardation film (8) under the same conditions as in Example 1. An ITO film (9), which is a transparent electrode layer, was deposited on the second retardation film (8), and then an alignment film (10) was formed. An ITO film (13) as a pixel electrode layer was attached to the light transmissive substrate (14), an alignment film (12) was formed, and then a weak rubbing treatment was performed. A TFT liquid crystal manufactured by DIC was injected into the liquid crystal layer (11) between the alignment film layers (10) and (12) to produce a VA mode liquid crystal display device of Comparative Example 13 (FIG. 13). The results obtained are shown in the table below.
  • the optical anisotropic body (Examples 1 to 23) having a residual monomer amount of 0.0001 to 3% by mass and a residual solvent amount of 2500 ppm or less has a residual monomer amount of 0.0001 to 3% by mass and a residual solvent amount of 2500 ppm.
  • optical anisotropic bodies that do not satisfy the following conditions (Comparative Examples 1 to 13), it is possible to obtain optical anisotropic bodies with good orientation, high transparency, and high retardation retention.
  • the temperature during UV irradiation of the polymerizable liquid crystal composition is set to 50 to 60 ° C.
  • an optical anisotropic body having good orientation after ITO film formation and baking treatment, and high transparency and retardation retention can be formed.

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

Abstract

L'invention concerne un corps optiquement anisotrope qui est obtenu par durcissement d'une composition de cristaux liquides polymérisable ; et un corps optiquement anisotrope qui présente une transparence élevée et un taux de rétention de retard élevé, tout en présentant une bonne orientation après le post-traitement dans un film mince tel qu'un film de retard. La présente invention réalise un corps optiquement anisotrope ayant une couche optiquement anisotrope qui utilise une composition de cristaux liquides polymérisable contenant un initiateur de polymérisation (I) et un ou plusieurs composés de cristaux liquides polymérisables (II) ayant au moins deux groupes fonctionnels polymérisables dans chaque molécule, tout en contenant facultativement un ou plusieurs composés de cristaux liquides polymérisables (II -1) ayant un groupe fonctionnel polymérisable dans chaque molécule. La teneur en composés de cristaux liquides polymérisables (II) et en composés de cristaux liquides polymérisables (II -1) contenus facultativement dans la couche optiquement anisotrope est de 0,0001 % massique à 3 % massiques (inclus).
PCT/JP2018/004800 2017-02-20 2018-02-13 Corps optiquement anisotrope WO2018151070A1 (fr)

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