WO2018016567A1 - 重合性組成物及びそれを用いた光学異方体 - Google Patents

重合性組成物及びそれを用いた光学異方体 Download PDF

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WO2018016567A1
WO2018016567A1 PCT/JP2017/026220 JP2017026220W WO2018016567A1 WO 2018016567 A1 WO2018016567 A1 WO 2018016567A1 JP 2017026220 W JP2017026220 W JP 2017026220W WO 2018016567 A1 WO2018016567 A1 WO 2018016567A1
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polymerizable
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French (fr)
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浩一 延藤
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Dic株式会社
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Priority to KR1020197002554A priority Critical patent/KR20190022774A/ko
Priority to JP2018528856A priority patent/JP6627978B2/ja
Publication of WO2018016567A1 publication Critical patent/WO2018016567A1/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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G85/00—General processes for preparing compounds provided for in this subclass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/041—Lenses
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/08—Mirrors
    • 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
    • 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 has been intensively studied focusing on a polymerizable composition using a specific polymerizable compound having one or two or more polymerizable groups and a specific photopolymerization initiator. As a result, the present invention has been provided.
  • the polymerizable composition of the present invention comprises a polymerizable compound having one or more polymerizable groups and having a maximum absorption peak of ultraviolet light at a wavelength of 320 to 380 nm, and a maximum of ultraviolet light at a wavelength of 260 to 330 nm.
  • One or more intramolecular bond cleavage type photopolymerization initiator (B) having an absorption peak, one or more hydrogen abstraction type photopolymerization initiator (C) having a maximum absorption peak of ultraviolet-visible light at a wavelength of 360 to 420 nm (C) Can be used simultaneously to obtain a polymerizable composition having excellent solubility and storage stability, and while maintaining excellent orientation, a polymer having excellent coating curability and excellent productivity. , Optically anisotropic bodies, retardation films and the like can be obtained.
  • the number of maximum absorption peaks of ultraviolet rays appearing at wavelengths of 320 to 380 nm may be plural, but is preferably 1 to 5, and more preferably 1 to 3.
  • S 11 to S 72 represent a spacer group or a single bond, and when a plurality of S 11 to S 72 are present, they may be the same or different, X 11 to X 72 are —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 —, —, —OCO—CH 2 CH 2 —, —,
  • a 11 and A 12 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl.
  • G is the following formula (G-1) to formula (G-6)
  • W 81 represents a group having 5 to 30 carbon atoms having at least one aromatic group, and the group may be unsubstituted or substituted by one or more L 1
  • the above —CH 2 — is independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—.
  • G represents Formula (G-6);
  • L 1 is a fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, nitro group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, diethylamino group, diisopropylamino.
  • these polymerizable groups are polymerized by radical polymerization, radical addition polymerization, cationic polymerization and anionic polymerization.
  • the formula (P-1), formula (P-2), formula (P-3), formula (P-4), formula (P-5), formula (P ⁇ 7), formula (P-11), formula (P-13), formula (P-15) or formula (P-18) are preferred, and formula (P-1), formula (P-2), formula (P-18) P-7), formula (P-11) or formula (P-13) is more preferred, formula (P-1), formula (P-2) or formula (P-3) is more preferred, and formula (P- Particular preference is given to 1) or formula (P-2).
  • X 11 to X 72 are —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—
  • a 11 and A 12 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidine-2. , 5-diyl group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group or 1,3-dioxane -2,5-diyl groups, these groups may be unsubstituted or substituted by one or more L, but when multiple occurrences of A 11 and / or A 12 appear, they are the same.
  • Z 11 and Z 12 are each independently —O—, —S—, —OCH 2 —, —CH 2 O—, —CH 2 CH 2 —, — CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, —OCO—NH—, — NH—COO—, —NH—CO—NH—, —NH—O—, —O—NH—, —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 —, —,
  • Z 11 and Z 12 are each independently a single bond, —OCH 2 —, —CH 2 O—, —COO—, —OCO— from the viewpoint of liquid crystallinity of the compound, availability of raw materials, and ease of synthesis.
  • R 11 and R 31 are hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, cyano group, nitro group, isocyano group, A thioisocyano group, or one —CH 2 — or two or more non-adjacent —CH 2 — are each independently —O—, —S—, —CO—, —COO—, —OCO—, 1 to 20 carbon atoms which may be substituted by —CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO— or —C ⁇ C—.
  • a linear or branched alkyl group is represented, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom.
  • R 1 is a hydrogen atom in view of easiness of the liquid crystal and synthetic, fluorine atom, chlorine atom, cyano group, or one -CH 2 - or nonadjacent two or more -CH 2 - are each independently It preferably represents a linear or branched alkyl group having 1 to 12 carbon atoms which may be substituted by —O—, —COO—, —OCO—, —O—CO—O—, a hydrogen atom, fluorine It is more preferable to represent an atom, a chlorine atom, a cyano group, or a linear alkyl group or linear alkoxy group having 1 to 12 carbon atoms, and a linear alkyl group or linear alkoxy group having 1 to 12 carbon atoms. It is particularly preferred to represent.
  • G represents a group selected from the formulas (G-1) to (G-6).
  • W 81 represents a group having 5 to 30 carbon atoms having at least one aromatic group, and the group may be unsubstituted or substituted by one or more L 1
  • W 82 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be linear or branched, and any hydrogen atom in the alkyl group may be substituted by a fluorine atom and / or -OH, 1 single -CH 2 in the alkyl group - or nonadjacent two or more -CH 2 - are each independently -O -, - S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, —CH ⁇ Substituted by CH—COO—, —CH ⁇ CH—OCO—, —COO—CH ⁇ CH—, —OCO—
  • Q 1 Represents —O—, —S—, —NR 4 — (wherein R 4 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms) or —CO—.
  • Each —CH ⁇ may be independently replaced by —N ⁇ , and each —CH 2 — independently represents —O—, —S—, —NR 4 — (wherein R 4 represents a hydrogen atom or carbon Represents an alkyl group having 1 to 8 atoms.) Or may be replaced by —CO—, but does not include an —O—O— bond, and the group represented by the formula (W-1) is unsubstituted. Or the following formula (W-1-1) to formula (W-1-8) which may be substituted by one or more L 1
  • these groups may have a bond at an arbitrary position), preferably a group selected from the group represented by formula (W-10) is unsubstituted. Or one or more of L 1 may be substituted by the following formulas (W-10-1) to (W-10-8)
  • these groups may have a bond at an arbitrary position, and R 6 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms).
  • R 6 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
  • these groups may have a bond at an arbitrary position, and R 6 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms).
  • R 6 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
  • Examples of the group represented by the formula (W-18) include the following formulas (W-18-1) to (W-18-6) which may be unsubstituted or substituted with one or more L 1 groups.
  • R 6 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, each identical if R 6 there are a plurality of It is preferable that the group represented by the formula (W-19) is unsubstituted or substituted with one or more L 1 groups.
  • r represents an integer of 0 to 5
  • s represents an integer of 0 to 4
  • t represents an integer of 0 to 3.
  • W 82 represents a hydrogen atom, or one -CH 2 - or nonadjacent two or more -CH 2 - are each independently -O -, - S -, - CO -, - COO -, - OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, —CH ⁇ CH—COO—, —CH ⁇ CH—OCO—.
  • W 82 may represent the same meaning as W 81 , W 81 and W 82 may be combined to form a ring structure, or W 82 may be
  • P W82 represents the same meaning as P 11
  • S W82 represents the same meaning as S 11
  • X W82 represents the same meaning as X 11
  • n W82 represents the same meaning as m 11).
  • W 82 is a hydrogen atom, or an arbitrary hydrogen atom may be substituted with a fluorine atom from the viewpoint of easy availability of raw materials and synthesis, and one —CH 2 — or two not adjacent to each other
  • the above —CH 2 — is independently —O—, —CO—, —COO—, —OCO—, —CH ⁇ CH—COO—, —OCO—CH ⁇ CH—, —CH ⁇ CH—, — It preferably represents a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted by CF ⁇ CF— or —C ⁇ C—, and represents a hydrogen atom or a carbon atom having 1 to 20 carbon atoms.
  • W 82 represents a linear or branched alkyl group, and particularly preferably represents a hydrogen atom or a linear alkyl group having 1 to 12 carbon atoms.
  • W 82 may be different even identical to W 81, the preferred group is the same as described for W 81.
  • the cyclic group represented by —NW 81 W 82 may be unsubstituted or substituted with one or more L 1 Formula (Wb-1) to Formula (Wb-42)
  • CW 81 W 82 may be unsubstituted or may be substituted with one or more L 1.
  • R 6 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and when there are a plurality of R 6 s , they may be the same or different from each other).
  • R 6 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and when there are a plurality of R 6 s , they may be the same or different from each other.
  • Formula (Wc-11), Formula (Wc-12), which may be unsubstituted or substituted by one or more L, Formula (Wc-13), Formula (Wc-14), Formula (Wc-53), Formula (Wc-54), Formula (Wc-55), Formula (Wc -56), a group selected from formula (Wc-57) or formula (Wc-78) is particularly preferred.
  • the total number of ⁇ electrons contained in W 81 and W 82 is preferably 4 to 24 from the viewpoint of wavelength dispersion characteristics, storage stability, liquid crystallinity, and ease of synthesis.
  • W 83 and W 84 each independently has 5 to 30 carbon atoms having a halogen atom, a cyano group, a hydroxy group, a nitro group, a carboxyl group, a carbamoyloxy group, an amino group, a sulfamoyl group, or at least one aromatic group.
  • alkyl groups having 1 to 20 carbon atoms alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, cycloalkenyl groups having 3 to 20 carbon atoms, and 1 to 20 carbon atoms.
  • a cyano group, a carboxyl group, one —CH 2 — or two or more non-adjacent —C H 2 — is each independently substituted by —CO—, —COO—, —OCO—, —O—CO—O—, —CO—NH—, —NH—CO— or —C ⁇ C—
  • W84 is a cyano group, a nitro group, a carboxyl group, one —CH 2 — or adjacent group.
  • Two or more —CH 2 — that are not present are each independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O.
  • m11 represents an integer of 0 to 8, and preferably represents an integer of 0 to 4 from the viewpoint of liquid crystallinity, availability of raw materials and ease of synthesis, and an integer of 0 to 2 Is more preferable, 0 or 1 is more preferable, and 1 is particularly preferable.
  • m2 to m7 represent an integer of 0 to 5, but represent an integer of 0 to 4 from the viewpoints of liquid crystallinity, availability of raw materials, and ease of synthesis. Is preferable, it is more preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 1.
  • the compounds represented by the general formula (1) are preferably compounds represented by the following formulas (1-a-1) to (1-a-105).
  • the compound represented by the general formula (2) is preferably a compound represented by the following formula (2-a-1) to formula (2-a-71).
  • liquid crystalline compounds can be used alone or in admixture of two or more. .
  • n represents an integer of 1 to 10.
  • the compound represented by the general formula (6) is preferably a compound represented by the following formula (6-a-1) to formula (6-a-25)
  • liquid crystalline compounds can be used alone or in combination of two or more. You can also
  • the compound represented by the general formula (7) is preferably a compound represented by the following formula (7-a-1) to formula (7-a-26).
  • liquid crystalline compounds can be used alone or in combination of two or more.
  • the total content of the liquid crystal compound having one or more polymerizable groups is preferably 60 to 100% by mass, and preferably 65 to 98% by mass, based on the total amount of the liquid crystal compound used in the polymerizable composition. More preferably, the content is 70 to 95% by mass.
  • the polymerizable composition of the present invention comprises one or more intramolecular bond-cleavage photopolymerization initiators (B) having a maximum absorption peak of ultraviolet light at a wavelength of 250 to 330 nm, an ultraviolet-ray at a wavelength of 360 to 420 nm. 1 type, or 2 or more types of hydrogen abstraction type photoinitiators (C) which have the maximum absorption peak of visible light are contained simultaneously.
  • the intramolecular bond cleavage type polymerization initiator refers to a photopolymerization initiator that is excited when irradiated with light and generates cleavage in itself to generate a radical polymerization initiation point.
  • the hydrogen abstraction type photopolymerization initiator refers to a photopolymerization initiator that extracts hydrogen from a polymer and creates a radical polymerization initiation point in the polymer.
  • the photopolymerization initiator (B) is preferably at least one photopolymerization initiator selected from the group consisting of alkylphenone compounds, acylphosphine oxide compounds, and oxime ester compounds.
  • alkylphenone photopolymerization initiator examples include compounds represented by the formula (b-1).
  • R 2a , R 2b and R 2c each independently represent a group selected from the following formulas (R 2 -1) to (R 2 -7).
  • acylphosphine oxide photopolymerization initiator examples include compounds represented by the formula (b-2).
  • R 24 represents an alkyl group, an aryl group or a heterocyclic group
  • R 25 and R 26 each independently represents an alkyl group, an aryl group, a heterocyclic group or an alkanoyl group. May be substituted with an alkyl group, a hydroxyl group, a carboxyl group, a sulfone group, an aryl group, an alkoxy group, or an arylthio group.
  • compounds represented by the following formulas (b-2-1) to (b-2-5) are preferable.
  • -1) or formula (b-2-5) is more preferable.
  • Examples of the oxime ester photopolymerization initiator include compounds represented by formula (b-3-1) or formula (b-3-2).
  • R 27 to R 31 each independently represents a hydrogen atom, a cyclic, straight-chain or branched alkyl group having 1 to 12 carbon atoms, or a phenyl group. May be substituted with a substituent selected from the group consisting of a halogen atom, an alkoxyl group having 1 to 6 carbon atoms, and a phenyl group, X 1 represents an oxygen atom or a nitrogen atom, and X 2 represents Represents an oxygen atom or NR, and R represents an alkyl group having 1 to 6 carbon atoms.
  • Specific examples of the compounds represented by the above formulas (b-3-1) and (b-3-2) include the following formulas (b-3-1-1) to (b-3-1-1): 2) and the compounds represented by formulas (b-3-2-1) to (b-3-2-2) are preferred, and the compounds represented by formula (b-3-1-1) and formula (b-3-2-2) More preferred is 1) or formula (b-3-2-2).
  • Examples of the photopolymerization initiator (C) include compounds represented by general formula (c-1).
  • R 11 to R 18 each independently represents a hydrogen atom, a chlorine atom, or a linear or branched alkyl group.
  • the compounds represented by the above formula (c-1) are preferably compounds represented by the following formulas (c-1-1) to (c-1-8), ⁇ 5) or formula (c-1-7) is more preferable.
  • the content of the photopolymerization initiator (B) is preferably 0.1 to 15% by mass, more preferably 1 to 12% by mass, and more preferably 2 to 10% by mass with respect to the total amount of the polymerizable compound contained in the polymerizable composition. % Is particularly preferred. These can be used alone or in combination of two or more.
  • the content of the photopolymerization initiator (C) is preferably from 0.1 to 5% by weight, more preferably from 0.5 to 4% by weight, based on the total amount of the polymerizable compounds contained in the polymerizable composition. 3% by mass is particularly preferred. These can be used alone or in combination of two or more.
  • additives can be used according to each purpose.
  • Additives such as liquid crystalline compounds, other liquid crystal compounds, and alignment materials can be added to the extent that the alignment of the liquid crystal is not significantly reduced.
  • the polymerizable composition used in the present invention can contain a polymerization inhibitor as necessary.
  • a polymerization inhibitor there is no limitation in particular as a polymerization inhibitor to be used, A well-known usual thing can be used.
  • N'-diphenyl-p-phenylenediamine Ni-propyl-N'-phenyl-p-phenylenediamine, N- (1.3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N.I.
  • Amine compounds such as N′-di-2-naphthyl-p-phenylenediamine, diphenylamine, N-phenyl- ⁇ -naphthylamine, 4.4′-dicumyl-diphenylamine, 4.4′-dioctyl-diphenylamine, phenothiazine, Thioether compounds such as distearyl thiodipropionate, N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, N-nitrosodinaphthylamine, p-nitrosophenol, nitrosobenzene, p-nitrosodiphenylamine, ⁇ -nitroso- ⁇ -naphthol N, N-dimethyl p-nitrosoaniline, p-nitrosodiphenylamine, p-nitronedimethylamine, p-nitrone-N, N-diethylamine, N
  • the polymerizable composition used in the present invention can contain an antioxidant and the like as necessary.
  • antioxidants include hydroquinone derivatives, nitrosamine polymerization inhibitors, hindered phenol antioxidants, and more specifically, tert-butyl hydroquinone, “Q-1300” manufactured by Wako Pure Chemical Industries, Ltd.
  • non-polymerizable liquid crystal compounds and the like can be added as necessary to adjust physical properties.
  • a polymerizable compound having no liquid crystallinity is preferably added in the step of preparing a polymerizable solution by mixing the polymerizable compound with an organic solvent and stirring under heating. You may add in the process of mixing a polymerization initiator with a solution, and may add in both processes. The amount of these compounds added is preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less, based on the polymerizable composition.
  • n and n each independently represents an integer of 1 to 10
  • R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a fluorine atom. These may be the same or different.
  • chiral compound having no polymerizable group examples include, for example, pelargonic acid cholesterol having a cholesteryl group as a chiral group, cholesterol stearate, and a product of BDH having a 2-methylbutyl group as a chiral group.
  • a 83 and A 84 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2.
  • L 2 is fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, nitro group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, diethylamino group, diisopropylamino.
  • R 111 and R 112 independently represent a hydrogen atom, an alkyl group or a fluorine atom having 1 to 10 carbon atoms, R 113 hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, pentafluorosulfuranyl group, a cyano group, a nitro group, an isocyano group, Chioisoshiano group, or one -CH 2 - 2 pcs or nonadjacent
  • the above —CH 2 — is independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—.
  • n and n each independently represents an integer of 1 to 18, and R represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or a cyano group.
  • R represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or a cyano group.
  • these groups are alkyl groups having 1 to 6 carbon atoms or alkoxy groups having 1 to 6 carbon atoms, they are all unsubstituted or substituted by one or more halogen atoms.
  • These liquid crystal compounds can be used alone or in combination of two or more.
  • Specific examples of the compound represented by the general formula (3-b) include compounds represented by the following formulas (3-b-1) to (3-b-16).
  • liquid crystalline compounds can be used alone or in combination of two or more.
  • R represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cyano group.
  • these groups are alkyl groups having 1 to 6 carbon atoms or alkoxy groups having 1 to 6 carbon atoms, they are all unsubstituted or substituted by one or more halogen atoms.
  • These liquid crystalline compounds can be used alone or in combination of two or more.
  • each n independently represents an integer of 1 to 10.
  • R represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cyano group.
  • these groups are alkyl groups having 1 to 6 carbon atoms, or alkoxy groups having 1 to 6 carbon atoms, they are all unsubstituted or substituted by one or more halogen atoms.
  • These liquid crystalline compounds can be used alone or in combination of two or more.
  • Specific examples of the compound represented by the general formula (6-b) include compounds represented by the following formulas (6-b-1) to (6-b-23).
  • R represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy having 1 to 6 carbon atoms.
  • These liquid crystal compounds may be used alone or in combination of two or more.
  • Specific examples of the compound represented by the general formula (7-b) include compounds represented by the following formulas (7-b-1) to (7-b-25).
  • R represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cyano group.
  • These groups are alkyl groups having 1 to 6 carbon atoms. Or in the case of an alkoxy group having 1 to 6 carbon atoms, all may be unsubstituted or substituted by one or more halogen atoms.
  • These liquid crystalline compounds It can also be used and can also be used in mixture of 2 or more types.
  • the polymerizable composition of the present invention may contain an alignment material that improves the orientation in order to improve the orientation.
  • the alignment material to be used may be a known and usual one as long as it is soluble in a solvent capable of dissolving the liquid crystalline compound having a polymerizable group used in the polymerizable composition of the present invention. It can be added as long as the orientation is not significantly deteriorated. Specifically, it is preferably 0.05 to 30% by weight, more preferably 0.5 to 15% by weight, and more preferably 1 to 10% by weight based on the total amount of the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition. Particularly preferred.
  • the alignment material is polyimide, polyamide, BCB (Penzocyclobutene Polymer), polyvinyl alcohol, polycarbonate, polystyrene, polyphenylene ether, polyarylate, polyethylene terephthalate, polyether sulfone, epoxy resin, epoxy acrylate resin, acrylic Resin, coumarin compound, chalcone compound, cinnamate compound, fulgide compound, anthraquinone compound, azo compound, arylethene compound, and other compounds that can be photoisomerized or photodimerized, but materials that are oriented by UV irradiation or visible light irradiation (Photo-alignment material) is preferable.
  • R represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group, a nitro group
  • R ′ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. May be linear or branched, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom, and one —CH 2 — or adjacent group in the alkyl group may be substituted.
  • two or more —CH 2 — groups independently represent —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—.
  • the polymer of the present invention is obtained by polymerizing the polymerizable composition of the present invention in a state containing an initiator.
  • the polymer of the present invention is used for optical anisotropic bodies, retardation films, lenses, colorants, printed materials and the like.
  • optical anisotropic body manufacturing method (Optical anisotropic)
  • the polymerizable composition of the present invention is coated on a substrate or a substrate having an alignment function, and the liquid crystal molecules in the polymerizable liquid crystal composition of the present invention are uniformly retained in a nematic phase or a smectic phase.
  • the optical anisotropic body of the present invention is obtained by orienting and polymerizing.
  • the base material used for the optical anisotropic body of the present invention is a base material usually used for liquid crystal display elements, organic light emitting display elements, other display elements, optical components, colorants, markings, printed matter and optical films, If it is the material which has heat resistance which can endure the heating at the time of drying after application
  • base materials include glass base materials, metal base materials, ceramic base materials, plastic base materials, and organic materials such as paper.
  • the substrate when the substrate is an organic material, examples thereof include cellulose derivatives, polyolefins, polyesters, polyolefins, polycarbonates, polyacrylates, polyarylates, polyether sulfones, polyimides, polyphenylene sulfides, polyphenylene ethers, nylons, and polystyrenes.
  • plastic substrates such as polyester, polystyrene, polyolefin, cellulose derivatives, polyarylate, and polycarbonate are preferable.
  • 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. Among these, a pickup lens, a retardation film, a light diffusion film, and a color filter that have higher added value are preferable.
  • the base material may be subjected to a normal orientation treatment or may be provided with an orientation film so that the polymerizable composition is oriented when the polymerizable composition of the present invention is applied and dried.
  • an orientation film so that the polymerizable composition is oriented when the polymerizable composition of the present invention is applied and dried.
  • stretching, rubbing, polarization ultraviolet visible light irradiation treatment, ion beam treatment, oblique deposition process of the SiO 2 to the substrate, and the like When the alignment film is used, a known and conventional alignment film is used.
  • Such alignment films include polyimide, polysiloxane, polyamide, polyvinyl alcohol, polycarbonate, polystyrene, polyphenylene ether, polyarylate, polyethylene terephthalate, polyethersulfone, epoxy resin, epoxy acrylate resin, acrylic resin, azo compound, coumarin.
  • Examples thereof include compounds such as compounds, chalcone compounds, cinnamate compounds, fulgide compounds, anthraquinone compounds, azo compounds and arylethene compounds, and polymers and copolymers of the above compounds.
  • the compound subjected to the alignment treatment by rubbing is preferably an alignment treatment or a compound in which crystallization of the material is promoted by inserting a heating step after the alignment treatment.
  • an alignment film used for a TN type liquid crystal display element is provided on the substrate, a polymerizable liquid crystal layer having a slightly inclined alignment is obtained, and the alignment film used for an STN type liquid crystal display element is obtained.
  • a polymerizable liquid crystal layer having a large alignment gradient can be obtained.
  • 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. Methods, cap coating methods, dip coating methods, slit coating methods, spray coating methods, and the like can be used. After applying the polymerizable composition, it is dried.
  • the liquid crystal molecules in the polymerizable composition of the present invention are preferably uniformly aligned while maintaining the smectic phase or nematic phase.
  • One of the methods is a heat treatment method. Specifically, after coating the polymerizable composition of the present invention on a substrate, the N (nematic phase) -I (isotropic liquid phase) transition temperature (hereinafter abbreviated as the NI transition temperature) of the liquid crystal composition. ) By heating to the above, the liquid crystal composition is brought into an isotropic liquid state. From there, it is gradually cooled as necessary to develop a nematic phase.
  • a heat treatment may be performed such that the temperature is maintained for a certain time within a temperature range in which the nematic phase of the polymerizable composition of the present invention is expressed.
  • the heating temperature is too high, the polymerizable liquid crystal compound may deteriorate due to an undesirable polymerization reaction. Moreover, when it cools too much, a polymeric composition raise
  • the liquid crystal phase is cooled to a minimum temperature at which phase separation does not occur, that is, is supercooled, and polymerization is performed in a state where the liquid crystal phase is aligned at the temperature.
  • a minimum temperature at which phase separation does not occur that is, is supercooled
  • polymerization is performed in a state where the liquid crystal phase is aligned at the temperature.
  • the polymerization treatment of the dried polymerizable composition is generally performed by light irradiation such as visible ultraviolet rays or heating in a uniformly oriented state.
  • light irradiation such as visible ultraviolet rays or heating in a uniformly oriented state.
  • visible ultraviolet light having a wavelength of 420 nm or less is preferably irradiated, and ultraviolet light having a wavelength of 250 to 400 nm is most preferably irradiated.
  • the polymerizable composition causes decomposition or the like due to visible ultraviolet light of 420 nm or less, it may be preferable to perform polymerization treatment with visible ultraviolet light of 420 nm or more.
  • Examples of the method for polymerizing the polymerizable composition of the present invention include a method of irradiating active energy rays and a thermal polymerization method. However, the reaction proceeds at room temperature without requiring heating, and the active energy rays are irradiated. Among them, a method of irradiating light such as ultraviolet rays is preferable because the operation is simple.
  • the temperature at the time of irradiation is preferably set to 30 ° C. or less as much as possible in order to avoid the induction of thermal polymerization of the polymerizable composition by setting the temperature at which the polymerizable composition of the present invention can maintain the liquid crystal phase.
  • the polymerizable liquid crystal composition usually has a temperature within the range from the C (solid phase) -N (nematic) transition temperature (hereinafter abbreviated as the CN transition temperature) to the NI transition temperature range during the temperature rising process. Shows liquid crystal phase.
  • the CN transition temperature N (nematic) transition temperature
  • the NI transition temperature N (nematic) transition temperature range during the temperature rising process. Shows liquid crystal phase.
  • 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 400 nm or less is preferable, and irradiation with light having a wavelength of 250 to 400 nm is most preferable.
  • the polymerizable composition causes decomposition or the like due to ultraviolet light of 400 nm or less, it may be preferable to perform the polymerization treatment with visible light of 400 nm or more.
  • 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. In particular, the range of 0.1 kW / m 2 to 2 kW / m 2 is preferable.
  • the ultraviolet intensity is less than 0.05 kW / m 2 , it takes a lot of time to complete the polymerization.
  • the strength exceeds 2 kW / m 2 , the liquid crystal molecules in the polymerizable composition tend to be photodegraded, or a large amount of polymerization heat is generated to increase the temperature during the polymerization. May change, and the retardation of the film after polymerization may be distorted.
  • 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 retardation film of the present invention contains the optical anisotropic body, and the liquid crystalline compound forms a uniform continuous alignment state with respect to the substrate, and is in-plane with respect to the substrate. It is only necessary to have biaxiality outside, in-plane and out-of-plane, or in-plane.
  • an adhesive, an adhesive layer, an adhesive, an adhesive layer, a protective film, a polarizing film, or the like may be laminated.
  • a retardation film for example, a positive A plate in which a rod-like liquid crystalline compound is substantially horizontally aligned with respect to a base material, and a negative A plate in which a disk-like liquid crystalline compound is vertically uniaxially oriented with respect to a base material
  • a positive C plate in which rod-like liquid crystalline compounds are aligned substantially vertically with respect to the substrate, a rod-like liquid crystalline compound is cholesteric aligned with respect to the substrate, or a negative C in which disc-like liquid crystalline compounds are horizontally aligned uniaxially.
  • orientation mode of a plate, a biaxial plate, a positive O plate in which a rod-like liquid crystalline compound is hybrid-aligned with respect to a substrate, and a negative O plate in which a disc-like liquid crystalline compound is hybrid-aligned with respect to a substrate can be applied.
  • various orientation modes can be applied without particular limitation as long as the viewing angle dependency is improved.
  • orientation modes of positive A plate, negative A plate, positive C plate, negative C plate, biaxial plate, positive O plate, and negative O plate can be applied.
  • the positive A plate means an optical anisotropic body in which the polymerizable liquid crystal composition is homogeneously aligned.
  • a negative C plate means the optically anisotropic body which made the polymerizable liquid crystal composition the cholesteric orientation.
  • a positive A plate it is preferable to use a positive A plate as the first retardation layer in order to compensate the viewing angle dependence of polarization axis orthogonality and widen the viewing angle.
  • the positive A plate has a refractive index in the in-plane slow axis direction of the film as nx, a refractive index in the in-plane fast axis direction of the film as ny, and a refractive index in the thickness direction of the film as nz,
  • the positive A plate preferably has an in-plane retardation value in the range of 30 to 500 nm at a wavelength of 550 nm.
  • the thickness direction retardation value is not particularly limited.
  • the Nz coefficient is preferably in the range of 0.9 to 1.1.
  • a so-called negative C plate having negative refractive index anisotropy as the second retardation layer.
  • a negative C plate may be laminated on a positive A plate.
  • the negative C plate has a refractive index nx in the in-plane slow axis direction of the retardation layer, ny in the in-plane fast axis direction of the retardation layer, and a refractive index in the thickness direction of the retardation layer.
  • the thickness direction retardation value of the negative C plate 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 following formula (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 polymerizable composition of the present invention is coated on a base material or a base material having an orientation function, or injected into a lens-shaped mold, and uniformly oriented while maintaining a nematic phase or a smectic phase. By polymerizing, it can be used for the lens of the present invention.
  • the shape of the lens include a simple cell type, a prism type, and a lenticular type.
  • the polymerizable composition of the present invention is coated on a substrate or a substrate having an alignment function, and is uniformly aligned and polymerized while maintaining a nematic phase or a smectic phase. It can be used for an element. Examples of usage forms include optical compensation films, patterned retardation films for liquid crystal stereoscopic display elements, retardation correction layers for color filters, overcoat layers, alignment films for liquid crystal media, and the like.
  • the liquid crystal display element has a liquid crystal medium layer, a TFT drive circuit, a black matrix layer, a color filter layer, a spacer, and a liquid crystal medium layer at least sandwiched by corresponding electrode circuits on at least two base materials.
  • the layer, the polarizing plate layer, and the touch panel layer are arranged outside the two substrates, but in some cases, the optical compensation layer, the overcoat layer, the polarizing plate layer, and the electrode layer for the touch panel are narrowed in the two substrates. May be held.
  • Alignment modes of liquid crystal display elements include TN mode, VA mode, IPS mode, FFS mode, OCB mode, etc.
  • a phase difference corresponding to the orientation mode is used.
  • the liquid crystalline compound in the polymerizable composition may be substantially horizontally aligned with the substrate.
  • a liquid crystalline compound having more polymerizable groups in one molecule may be thermally polymerized.
  • the organic light emitting display of the present invention can be used for an element.
  • it can be used as an antireflection film of an organic light emitting display element by combining the retardation film obtained by the polymerization and a polarizing plate.
  • the angle formed by the polarizing axis of the polarizing plate and the slow axis of the retardation film is preferably about 45 °.
  • the polarizing plate and the retardation film may be bonded together with an adhesive or a pressure-sensitive adhesive. Moreover, you may laminate
  • the polarizing plate used at this time may be in the form of a film doped with a pigment or in the form of a metal such as a wire grid.
  • a polymer obtained by polymerizing the polymerizable composition of the present invention in a nematic phase, a smectic phase, or in a state of being oriented on a substrate having an orientation function should be used as a heat dissipation material for an illumination element, particularly a light emitting diode element. You can also.
  • the form of the heat dissipation material is preferably a prepreg, a polymer sheet, an adhesive, a sheet with metal foil, or the like.
  • the polymerizable composition of the present invention can be used as the optical component of the present invention by polymerizing the polymerizable composition while maintaining a nematic phase or a smectic phase, or in combination with an alignment material.
  • the polymerizable composition of the present invention can be combined with or added to a dichroic dye, a lyotropic liquid crystal, a chromonic liquid crystal, or the like to be used as a polarizing film.
  • CPN cyclopentanone
  • Example 1 After the dissolution was confirmed, the solution was returned to room temperature, and 4 parts of the compound represented by the formula (b-1-1), the formula (b-3-1) -1), 2 parts of the compound represented by the formula (c-1-7), and 0.1 part of Megafac F-554 (F-554: manufactured by DIC Corporation) were added. Further stirring was performed to obtain a solution. The solution was clear and uniform. The resulting solution was filtered through a 0.20 ⁇ m membrane filter to obtain the polymerizable composition (1) of Example 1.
  • Examples 2 to 52, Comparative Examples 1 to 4 The polymerizable compositions (2) to 52 of Examples 2 to 52 were prepared under the same conditions as the preparation of the polymerizable composition (1) of Example 1 except that the respective compounds shown in the following table were changed to the ratios shown in the following table. Polymeric compositions (C1) to (C4) of (52) and Comparative Examples 1 to 4 were obtained.
  • Tables 1 to 6 below show specific compositions of the polymerizable compositions (1) to (52) of Examples 1 to 52 of the present invention and the polymerizable compositions (C1) to (C4) of Comparative Examples 1 to 4. Indicates.
  • Examples 91 to 99, 102 The polymerizable composition used was changed to the polymerizable composition (4) to (6), (12), (19), (20), (24) to (27), and (40) of the present invention, respectively. Obtained optical anisotropic bodies of Examples 91 to 99 and Example 102 under the same conditions as in Example 90. The orientation evaluation, retardation ratio, and curability evaluation of the obtained optical anisotropic body were performed in the same manner as in Example 53.
  • Example 111 The polymerizable composition (49) obtained in Example 49 was applied to a glass substrate having a thickness of 0.7 mm using a spin coating method, dried at 60 ° C. for 2 minutes, and further dried at 120 ° C. for 2 minutes. Then, the temperature was returned to 60 ° C., and 313 nm linearly polarized light was irradiated at an intensity of 10 mW / cm 2 for 50 seconds. Thereafter, the coating film was returned to room temperature and irradiated with ultraviolet rays at an intensity of 30 mW / cm 2 for 30 seconds using a high-pressure mercury lamp to obtain the optical anisotropic body of Example 111.
  • Example 115 to 137 The polymerizable compositions (53) to 115 of Examples 115 to 137 were prepared under the same conditions as the preparation of the polymerizable composition (1) of Example 1 except that the respective compounds shown in the following table were changed to the ratios shown in the following table. (75) was obtained.
  • the maximum absorption wavelength of UV-visible light of the polymerizable compound satisfying the general formula (I) is shown in the table below.
  • the maximum absorption wavelength of UV-visible light is determined by dissolving the polymerizable compound and the photopolymerization initiator in acetonitrile so as to have a concentration of 20 ppm, and placing the solution in a quartz cell having an optical path length of 1 cm. This is a value measured with a photometer “V-560” (manufactured by JASCO Corporation).
  • phase transition temperature T NI Phase transition temperature T NI
  • N a nematic phase
  • I an isotropic phase
  • T NI a transition temperature (unit: ° C.) between the nematic phase and the isotropic phase.
  • the polymerizable compositions (53) to (75) of the present invention were applied to the rubbed substrate by a spin coating method and dried at 80 ° C. for 2 minutes. After the obtained coating film was cooled to room temperature, the temperature was raised from 80 ° C. at a rate of temperature rise of 2 ° C./min using a melting point measuring device, and the phase transition temperature T NI was measured. The results obtained are shown in the table below.
  • Example 138 The polyimide solution for alignment film was applied to a glass substrate having a thickness of 0.7 mm using a spin coating method, dried at 100 ° C. for 10 minutes, and then baked at 200 ° C. for 60 minutes to obtain a coating film. The obtained coating film was rubbed. The rubbing treatment was performed using a commercially available rubbing apparatus.
  • the polymerizable composition (53) of the present invention was applied to the rubbed substrate by a spin coating method and dried at a phase transition temperature T NI -20 ° C. for 2 minutes so that a nematic phase could be developed.
  • the obtained coating film was cooled to room temperature, and then irradiated with ultraviolet rays at an intensity of 30 mW / cm 2 for 30 seconds using a high pressure mercury lamp, to obtain an optical anisotropic body of Example 53.
  • the obtained optical anisotropic body was evaluated for orientation, retardation ratio, and curability according to the following criteria.
  • an in-plane retardation (Re ( 550)) was 138 nm.
  • the ratio Re (450) / Re (550) between the in-plane retardation (Re (450)) and Re (550) at a wavelength of 450 nm was 0.864, and a retardation film with good uniformity was obtained.
  • An optical anisotropic body prepared as a sample for evaluation was placed under crossed Nicols, and the film surface as an optical anisotropic body was rubbed with a cotton swab soaked with methyl isobutyl ketone, and the number of times until the film was peeled off was visually evaluated.
  • Examples 139 to 154 Optical anisotropic bodies of Examples 139 to 154 were obtained under the same conditions as in Example 138, except that the polymerizable compositions used were changed to the polymerizable compositions (54) to (69) of the present invention, respectively. .
  • the orientation evaluation, retardation ratio, and curability evaluation of the obtained optical anisotropic body were performed in the same manner as in Example 53.
  • Example 155 After laminating a silane coupling type vertical alignment film on the TAC film substrate, the polymerizable composition (70) of the present invention was applied by a bar coating method and dried at 90 ° C. for 2 minutes. The obtained coating film is cooled to room temperature, and then irradiated with ultraviolet rays at a conveyor speed of 6 m / min using a UV conveyor device (manufactured by GS Yuasa Co., Ltd.), and is an optical anisotropic body that is a positive C plate of Example 155 Got. The orientation evaluation, retardation ratio, and coating unevenness evaluation of the obtained optical anisotropic body were performed in the same manner as in Example 138.
  • Examples 156 to 158 Under the same conditions as in Example 155, except that the polymerizable composition used was changed to the polymerizable compositions (71) to (73) of the present invention, the homeotropically aligned optically anisotropic bodies of Examples 156 to 158 were used. Obtained. The orientation evaluation, retardation ratio, and curability evaluation of the obtained optical anisotropic body were performed in the same manner as in Example 155.
  • Example 160 A hybrid-oriented optically anisotropic body of Example 160 was obtained under the same conditions as Example 159 except that the polymerizable composition used was changed to the polymerizable composition (75) of the present invention.
  • the orientation evaluation, retardation ratio, and curability evaluation of the obtained optical anisotropic body were performed in the same manner as in Example 138.
  • Example 161 A PET film having a thickness of 180 ⁇ m was rubbed using a commercially available rubbing apparatus, and then the polymerizable composition (60) of the present invention was applied by a bar coating method and dried at 80 ° C. for 2 minutes. The obtained coating film is cooled to room temperature, and then irradiated with ultraviolet rays at a conveyor speed of 5 m / min using a UV conveyor device (manufactured by GS Yuasa Co., Ltd.) having a lamp output of 2 kW to obtain a homogeneously oriented optical anisotropic body. It was. The orientation evaluation, retardation ratio, and curability evaluation of the obtained optical anisotropic body were performed in the same manner as in Example 138.
  • the obtained optical anisotropic body has a phase difference Re (550) of 137 nm and a ratio Re (450) / Re (550) of the in-plane phase difference (Re (450)) and Re (550) at a wavelength of 450 nm of 0.837.
  • a retardation film with good uniformity was obtained.
  • the film did not peel at all even when rubbed 20 times or more.
  • a polyvinyl alcohol film having an average degree of polymerization of about 2400 and a saponification degree of 99.9 mol% or more and a thickness of 75 ⁇ m was uniaxially stretched about 5.5 times in a dry manner, and further kept at 60 ° C.
  • After being immersed in pure water for 60 seconds it was immersed in an aqueous solution having a weight ratio of iodine / potassium iodide / water of 0.05 / 5/100 at 28 ° C. for 20 seconds. Then, it was immersed in an aqueous solution having a weight ratio of potassium iodide / boric acid / water of 8.5 / 8.5 / 100 at 72 ° C. for 300 seconds.
  • the film was washed with pure water at 26 ° C. for 20 seconds and then dried at 65 ° C. to obtain a polarizing film in which iodine was adsorbed and oriented on a polyvinyl alcohol resin.
  • the optically anisotropic body formed from the polymerizable compositions (1) to (75) of the present invention using one or more hydrogen abstraction type photopolymerization initiators (C) having a peak is evaluated for orientation.
  • the retardation ratio and curability evaluation results are all good, and it can be said that the productivity is excellent.
  • a photopolymerization initiator a compound represented by formula (b-1-1), a compound represented by formula (b-3-2-1), and a compound represented by formula (c-1-5)
  • the results of evaluation of alignment, retardation ratio, and evaluation of curability were very good.

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WO2020137529A1 (ja) * 2018-12-28 2020-07-02 日本ゼオン株式会社 位相差フィルム及びその製造方法、並びに偏光板
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WO2021060427A1 (ja) * 2019-09-27 2021-04-01 富士フイルム株式会社 重合性液晶組成物、硬化物、光学フィルム、偏光板および画像表示装置

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