WO2016060172A1 - 化合物および組成物 - Google Patents
化合物および組成物 Download PDFInfo
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- WO2016060172A1 WO2016060172A1 PCT/JP2015/079071 JP2015079071W WO2016060172A1 WO 2016060172 A1 WO2016060172 A1 WO 2016060172A1 JP 2015079071 W JP2015079071 W JP 2015079071W WO 2016060172 A1 WO2016060172 A1 WO 2016060172A1
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- 0 CC1C=CC(*)=CC1 Chemical compound CC1C=CC(*)=CC1 0.000 description 7
- BPYMORNAGAUTIK-ISLYRVAYSA-N CC(Nc(cc1)ccc1/N=N/c1cc([s]c(I)n2)c2[s]1)=O Chemical compound CC(Nc(cc1)ccc1/N=N/c1cc([s]c(I)n2)c2[s]1)=O BPYMORNAGAUTIK-ISLYRVAYSA-N 0.000 description 1
- SYCLARANGXPZAB-UHFFFAOYSA-N Cc(cc1)ccc1OC(C(CC1)CCC1C(O)OC1C=CC(C)=CC1)=O Chemical compound Cc(cc1)ccc1OC(C(CC1)CCC1C(O)OC1C=CC(C)=CC1)=O SYCLARANGXPZAB-UHFFFAOYSA-N 0.000 description 1
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- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D11/00—Producing optical elements, e.g. lenses or prisms
- B29D11/00634—Production of filters
- B29D11/00644—Production of filters polarizing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D11/00—Producing optical elements, e.g. lenses or prisms
- B29D11/0074—Production of other optical elements not provided for in B29D11/00009- B29D11/0073
- B29D11/00788—Producing optical films
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- C07C22/04—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings containing six-membered aromatic rings
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- C07C245/02—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides
- C07C245/06—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings
- C07C245/08—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings with the two nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings, e.g. azobenzene
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- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
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- C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
- C07D513/04—Ortho-condensed systems
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- C09K19/60—Pleochroic dyes
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- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
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- 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
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- 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
- G02F1/133528—Polarisers
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- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/868—Arrangements for polarized light emission
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- C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
- C09K2019/0448—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate
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- 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
- G02F1/13356—Structural association of cells with optical devices, e.g. polarisers or reflectors characterised by the placement of the optical elements
- G02F1/133565—Structural association of cells with optical devices, e.g. polarisers or reflectors characterised by the placement of the optical elements inside the LC elements, i.e. between the cell substrates
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- G02F2202/00—Materials and properties
- G02F2202/02—Materials and properties organic material
- G02F2202/022—Materials and properties organic material polymeric
Definitions
- the present invention relates to a compound and a composition.
- Patent Document 1 describes a polarizing film containing a dichroic dye dispersed in an aligned polymerizable liquid crystal compound.
- Patent Document 2 describes a bisazo dye having a 1,4-naphthyl structure as a dichroic dye having a maximum absorption in a wavelength range of 350 nm to 550 nm. However, the dichroic ratio of the polarizing film containing the dichroic dye was low.
- R 1 represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an acyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, or 1 to 20 carbon atoms.
- R 10 is an acyl group having 1 to 20 carbon atoms, an alkylsulfonyl group or an arylsulfonyl group having 6 to 20 carbon atoms having 1 to 20 carbon atoms
- R 11 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms
- R 10 and R 11 are bonded to each other, and together with the nitrogen atom to which they are bonded, —N—CO— or —N—SO
- a ring containing 2- may be formed.
- One or more hydrogen atoms constituting the alkyl group, the alkoxy group, the acyl group, the alkoxycarbonyl group, the acyloxy group, the alkylsulfonyl group and the arylsulfonyl group are a halogen atom, a hydroxy group, an amino group or It may be replaced with an amino group having a substituent.
- —O— or —NR 20 — may be inserted between the carbon atoms constituting the alkyl group and the alkoxy group, and R 20 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
- R 7 and R 8 are substituents other than a hydrogen atom, and each independently represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, or a cyano group, At least one hydrogen atom constituting the alkyl group having 1 to 4 carbon atoms and the alkoxy group having 1 to 4 carbon atoms may be substituted with a halogen atom or a hydroxy group, and p and q are each independently 0 It is an integer of ⁇ 2.
- R 2 represents an acyl group having 1 to 20 carbon atoms, an alkylsulfonyl group having 1 to 20 carbon atoms, or an arylsulfonyl group having 6 to 20 carbon atoms
- R 3 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
- R 2 and R 3 may be bonded to each other to form a ring containing —N—CO— or —N—SO 2 — together with the nitrogen atom to which they are bonded.
- One or more hydrogen atoms constituting the acyl group, the alkylsulfonyl group and the arylsulfonyl group may be replaced with a halogen atom, a hydroxy group, an amino group or an amino group having a substituent.
- —O— or —NR 21 — may be inserted between the carbon atoms constituting the alkyl group and the alkoxy group, and R 21 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
- Y represents the formula (Y1): (In the formula, * represents a bonding site with N.
- R 9 is a substituent other than a hydrogen atom, and each independently represents an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. Represents a halogen atom or a cyano group, and at least one hydrogen atom constituting the alkyl group having 1 to 4 carbon atoms and the alkoxy group having 1 to 4 carbon atoms may be substituted with a halogen atom or a hydroxy group R is an integer from 0 to 2.) Or a group represented by formula (Y2): (In the formula, * represents a bonding site with N, P 1 and P 2 each independently represent —S—, —O— or —N (R 12 ) —, and R 12 represents a hydrogen atom.
- an alkyl group having 1 to 4 carbon atoms, and Q 1 and Q 2 each independently represent ⁇ N— or ⁇ CH—.
- Represents a group represented by ] A compound represented by [2] The compound according to [1], wherein p, q and r are 0.
- a composition comprising a polymerizable liquid crystal compound and the compound according to [1] or [2].
- a polarizing film comprising the compound according to [1] or [2].
- [7] A polarizing film formed from the composition according to any one of [3] to [5].
- [8] The polarizing film according to [6] or [7], wherein the maximum absorption wavelength ( ⁇ max1 ) of the polarizing film is longer than the maximum absorption wavelength ( ⁇ max2 ) of the compound represented by formula (1).
- the polarizing film according to any one of [6] to [9] which exhibits a Bragg peak in X-ray diffraction measurement.
- a liquid crystal display device comprising the polarizing film according to any one of [6] to [10].
- a liquid crystal cell comprising the polarizing film according to any one of [6] to [10], a liquid crystal layer, and a substrate.
- a color filter is further disposed between the substrate and the liquid crystal layer.
- a circularly polarizing plate comprising the polarizing film according to any one of [6] to [10] and a quarter-wave plate.
- An organic EL display device comprising the polarizing film according to any one of [6] to [10] and an organic EL element.
- An organic EL display device comprising the circularly polarizing plate according to [15] and an organic EL element.
- Formula (2) [Wherein, X represents a chlorine atom, a bromine atom or an iodine atom.
- R 1 is an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an acyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, an acyloxy group having 1 to 20 carbon atoms, or represents -N (R 10) (R 11 ),
- R 10 represents an acyl group, an alkylsulfonyl group or an arylsulfonyl group having 6 to 20 carbon atoms having 1 to 20 carbon atoms having 1 to 20 carbon atoms,
- R 11 Represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R 10 and R 11 are bonded to each other, and together with the nitrogen atom to which they are bonded, includes —N—CO— or —N—SO 2 —.
- a ring may be formed.
- One or more hydrogen atoms constituting the alkyl group, the alkoxy group, the acyl group, the alkoxycarbonyl group, the acyloxy group, the alkylsulfonyl group and the arylsulfonyl group are a halogen atom, a hydroxy group, an amino group or It may be replaced with an amino group having a substituent.
- —O— or —NR 20 — may be inserted between the carbon atoms constituting the alkyl group and the alkoxy group, and R 20 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
- R 7 is a substituent other than a hydrogen atom, and each independently represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, or a cyano group. At least one hydrogen atom constituting the alkyl group having 4 to 4 and the alkoxy group having 1 to 4 carbon atoms may be substituted with a halogen atom or a hydroxy group, and p is an integer of 0 to 2.
- Y represents the formula (Y1): (Wherein * represents a bonding site with N.
- R represents an alkoxy group having 1 to 4 carbon atoms, a halogen atom, or a cyano group, the alkyl group having 1 to 4 carbon atoms and the alkoxy group having 1 to 4 carbon atoms) And at least one hydrogen atom constituting R may be substituted with a halogen atom or a hydroxy group, and r is an integer of 0 to 2.
- Y2 a group represented by formula (Y2): (In the formula, * represents a bonding site with N, P 1 and P 2 each independently represent —S—, —O— or —N (R 12 ) —, and R 12 represents a hydrogen atom.
- R 2 represents an acyl group having 1 to 20 carbon atoms, an alkylsulfonyl group having 1 to 20 carbon atoms, or an arylsulfonyl group having 6 to 20 carbon atoms
- R 3 represents a hydrogen atom or an alkylsulfonyl group having 1 to 20 carbon atoms.
- R 2 and R 3 may be bonded to each other to form a ring containing —N—CO— or —N—SO 2 — together with the nitrogen atom to which they are bonded.
- One or more hydrogen atoms constituting the acyl group, the alkylsulfonyl group and the arylsulfonyl group may be replaced with a halogen atom, a hydroxy group, an amino group or an amino group having a substituent.
- —O— or —NR 21 — may be inserted between the carbon atoms constituting the alkyl group and the alkoxy group, and R 21 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
- R 8 is a substituent other than a hydrogen atom, and each independently represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, or a cyano group. And at least one hydrogen atom constituting the alkyl group having 1 to 4 and the alkoxy group having 1 to 4 carbon atoms may be substituted with a halogen atom or a hydroxy group, and q is an integer of 0 to 2.
- R 4 and R 5 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R 4 and R 5 are bonded to each other, and together with the oxygen atom and boron atom to which they are bonded, A ring containing O—B—O— may be formed.
- the compound represented by formula (1) is reacted: [Wherein, R 1 , R 2 , R 3 , R 7 , R 8 and Y represent the same meaning as described above. ] The manufacturing method of the compound represented by these.
- the compound of the present invention is a novel compound that functions as a dichroic dye having a maximum absorption in the wavelength range of 350 nm to 550 nm, and forms a polarizing film having a high dichroic ratio from the composition containing the compound. Can do.
- the azo group of the compound represented by the formula (1) of the present invention (hereinafter sometimes referred to as compound (1)) is preferably a trans azo group.
- R 1 is an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an acyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, or 1 carbon atom. Represents an acyloxy group of ⁇ 20 or —N (R 10 ) (R 11 ).
- alkyl group having 1 to 20 carbon atoms examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n -Hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, etc., unsubstituted (not having a substituent) linear or branched carbon number of 1 to There are 20 alkyl groups.
- One or more hydrogen atoms constituting the alkyl group having 1 to 20 carbon atoms may be substituted with a halogen atom (for example, a fluorine atom), a hydroxy group, an amino group, or an amino group having a substituent.
- a halogen atom for example, a fluorine atom
- the amino group having a substituent include one or two carbon atoms having 1 to 20 carbon atoms such as an N-methylamino group, an N-ethylamino group, an N, N-dimethylamino group, and an N, N-diethylamino group.
- Examples thereof include an amino group substituted with an alkyl group.
- Examples of the alkyl group in which one or more hydrogen atoms are replaced with a halogen atom or the like include a haloalkyl group having 1 to 20 carbon atoms such as a fluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, and a nonafluorobutyl group, and a hydroxymethyl group 1 having a non-substituted or substituted amino group such as a hydroxyalkyl group having 1 to 20 carbon atoms such as 2-hydroxyethyl group, aminomethyl group, 2- (N, N-dimethylamino) ethyl group, etc.
- a haloalkyl group having 1 to 20 carbon atoms such as a fluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, and a nonafluorobutyl group
- R 20 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
- Examples of the 20 alkyl groups include the same groups as described above.
- Examples of the alkyl group having —O— or —NR 20 — inserted between carbon atoms include a methoxymethyl group, 2-ethoxyethyl group, 2- (2-ethoxyethoxy) ethyl group, 2- [2- (ethyl Amino) ethyl) amino] ethyl group and the like.
- alkoxy group having 1 to 20 carbon atoms examples include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, n-pentyloxy group, isopentyloxy group, Non-substituted linear or branched carbon atoms such as neopentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, etc. There are 20 alkoxy groups.
- One or more hydrogen atoms constituting the alkoxy group having 1 to 20 carbon atoms may be substituted with a halogen atom (for example, a fluorine atom), a hydroxy group, an amino group, or an amino group having a substituent.
- a halogen atom for example, a fluorine atom
- the amino group having a substituent include one or two carbon atoms having 1 to 20 carbon atoms such as an N-methylamino group, an N-ethylamino group, an N, N-dimethylamino group, and an N, N-diethylamino group.
- Examples thereof include an amino group substituted with an alkyl group.
- Examples of the alkoxy group in which one or more hydrogen atoms are replaced by a halogen atom or the like include haloalkoxy groups having 1 to 20 carbon atoms such as fluoromethoxy group, trifluoromethoxy group, pentafluoroethoxy group, and nonafluorobutoxy group, hydroxymethoxy Carbon number having an unsubstituted or substituted amino group such as a hydroxyalkoxy group having 1 to 20 carbon atoms such as 2-hydroxyethoxy group, aminomethoxy group, 2- (N, N-dimethylamino) ethoxy group, etc. Examples include 1 to 20 alkoxy groups.
- Examples include methoxymethoxy group, 2-ethoxyethoxy group, 2- (2-ethoxyethoxy) ethoxy group, 2- [2- (ethylamino) ethyl) amino] ethoxy group, and the like.
- acyl group having 1 to 20 carbon atoms examples include formyl group, acetyl group, ethylcarbonyl group, n-propylcarbonyl group, isopropylcarbonyl group, n-butylcarbonyl group, isobutylcarbonyl group, tert-butylcarbonyl group, and n-pentyl.
- Unsubstituted carbon number such as carbonyl group, isopentylcarbonyl group, neopentylcarbonyl group, n-hexylcarbonyl group, n-heptylcarbonyl group, n-octylcarbonyl group, n-nonylcarbonyl group, n-decylcarbonyl group, etc. ⁇ 20 acyl groups.
- One or more hydrogen atoms constituting the acyl group may be substituted with a halogen atom (for example, a fluorine atom), a hydroxy group, an amino group, or an amino group having a substituent.
- Examples of the amino group having a substituent include one or two carbon atoms having 1 to 20 carbon atoms such as an N-methylamino group, an N-ethylamino group, an N, N-dimethylamino group, and an N, N-diethylamino group. Examples thereof include an amino group substituted with an alkyl group.
- Examples of the acyl group in which one or more hydrogen atoms are replaced by a halogen atom include haloacyl groups having 1 to 20 carbon atoms such as a trifluoroacetyl group, a pentafluoroethylcarbonyl group, and a nonafluorobutylcarbonyl group.
- alkoxycarbonyl group having 2 to 20 carbon atoms examples include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, isobutoxycarbonyl group, tert-butoxycarbonyl group, n- Pentyloxycarbonyl group, isopentyloxycarbonyl group, neopentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, n-nonyloxycarbonyl group, n-decyloxycarbonyl And an unsubstituted alkoxycarbonyl group having 2 to 20 carbon atoms such as a group.
- One or more hydrogen atoms constituting the alkoxycarbonyl group may be substituted with a halogen atom (for example, a fluorine atom), a hydroxy group, an amino group, or an amino group having a substituent.
- a halogen atom for example, a fluorine atom
- the amino group having a substituent include one or two carbon atoms having 1 to 20 carbon atoms such as an N-methylamino group, an N-ethylamino group, an N, N-dimethylamino group, and an N, N-diethylamino group.
- Examples thereof include an amino group substituted with an alkyl group.
- alkoxycarbonyl group in which one or more hydrogen atoms are replaced by a halogen atom or the like examples include halo of 2 to 20 carbon atoms such as a fluoromethoxycarbonyl group, a trifluoromethoxycarbonyl group, a pentafluoroethoxycarbonyl group, and a nonafluorobutoxycarbonyl group.
- halo of 2 to 20 carbon atoms such as a fluoromethoxycarbonyl group, a trifluoromethoxycarbonyl group, a pentafluoroethoxycarbonyl group, and a nonafluorobutoxycarbonyl group.
- An alkoxycarbonyl group is mentioned.
- acyloxy group having 1 to 20 carbon atoms examples include acetyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, isopropylcarbonyloxy group, n-butylcarbonyloxy group, isobutylcarbonyloxy group, tert-butylcarbonyloxy group N-pentylcarbonyloxy group, isopentylcarbonyloxy group, neopentylcarbonyloxy group, n-hexylcarbonyloxy group, n-heptylcarbonyloxy group, n-octylcarbonyloxy group, n-nonylcarbonyloxy group, n- Examples thereof include an unsubstituted acyloxy group having 1 to 20 carbon atoms such as a decylcarbonyloxy group.
- One or more hydrogen atoms constituting the acyloxy group may be substituted with a halogen atom (for example, a fluorine atom), a hydroxy group, an amino group, or an amino group having a substituent.
- a halogen atom for example, a fluorine atom
- the amino group having a substituent include one or two carbon atoms having 1 to 20 carbon atoms such as an N-methylamino group, an N-ethylamino group, an N, N-dimethylamino group, and an N, N-diethylamino group.
- Examples thereof include an amino group substituted with an alkyl group.
- acyloxy group in which one or more hydrogen atoms are replaced with a halogen atom or the like examples include those having 1 to 20 carbon atoms such as a fluoroacetyloxy group, a trifluoroacetyloxy group, a pentafluoroethylcarbonyloxy group, and a nonafluorobutylcarbonyloxy group.
- a haloacyloxy group is mentioned.
- R 10 in -N (R 10) (R 11 ) represents an acyl group, an alkylsulfonyl group or an arylsulfonyl group having 6 to 20 carbon atoms having 1 to 20 carbon atoms having 1 to 20 carbon atoms
- R 11 is Represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, wherein R 10 and R 11 are bonded to each other, and together with the nitrogen atom to which they are bonded, a ring containing —N—CO— or —N—SO 2 — It may be formed.
- One or more hydrogen atoms constituting the acyl group, alkylsulfonyl group and arylsulfonyl group in R 10 are substituted with a halogen atom (for example, fluorine atom), a hydroxy group, an amino group or an amino group having a substituent. Also good.
- a halogen atom for example, fluorine atom
- the amino group having a substituent include one or two carbon atoms having 1 to 20 carbon atoms such as an N-methylamino group, an N-ethylamino group, an N, N-dimethylamino group, and an N, N-diethylamino group. Examples thereof include an amino group substituted with an alkyl group.
- acyl group having 1 to 20 carbon atoms in R 10 include those similar to the acyl group having 1 to 20 carbon atoms in R 1 described above, and one or more hydrogen atoms constituting the acyl group are halogenated.
- Examples of the acyl group replaced with an atom and the like include the same groups as those described above for R 1 .
- alkylsulfonyl group having 1 to 20 carbon atoms examples include unsubstituted alkylsulfonyl groups having 1 to 20 carbon atoms such as a methylsulfonyl group, an ethylsulfonyl group, and an n-propylsulfonyl group, and constitute such an alkylsulfonyl group.
- Examples of the group in which one or more hydrogen atoms are replaced with a halogen atom or the like include a haloalkylsulfonyl group having 1 to 20 carbon atoms such as a trifluoromethylsulfonyl group, a pentafluoroethylsulfonyl group, and a heptafluoro-n-propylsulfonyl group. Can be mentioned.
- Examples of the arylsulfonyl group having 6 to 20 carbon atoms include a benzenesulfonyl group and a p-toluenesulfonyl group.
- Examples of the alkyl group having 1 to 20 carbon atoms in R 11 include those similar to the alkyl group having 1 to 20 carbon atoms in R 1 , and one or more hydrogen atoms constituting the alkyl group are halogenated
- Examples of the alkyl group replaced with an atom and the like include the same groups as those described above for R 1 .
- —N (R 10 ) (R 11 ) include acylamino group, ethylcarbonylamino group, n-propylcarbonylamino group, isopropylcarbonylamino group, n-butylcarbonylamino group, isobutylcarbonylamino group, tert- Butylcarbonylamino group, n-pentylcarbonylamino group, isopentylcarbonylamino group, neopentylcarbonylamino group, n-hexylcarbonylamino group, n-heptylcarbonylamino group, n-octylcarbonylamino group, n-nonylcarbonylamino Group, n-decylcarbonylamino group, trifluoroacylamino group.
- the ring containing —N—CO— or —N—SO 2 — formed by combining R 10 and R 11 together with the nitrogen atom to which they are bonded is preferably a 4- to 10-membered ring. More preferred is a 7-membered ring. Specific examples include a 2-pyrrolidone-1-yl group.
- R 1 is preferably an alkyl group having 1 to 10 carbon atoms which may have a halogen atom (preferably a fluorine atom), and 1 to 20 carbon atoms in which —O— is inserted between the constituting carbon atoms.
- a halogen atom preferably a fluorine atom
- an acyl group having 1 to 20 carbon atoms, and R 11 is preferably a hydrogen atom.
- R 1 is more preferably a linear alkyl group having 1 to 10 carbon atoms which may have a fluorine atom or —N (R 10 ) (R 11 ), and R 10 is more preferably , An acyl group having 1 to 10 carbon atoms which may have a fluorine atom, and R 11 is preferably a hydrogen atom.
- R 1 is particularly preferably a linear alkyl group having 1 to 10 carbon atoms which may have a fluorine atom.
- At least one hydrogen atom constituting each of the two phenylene groups may be substituted with a substituent R 7 or R 8 other than hydrogen.
- R 7 and R 8 each independently represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, or a cyano group.
- R 7 and R 8 may each be substituted with a hydrogen atom at any position of the phenylene group.
- alkyl group having 1 to 4 carbon atoms examples include a straight chain having no substituent such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group. Or a branched alkyl group is mentioned. At least one hydrogen atom constituting the alkyl group having 1 to 4 carbon atoms may be substituted with a halogen atom such as a fluorine atom or a hydroxy group.
- haloalkyl groups having 1 to 4 carbon atoms such as a fluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, and a nonafluorobutyl group; 1 to carbon atoms such as a hydroxymethyl group and a 2-hydroxyethyl group. 4 hydroxyalkyl groups;
- alkoxy group having 1 to 4 carbon atoms examples include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, etc. And a branched alkoxy group. At least one hydrogen atom constituting the alkoxy group having 1 to 4 carbon atoms may be substituted with a halogen atom such as a fluorine atom or a hydroxy group.
- haloalkoxy groups having 1 to 4 carbon atoms such as a fluoromethoxy group, a trifluoromethoxy group, a pentafluoroethoxy group, and a nonafluorobutoxy group; 1 carbon atoms such as a hydroxymethoxy group and a 2-hydroxyethoxy group. ⁇ 4 hydroxyalkoxy groups.
- R 2 represents an acyl group having 1 to 20 carbon atoms, an alkylsulfonyl group having 1 to 20 carbon atoms or an arylsulfonyl group having 6 to 20 carbon atoms
- R 3 represents a hydrogen atom or 1 to 20 carbon atoms.
- R 20 represents an alkyl group
- R 2 and R 3 may be bonded to each other to form a ring containing —N—CO— or —N—SO 2 — together with the nitrogen atom to which they are bonded
- One or more hydrogen atoms constituting the acyl group, the alkylsulfonyl group and the arylsulfonyl group may be substituted with a halogen atom (for example, a fluorine atom), a hydroxy group, an amino group or an amino group having a substituent.
- a halogen atom for example, a fluorine atom
- Examples of the amino group having a substituent include one or two carbon atoms having 1 to 20 carbon atoms such as N-methylamino group, N-ethylamino group, N, N-dimethylamino group, N, N-diethylamino group and the like. Examples thereof include an amino group substituted with an alkyl group. —O— or —NR 21 — may be inserted between the carbon atoms constituting the alkyl group and the alkoxy group, and R 21 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
- Examples of the acyl group having 1 to 20 carbon atoms in R 2 include the same groups as those described above for R 1 .
- the alkylsulfonyl group having 1 to 20 carbon atoms and the arylsulfonyl group having 6 to 20 carbon atoms in R 2 respectively, the alkylsulfonyl group having 1 to 20 carbon atoms and the arylsulfonyl group having 6 to 20 carbon atoms in the above R 10
- the same thing as a group is mentioned.
- the ring containing —N—CO— or —N—SO 2 — formed by combining R 2 and R 3 together with the nitrogen atom to which they are bonded is preferably a 4- to 10-membered ring. More preferred is a 7-membered ring. Specific examples include a 2-pyrrolidone-1-yl group.
- Examples of the alkyl group having 1 to 20 carbon atoms for R 21 include the same groups as described above.
- R 2 is preferably an acyl group having 1 to 20 carbon atoms which may have a halogen atom (preferably a fluorine atom) or a carbon atom which has 1 to 20 carbon atoms which may have a halogen atom (preferably a fluorine atom).
- R 3 is preferably a hydrogen atom.
- Y represents formula (Y1): (In the formula, * represents a bonding site with N.
- R 9 is a substituent other than a hydrogen atom, and each independently represents an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.
- an alkyl group having 1 to 4 carbon atoms, and Q 1 and Q 2 each independently represent ⁇ N— or ⁇ CH—.
- R 9 examples include the same as those exemplified for R 7 and R 8 above.
- P 1 is preferably —S—.
- P 2 is preferably —S—.
- the alkyl group having 1 to 4 carbon atoms for R 12 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group.
- Q 1 is preferably ⁇ CH—.
- Q 2 is preferably ⁇ N—.
- p, q and r are each independently an integer of 0 to 2, preferably 0.
- Specific examples of the compound (1) include compounds represented by the following formulas (1-1) to (1-24).
- Compound (1) has the formula (2): [Wherein, X represents a chlorine atom, a bromine atom or an iodine atom. R 1 , R 7 , p and Y each have the same meaning as described above. ]
- X in the compound (2) is preferably a bromine atom.
- the alkyl group having 1 to 10 carbon atoms represented by R 4 and the alkyl group having 1 to 10 carbon atoms represented by R 5 in the compound (3) include a methyl group, an ethyl group, an n-propyl group, Isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl Examples thereof include an unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms.
- Examples of the ring containing —O—B—O— formed by combining R 4 and R 5 with each other and the oxygen atom and boron atom to which they are bonded include the following rings.
- * represents a bond with a benzene ring.
- Examples of —B (OR 4 ) (OR 5 ) include the following groups, and —B (OH) 2 is preferable.
- * represents a bond with a benzene ring.
- Compound (2) may be commercially available, or synthesized according to the method described in Synthesis, 1997, 6, 681, Journal of Chemical Society, 1970, 35, 505. It may be synthesized by the Sandmeyer reaction from an amino compound synthesized according to the method described in JP-A-58-38756. Sandmeyer reaction can be performed by the method described in JournalJof Chemical society, tyPerkin Trans.1998,685.
- compound (2) examples include compounds represented by the following formulas (2-1) to (2-18).
- Specific examples of the compound (3) include compounds represented by the following formulas (3-1) to (3-7).
- Compound (3) may be commercially available, or may be synthesized according to the method described in Journal of Organic Chemistry, 1995, 60, 7508.
- the reaction between the compound (2) and the compound (3) can be carried out according to the method described in Chemical Reviews, 1995, 95 (7), 2457.
- the compound (1) can be taken out by a usual take-out means such as recrystallization, reprecipitation, extraction, various chromatographies, etc. after completion of the reaction.
- Compound (1) is a compound that functions as a dichroic dye, and particularly exhibits higher dichroism when aligned with a polymerizable liquid crystal compound. Therefore, the polarizing film in which the compound (1) is aligned with the polymerizable liquid crystal compound exhibits higher dichroism.
- the compound (1) has a maximum absorption in the wavelength range of 350 nm to 510 nm, preferably in the wavelength range of 400 nm to 500 nm, more preferably in the wavelength range of 410 nm to 490 nm, and still more preferably in the wavelength range of 420 nm to 480 nm. Moreover, since compound (1) has light resistance, the polarizing film containing the compound of this invention is excellent in light resistance.
- the light resistance of the polarizing film can be determined, for example, by the following method.
- a protective film is arrange
- the light resistance is determined from the ratio of the absorbance of the polarizing film having the maximum absorption wavelength of 501 nm after the light resistance test to the absorbance of the polarizing film having the maximum absorption wavelength of 501 nm of the polarizing film before the test.
- a polarizing film is formed using a dichroic dye represented by the formula (1-10) described in JP2013-101328A and a light resistance test is performed, the polarizing film has a maximum absorption wavelength of 548 nm.
- the absorbance of the polarizing film after the light resistance test is 47% before the test.
- composition of this invention containing a polymeric liquid crystal compound and a compound (1) is demonstrated.
- the composition of the present invention may contain two or more compounds (1).
- the polymerizable liquid crystal compound is a compound having a polymerizable group in the molecule and capable of exhibiting a liquid crystal phase by alignment, and preferably a compound capable of exhibiting a liquid crystal phase by aligning alone. .
- the polymerizable group means a group involved in the polymerization reaction, and is preferably a photopolymerizable group.
- the polymerizable group means a group that can participate in a polymerization reaction by an active radical, an acid, or the like generated from a polymerization initiator described later.
- Examples of the polymerizable group include a vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, acryloyloxy group, methacryloyloxy group, oxiranyl group and oxetanyl group.
- the polymerizable liquid crystal compound may be a thermotropic liquid crystal type or a lyotropic liquid crystal type.
- the polymerizable liquid crystal compound may exhibit a nematic liquid crystal phase, may exhibit a smectic liquid crystal phase, or may exhibit both a nematic liquid crystal phase and a smectic liquid crystal phase. Preferably, it shows a smectic liquid crystal phase, and more preferably shows a higher order smectic liquid crystal phase.
- the composition of the present invention containing a polymerizable liquid crystal compound exhibiting a smectic liquid crystal phase can provide a polarizing film having more excellent polarization performance.
- the composition of the present invention may contain two or more polymerizable liquid crystal compounds.
- the compound (1) can exhibit high dichroism even when dispersed between dense molecular chains formed from a polymerizable liquid crystal compound exhibiting a smectic liquid crystal phase, and includes the compound (1).
- the composition can provide a polarizing film having a high dichroic ratio.
- Examples of the high-order smectic liquid crystal phase include a smectic B phase, a smectic D phase, a smectic E phase, a smectic F phase, a smectic G phase, a smectic H phase, a smectic I phase, a smectic J phase, a smectic K phase, and a smectic L phase.
- a smectic B phase, a smectic F phase, and a smectic I phase are preferable.
- a polarizing film having a higher degree of alignment order can be obtained.
- a polarizing film obtained from a composition containing a polymerizable liquid crystal compound exhibiting a high-order smectic liquid crystal phase having a high degree of orientational order exhibits a Bragg peak derived from a higher-order structure such as a hexatic phase or a crystal phase in X-ray diffraction measurement.
- the Bragg peak is a peak derived from the surface periodic structure of molecular orientation.
- the period interval of the polarizing film obtained from the composition of the present invention is preferably 3.0 to 5.0 mm (0.30 nm to 0.50 nm).
- the kind of liquid crystal phase exhibited by the polymerizable liquid crystal compound can be confirmed, for example, as follows. Prepare an appropriate base material, apply a solution containing a polymerizable liquid crystal compound and a solvent to the base material to form a coating film, and then remove the solvent contained in the coating film by heat treatment or reduced pressure treatment. To do. Subsequently, the coating film formed on the substrate is heated to the isotropic phase temperature, and the liquid crystal phase that is expressed by gradually cooling is inspected by texture observation, X-ray diffraction measurement or differential scanning calorimetry using a polarizing microscope. To do. In this inspection, for example, it can be confirmed that a nematic liquid crystal phase is exhibited by cooling to the first temperature, and a smectic liquid crystal phase is exhibited by gradually cooling to the second temperature.
- the polymerizable liquid crystal composition is preferably a compound represented by formula (4) (hereinafter sometimes referred to as compound (4)).
- X 1 , X 2 and X 3 each independently represent a 1,4-phenylene group which may have a substituent or a cyclohexane-1,4-diyl group which may have a substituent.
- at least one of X 1 , X 2 and X 3 is a 1,4-phenylene group which may have a substituent.
- —CH 2 — constituting the cyclohexane-1,4-diyl group may be replaced by —O—, —S— or —NR—.
- R represents an alkyl group having 1 to 6 carbon atoms or a phenyl group.
- R a and R b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
- U 1 represents a hydrogen atom or a polymerizable group.
- U 2 represents a polymerizable group.
- W 1 and W 2 each independently represent a single bond, —O—, —S—, —COO— or —OCOO—.
- V 1 and V 2 each independently represents an optionally substituted alkanediyl group having 1 to 20 carbon atoms, and —CH 2 — constituting the alkanediyl group is —O—, — S— or —NH— may be substituted.
- At least one of X 1 , X 2 and X 3 is preferably a 1,4-phenylene group which may have a substituent.
- the 1,4-phenylene group which may have a substituent is preferably a 1,4-phenylene group having no substituent.
- the cyclohexane-1,4-diyl group which may have a substituent is preferably a trans-cyclohexane-1,4-diyl group which may have a substituent.
- the trans-cyclohexane-1,4-diyl group which may have a substituent is preferably a trans-cyclohexane-1,4-diyl group which has no substituent.
- Examples of the substituent that the optionally substituted 1,4-phenylene group or the optionally substituted cyclohexane-1,4-diyl group includes a methyl group, an ethyl group, Examples thereof include an alkyl group having 1 to 4 carbon atoms such as an n-butyl group, a cyano group and a halogen atom.
- Y 1 is preferably —CH 2 CH 2 —, —COO— or a single bond
- Y 2 is preferably —CH 2 CH 2 — or —CH 2 O—.
- U 2 is a polymerizable group.
- U 1 is a hydrogen atom or a polymerizable group, preferably a polymerizable group.
- U 1 and U 2 are preferably both polymerizable groups, and more preferably both are photopolymerizable groups.
- the polymerizable liquid crystal compound having a photopolymerizable group is advantageous in that it can be polymerized under a lower temperature condition.
- the polymerizable groups represented by U 1 and U 2 may be different from each other, but are preferably the same.
- the polymerizable group include a vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, acryloyloxy group, methacryloyloxy group, oxiranyl group and oxetanyl group.
- acryloyloxy group, methacryloyloxy group, vinyloxy group, oxiranyl group and oxetanyl group are preferable, and acryloyloxy group is more preferable.
- alkanediyl group represented by V 1 and V 2 examples include methylene group, ethylene group, propane-1,3-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, pentane- 1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, decane-1,10-diyl group, tetradecane-1,14-diyl Groups and icosane-1,20-diyl groups.
- V 1 and V 2 are preferably alkanediyl groups having 2 to 12 carbon atoms, and more preferably alkanediyl groups having 6 to 12 carbon atoms.
- substituents that the alkanediyl group having 1 to 20 carbon atoms which may have a substituent optionally have include a cyano group and a halogen atom.
- the alkanediyl group is preferably an alkanediyl group having no substituent, and more preferably an alkanediyl group having no substituent and a linear alkanediyl group.
- W 1 and W 2 are preferably each independently a single bond or —O—.
- the compound (4) include compounds represented by the following formulas (4-1) to (4-43).
- the cyclohexane-1,4-diyl group is preferably a trans type.
- the composition of the present invention may contain two or more compounds (4).
- the liquid crystal phase may be temporarily retained even at a temperature lower than the liquid crystal-crystal phase transition temperature.
- the mixing ratio when combining two kinds of polymerizable liquid crystal compounds is usually 1:99 to 50:50, preferably 5:95 to 50:50, and more preferably 10:90 to 50:50. is there.
- Compound (4) is, for example, Lub et al. Recl. Trav. Chim. It can be produced by a method described in known literature such as Pays-Bas, 115, 321-328 (1996), Japanese Patent No. 4719156.
- the content of the polymerizable liquid crystal compound in the composition of the present invention is preferably 70 to 99.100 based on 100 parts by mass of the solid content of the composition of the present invention from the viewpoint of increasing the orientation of the polymerizable liquid crystal compound. It is 5 parts by mass, more preferably 80 to 99 parts by mass, still more preferably 80 to 94 parts by mass, and particularly preferably 80 to 90 parts by mass.
- solid content means the total amount of components other than the solvent in the composition of this invention.
- composition of the present invention preferably contains a polymerization initiator and a solvent, and may contain a photosensitizer, a polymerization inhibitor and a leveling agent.
- the content of the compound (1) in the composition of the present invention is usually 50 parts by mass or less, preferably 0.1 parts by mass or more and 10 parts by mass or less, based on 100 parts by mass of the polymerizable liquid crystal compound. Preferably they are 0.1 mass part or more and 5 mass parts or less.
- the content of the compound (1) with respect to 100 parts by mass of the polymerizable liquid crystal compound is 50 parts by mass or less, there is a tendency that a polarizing film in which the alignment disorder of the polymerizable liquid crystal compound and the compound (1) is small can be obtained.
- the solvent is preferably one that can completely dissolve the polymerizable liquid crystal compound and the compound (1). Moreover, it is preferable that it is a solvent inactive to the polymerization reaction of a polymerizable liquid crystal compound.
- Solvents include alcohol solvents such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, propylene glycol monomethyl ether; ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, ⁇ -butyrolactone Ester solvents such as propylene glycol methyl ether acetate and ethyl lactate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone and methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane and heptane; toluene , Aromatic hydrocarbon solvents such as xylene, nitrile solvents such as acetonitrile; tetrahydrofuran, dimeth
- the content of the solvent is preferably 50 to 98% by mass with respect to the total amount of the composition of the present invention.
- the solid content in the composition of the present invention is preferably 2 to 50% by mass.
- the viscosity of the composition of the present invention is low, the thickness of the polarizing film obtained from the composition of the present invention is substantially uniform, and unevenness is less likely to occur in the polarizing film. Tend.
- Such solid content can be determined in consideration of the thickness of the polarizing film to be manufactured.
- the polymerization initiator is a compound that can initiate a polymerization reaction of the polymerizable liquid crystal compound.
- a photopolymerization initiator that generates an active radical by the action of light is preferable.
- polymerization initiator examples include benzoin compounds, benzophenone compounds, alkylphenone compounds, acylphosphine oxide compounds, triazine compounds, iodonium salts, and sulfonium salts.
- benzoin compound examples include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.
- benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone And 2,4,6-trimethylbenzophenone.
- alkylphenone compound examples include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane.
- -1-one 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1,2-diphenyl-2,2-dimethoxyethane-1-one, 2-hydroxy-2-methyl-1- [ 4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one
- An oligomer is mentioned.
- acylphosphine oxide compound examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide.
- triazine compounds examples include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2 -(5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3 , 5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine and 2,
- the salt represented by a following formula is mentioned, for example.
- polymerization initiator Only one type of polymerization initiator may be used, or two or more types may be used in combination. A commercially available thing can be used as a polymerization initiator.
- Commercially available polymerization initiators include Irgacure (registered trademark) 907, 184, 651, 819, 250 and 369 (manufactured by Ciba Specialty Chemicals Co., Ltd.); Sequol (registered trademark) BZ, Z and BEE (Seiko) Kayacure (registered trademark) BP100 and UVI-6992 (manufactured by Dow Chemical Co., Ltd.); Adekaoptomer SP-152 and SP-170 (manufactured by ADEKA Corporation); TAZ-A and TAZ -PP (manufactured by Nippon Shibel Hegner); and TAZ-104 (manufactured by Sanwa Chemical Co., Ltd.).
- the content of the polymerization initiator in the composition of the present invention is based on 100 parts by mass of the polymerizable liquid crystal compound from the viewpoint of hardly disturbing the alignment of the polymerizable liquid crystal compound.
- the amount is usually 0.1 to 30 parts by mass, preferably 0.5 to 10 parts by mass, and more preferably 0.5 to 8 parts by mass.
- the composition of the present invention contains a photopolymerization initiator
- the composition of the present invention preferably contains a photosensitizer.
- the composition of the present invention contains a photopolymerization initiator and a photosensitizer, the polymerization reaction of the polymerizable liquid crystal compound tends to be further promoted.
- the photosensitizer examples include xanthone compounds such as xanthone and thioxanthone (for example, 2,4-diethylthioxanthone and 2-isopropylthioxanthone); anthracene compounds such as anthracene and alkoxy group-containing anthracene (for example, dibutoxyanthracene); phenothiazine And rubrene.
- xanthone compounds such as xanthone and thioxanthone (for example, 2,4-diethylthioxanthone and 2-isopropylthioxanthone)
- anthracene compounds such as anthracene and alkoxy group-containing anthracene (for example, dibutoxyanthracene)
- phenothiazine And rubrene examples of the photosensitizer
- the content of the photosensitizer in the composition of the present invention is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. More preferably, it is 0.5 to 10 parts by mass, and still more preferably 0.5 to 8 parts by mass.
- polymerization inhibitor examples include radical scavengers such as hydroquinone, alkoxy group-containing hydroquinone, alkoxy group-containing catechol (eg, butyl catechol), pyrogallol, 2,2,6,6-tetramethyl-1-piperidinyloxy radical; Examples include thiophenols; ⁇ -naphthylamines and ⁇ -naphthols.
- radical scavengers such as hydroquinone, alkoxy group-containing hydroquinone, alkoxy group-containing catechol (eg, butyl catechol), pyrogallol, 2,2,6,6-tetramethyl-1-piperidinyloxy radical
- examples include thiophenols; ⁇ -naphthylamines and ⁇ -naphthols.
- the composition of the present invention contains a polymerization inhibitor
- the progress of the polymerization reaction of the polymerizable liquid crystal compound can be controlled.
- the content of the polymerization inhibitor in the composition of the present invention is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound, More preferably, it is 0.5 to 10 parts by mass, and still more preferably 0.5 to 8 parts by mass.
- the leveling agent has a function of adjusting the fluidity of the composition of the present invention and flattening a coating film obtained by applying the composition of the present invention.
- a leveling agent is mentioned. Can do.
- a preferred leveling agent is a leveling agent having a polyacrylate compound as a main component and a leveling agent having a fluorine atom-containing compound as a main component.
- Leveling agents mainly composed of polyacrylate compounds include BYK-350, BYK-352, BYK-353, BYK-354, BYK-355, BYK-358N, BYK-361N, BYK-380, BYK-381, and BYK. -392 (manufactured by BYK-Chemie GmbH).
- Examples of the leveling agent mainly composed of a fluorine atom-containing compound include Megafac (registered trademark) R-08, R-30, R-90, F-410, F-411, F-443, F-445, F- 470, F-471, F-477, F-479, F-482, F-482 (manufactured by DIC Corporation); Surflon (registered trademark) S-381, S-382, S-383, S-393, SC -101, SC-105, KH-40 and SA-100 (manufactured by AGC Seimi Chemical Co., Ltd.); E1830 and E5844 (manufactured by Daikin Fine Chemical Laboratories Co., Ltd.); Electronics Chemical Co., Ltd.).
- Megafac registered trademark
- the content of the leveling agent is preferably 0.3 parts by mass or more and 5 parts by mass or less, more preferably 0 with respect to 100 parts by mass of the polymerizable liquid crystal compound. .5 parts by mass or more and 3 parts by mass or less.
- the content of the leveling agent is within the above range, it is easy to horizontally align the polymerizable liquid crystal compound, and the obtained polarizing film tends to be smoother. If the content of the leveling agent with respect to the polymerizable liquid crystal compound exceeds the above range, unevenness tends to occur in the obtained polarizing film.
- the composition of the present invention may contain two or more leveling agents.
- the polarizing film containing the compound (1) can be obtained, for example, by applying the composition of the present invention. Preferably, it can be produced by a production method including the following steps (A) to (C).
- the substrate may be a glass substrate or a resin substrate, but is preferably a resin substrate.
- a film substrate made of resin By using a film substrate made of resin, a thin polarizing plate can be obtained.
- the resin base material is preferably a transparent resin base material.
- the transparent resin base material means a base material having translucency capable of transmitting light, particularly visible light, and the translucency is a visibility corrected transmittance with respect to a light beam having a wavelength of 380 nm to 780 nm. % Or more.
- the base material is preferably a retardation film having a 1/4 wavelength plate function (hereinafter sometimes referred to as a 1/4 wavelength plate).
- a circularly polarizing plate can be obtained by using a quarter wave plate for the substrate.
- the lamination is preferably performed so that the transmission axis of the polarizing film and the slow axis (optical axis) of the quarter-wave plate are substantially 45 °.
- Substantially 45 ° is usually in the range of 45 ⁇ 5 °.
- the polarizing film which functions as an optical compensation film can be obtained by making the optical axis of a polarizing film and a quarter wavelength plate correspond or make orthogonal.
- the quarter-wave plate usually has an optical characteristic represented by the formula (40), and preferably has an optical characteristic represented by the formula (40-1).
- Re (550) represents an in-plane retardation value for light having a wavelength of 550 nm.
- the quarter wave plate preferably has reverse wavelength dispersion characteristics.
- the inverse chromatic dispersion characteristic is that the in-plane retardation value at a short wavelength is larger than the in-plane retardation value at a long wavelength, and is preferably expressed by Expression (50) and Expression (51). Satisfy optical properties.
- Re ( ⁇ ) represents an in-plane retardation value for light having a wavelength of ⁇ nm.
- the circularly polarizing plate provided with the quarter wavelength plate having the optical characteristics represented by the formulas (50) and (51) has uniform polarization conversion characteristics for light of each wavelength in the visible light region. As a result, the antireflection properties tend to be excellent.
- the base material may be a retardation film having a half-wave plate function.
- the resin constituting the substrate examples include polyolefins such as polyethylene, polypropylene, and norbornene polymers; cyclic olefin resins; polyvinyl alcohol; polyethylene terephthalate; polymethacrylates; polyacrylates; triacetylcellulose, diacetylcellulose, and Cellulose esters such as cellulose acetate propionate; polyethylene naphthalate; polycarbonate; polysulfone; polyethersulfone; polyetherketone; polyphenylene sulfide; and polyphenylene oxide.
- Cellulose ester is obtained by esterifying at least a part of hydroxyl groups contained in cellulose, and can be obtained from the market. Moreover, the base material containing a cellulose ester can also be obtained from a market. Examples of the substrate containing a commercially available cellulose ester include Fujitac (registered trademark) film (Fuji Photo Film Co., Ltd.), KC8UX2M (KC8UY), KC4UY (Konica Minolta Opto Co., Ltd.), and the like.
- the cyclic olefin-based resin includes polymers of cyclic olefins such as norbornene or polycyclic norbornene-based monomers, or copolymers thereof.
- the cyclic olefin-based resin may include a ring-opening structure, or may be a hydrogenated cyclic olefin-based resin including a ring-opening structure.
- the cyclic olefin-based resin may contain a structural unit derived from a chain olefin and a vinylated aromatic compound as long as the transparency is not significantly impaired and the hygroscopicity is not significantly increased.
- the cyclic olefin resin may have a polar group introduced in its molecule. Examples of the chain olefin include ethylene and propylene, and examples of the vinylated aromatic compound include styrene, ⁇ -methylstyrene, and alkyl-substituted styrene.
- the cyclic olefin-based resin is a copolymer of a cyclic olefin and a chain olefin or a vinylated aromatic compound
- the content of structural units derived from the cyclic olefin is based on the total structural units of the copolymer. The amount is usually 50 mol% or less, preferably 15 to 50 mol%.
- the cyclic olefin-based resin is a ternary copolymer of a cyclic olefin, a chain olefin, and a vinylated aromatic compound
- the content of structural units derived from the chain olefin is the total structure of the copolymer.
- the content of the structural unit derived from the vinylated aromatic compound is usually 5 to 80 mol% based on the unit, and the content ratio of the structural unit derived from the vinylated aromatic compound is usually 5 to 80 mol% based on the total structural unit of the copolymer.
- Such a terpolymer has the advantage that the amount of expensive cyclic olefin used can be relatively reduced.
- Cyclic olefin resin is available from the market.
- Commercially available cyclic olefin resins include Topas (registered trademark) (manufactured by Ticona (Germany)), Arton (registered trademark) (manufactured by JSR Corporation), ZEONOR (registered trademark) (manufactured by Nippon Zeon Corporation).
- ZEONEX registered trademark
- Apel registered trademark
- Such a cyclic olefin-based resin can be formed into a substrate by forming a film by a known means such as a solvent casting method or a melt extrusion method.
- a base material containing a commercially available cyclic olefin resin Essina (registered trademark) (manufactured by Sekisui Chemical Co., Ltd.), SCA40 (registered trademark) (manufactured by Sekisui Chemical Co., Ltd.), Zeonore Film (registered trademark) (Optes Corporation) Company) and Arton Film (registered trademark) (manufactured by JSR Corporation).
- the substrate may be surface treated.
- the surface treatment method include a method of treating the surface of the substrate with corona or plasma in an atmosphere of vacuum to atmospheric pressure, a method of laser treating the substrate surface, a method of treating the substrate surface with ozone, A method of saponifying a material surface, a method of flame-treating a substrate surface, a method of applying a coupling agent to the substrate surface, a method of primer-treating the substrate surface, and a reactive monomer or a reactive polymer
- a graft polymerization method may be used in which the substrate is adhered to the surface of the substrate and then reacted by irradiation with radiation, plasma, or ultraviolet rays.
- a method of corona or plasma treatment of the substrate surface in an atmosphere of vacuum to atmospheric pressure is preferable.
- a method of performing surface treatment of a substrate with corona or plasma a method of performing surface treatment of the substrate by installing a substrate between opposed electrodes and generating corona or plasma under a pressure near atmospheric pressure.
- the surface treatment of a substrate by flowing a gas between opposed electrodes, converting the gas into a plasma between the electrodes, and blowing the plasmaized gas onto the substrate, and generating glow discharge plasma under low pressure conditions.
- a method of performing a surface treatment of a substrate by setting a substrate between opposed electrodes under a pressure near atmospheric pressure and generating corona or plasma, or flowing a gas between the opposed electrodes, A method is preferred in which the gas is converted into plasma and the plasmaized gas is sprayed onto the substrate.
- Such surface treatment with corona or plasma is usually performed by a commercially available surface treatment apparatus.
- the base material may have a protective film on the surface opposite to the surface on which the composition of the present invention is applied.
- the protective film include films such as polyethylene, polyethylene terephthalate, polycarbonate, and polyolefin, and films having an adhesive layer on the film. Of these, polyethylene terephthalate is preferred because of its small thermal deformation during drying.
- the thickness of the base material is preferably thinner in terms of weight that allows practical handling, but if it is too thin, the strength tends to decrease and workability tends to be poor.
- the thickness of the substrate is usually 5 to 300 ⁇ m, preferably 20 to 200 ⁇ m.
- the length of the substrate in the longitudinal direction is usually 10 to 3000 m, preferably 100 to 2000 m.
- the length in the short direction of the substrate is usually 0.1 to 5 m, preferably 0.2 to 2 m.
- the alignment film in the present invention has an alignment regulating force that aligns the polymerizable liquid crystal compound in a desired direction.
- the alignment film those having solvent resistance that does not dissolve by application of the composition of the present invention and heat resistance in heat treatment for removing the solvent or aligning the polymerizable liquid crystal compound are preferable.
- Examples of such an alignment film include an alignment film containing an alignment polymer, a photo-alignment film, and a groove alignment film that forms an uneven pattern or a plurality of grooves on the surface and aligns the film.
- orientation polymer examples include polyamides and gelatins having an amide bond in the molecule, polyimides having an imide bond in the molecule and hydrolyzates thereof, polyamic acid, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, polyoxazole, Examples include polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid and polyacrylic acid esters. Among these, polyvinyl alcohol is preferable. Two or more orientation polymers may be used in combination.
- the alignment film containing the alignment polymer is usually applied to a substrate with a composition in which the alignment polymer is dissolved in a solvent (hereinafter sometimes referred to as an alignment polymer composition), and the solvent is removed or alignment. It is formed on the surface of the substrate by applying the functional polymer composition to the substrate, removing the solvent, and rubbing (rubbing method).
- the solvent examples include water, methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether and other alcohol solvents, ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, ⁇ -butyrolactone, Propylene glycol methyl ether acetate, ester solvents such as ethyl lactate, ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone, methyl isobutyl ketone, aliphatic hydrocarbon solvents such as pentane, hexane, heptane, toluene, Aromatic hydrocarbon solvents such as xylene, nitrile solvents such as acetonitrile, solvents such as tetrahydrofur
- the concentration of the orienting polymer in the orienting polymer composition may be within a range in which the orienting polymer material can be completely dissolved in the solvent, but is preferably 0.1 to 20% by mass in terms of solid content with respect to the solution, About 0.1 to 10% by mass is more preferable.
- a commercially available alignment film material may be used as it is as the alignment polymer composition.
- Examples of commercially available alignment film materials include Sunever (registered trademark, manufactured by Nissan Chemical Industries, Ltd.), Optomer (registered trademark, manufactured by JSR Corporation), and the like.
- Examples of methods for applying the alignment polymer composition to the substrate include spin coating, extrusion, gravure coating, die coating, slit coating, bar coating, applicator and other application methods, flexo methods And publicly known methods such as printing methods.
- a printing method such as a gravure coating method, a die coating method, or a flexo method is usually employed.
- Examples of the method for removing the solvent contained in the oriented polymer composition include a natural drying method, a ventilation drying method, a heat drying method and a vacuum drying method.
- rubbing is performed as necessary (rubbing method).
- the direction of the orientation regulating force can be arbitrarily controlled.
- a rubbing cloth was wound, and the orientation polymer composition was applied to the rotating rubbing roll and annealed and formed on the substrate surface.
- membrane of an orientation polymer contact is mentioned.
- the photo-alignment film is usually obtained by applying a composition containing a polymer or monomer having a photoreactive group and a solvent (hereinafter sometimes referred to as “photo-alignment film-forming composition”) to a substrate, and applying light ( Preferably, it is formed on the surface of the substrate by irradiating polarized UV).
- the photo-alignment film is more preferable in that the direction of the alignment regulating force can be arbitrarily controlled by selecting the polarization direction of the irradiated light.
- the photoreactive group refers to a group that produces liquid crystal alignment ability when irradiated with light.
- groups involved in photoreactions that are the origin of liquid crystal alignment ability such as molecular orientation induction or isomerization reaction, dimerization reaction, photocrosslinking reaction or photodecomposition reaction caused by light irradiation.
- a group involved in the dimerization reaction or the photocrosslinking reaction is preferable in terms of excellent orientation.
- an unsaturated bond particularly a group having a double bond is preferable, and a carbon-carbon double bond (C ⁇ C bond), a carbon-nitrogen double bond (C ⁇ N bond), or a nitrogen-nitrogen two-bond.
- a group having at least one selected from the group consisting of a heavy bond (N ⁇ N bond) and a carbon-oxygen double bond (C ⁇ O bond) is particularly preferred.
- Examples of the photoreactive group having a C ⁇ C bond include a vinyl group, a polyene group, a stilbene group, a stilbazole group, a stilbazolium group, a chalcone group, and a cinnamoyl group.
- Examples of the photoreactive group having a C ⁇ N bond include groups having a structure such as an aromatic Schiff base and an aromatic hydrazone.
- Examples of the photoreactive group having an N ⁇ N bond include an azobenzene group, an azonaphthalene group, an aromatic heterocyclic azo group, a bisazo group, a formazan group, and a group having an azoxybenzene structure.
- Examples of the photoreactive group having a C ⁇ O bond include a benzophenone group, a coumarin group, an anthraquinone group, and a maleimide group. These groups may have a substituent such as an alkyl group, an alkoxy group, an aryl group, an allyloxy group, a cyano group, an alkoxycarbonyl group, a hydroxyl group, a sulfonic acid group, and a halogenated alkyl group.
- a photoreactive group involved in the photodimerization reaction is preferable, the amount of polarized light irradiation necessary for photoalignment is relatively small, and a photoalignment film excellent in thermal stability and temporal stability can be easily obtained.
- a cinnamoyl group and a chalcone group are preferred.
- the polymer having a photoreactive group a polymer having a cinnamoyl group in which the terminal portion of the polymer side chain has a cinnamic acid structure is particularly preferable.
- Examples of the solvent contained in the composition for forming a photoalignment film include the same solvents as those contained in the above-mentioned oriented polymer composition, and are appropriately selected according to the solubility of the polymer or monomer having a photoreactive group. can do.
- the content of the polymer or monomer having a photoreactive group in the composition for forming a photo-alignment film can be appropriately adjusted depending on the type of the polymer or monomer and the thickness of the target photo-alignment film, and is at least 0.2% by mass. The range is preferably 0.3 to 10% by mass. As long as the characteristics of the photo-alignment film are not significantly impaired, the composition for forming a photo-alignment film may contain a polymer material such as polyvinyl alcohol or polyimide, or a photosensitizer.
- Examples of the method for applying the composition for forming a photo-alignment film to a substrate include the same methods as those for applying the alignment polymer composition to a substrate.
- Examples of the method for removing the solvent from the applied composition for forming a photo-alignment film include the same method as the method for removing the solvent from the oriented polymer composition.
- polarized light In order to irradiate polarized light, it is possible to irradiate polarized light from the substrate side and transmit the polarized light even in the form of irradiating polarized UV directly to the composition from which the solvent is removed from the composition for forming a photo-alignment film applied on the substrate. It is also possible to irradiate.
- the polarized light is particularly preferably substantially parallel light.
- the wavelength of the polarized light to be irradiated is preferably in a wavelength region where the photoreactive group of the polymer or monomer having a photoreactive group can absorb light energy. Specifically, UV (ultraviolet light) having a wavelength in the range of 250 to 400 nm is particularly preferable.
- Examples of the light source used for the polarized light irradiation include xenon lamps, high pressure mercury lamps, ultra high pressure mercury lamps, metal halide lamps, ultraviolet lasers such as KrF and ArF, and the like. High pressure mercury lamps, ultra high pressure mercury lamps and metal halides. A lamp is more preferred. These lamps are preferable because of high emission intensity of ultraviolet rays having a wavelength of 313 nm.
- a polarizing prism such as a polarizing filter, Glan Thompson, or Grand Taylor, or a wire grid type polarizer can be used.
- a plurality of regions (patterns) having different directions of liquid crystal alignment can be formed by performing masking when performing rubbing or polarized light irradiation.
- the Glub alignment film is a film in which liquid crystal alignment is obtained by a concavo-convex pattern or a plurality of grooves on the film surface.
- H. V. Kennel et al. Reported the fact that when liquid crystal molecules are placed on a substrate having a plurality of linear grooves (grooves) arranged at equal intervals, the liquid crystal molecules are aligned in the direction along the grooves ( Physical Review A24 (5), page 2713, 1981).
- a method of removing the polyimide film to form a concavo-convex pattern, a method of forming a UV curable resin layer on a plate-shaped master having grooves on the surface, a method of curing after transferring the resin layer to a base film, and forming a UV curable resin layer examples include a method in which the base film is conveyed and a roll-shaped master having a plurality of grooves is pressed against the surface of the UV curable resin layer to form an unevenness and then cured, as disclosed in JP-A-6-34976 and JP-2011. The method described in JP-A-2424243 can be used.
- a method in which a roll-shaped master having a plurality of grooves is pressed against the surface of the UV curable resin layer to form unevenness and then cured is preferable.
- the roll-shaped master stainless steel (SUS) steel can be used from the viewpoint of durability.
- a polymer of a monofunctional acrylate, a polymer of a polyfunctional acrylate, or a polymer of a mixture thereof can be used.
- the monofunctional acrylate is a group selected from the group consisting of an acryloyloxy group (CH2 ⁇ CH—COO—) and a methacryloyloxy group (CH2 ⁇ C (CH3) —COO—) (hereinafter referred to as a (meth) acryloyloxy group).
- a compound having 1 in the molecule is a group selected from the group consisting of an acryloyloxy group (CH2 ⁇ CH—COO—) and a methacryloyloxy group (CH2 ⁇ C (CH3) —COO—) (hereinafter referred to as a (meth) acryloyloxy group).
- Monofunctional acrylates having one (meth) acryloyloxy group include alkyl (meth) acrylates having 4 to 16 carbon atoms, ⁇ -carboxyalkyl (meth) acrylates having 2 to 14 carbon atoms, and alkylation having 2 to 14 carbon atoms. Examples include phenyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, and isobornyl (meth) acrylate.
- the polyfunctional acrylate is usually a compound having 2 to 6 (meth) acryloyloxy groups in the molecule.
- Examples of the bifunctional acrylate having two (meth) acryloyloxy groups include 1,3-butanediol di (meth) acrylate; 1,6-hexanediol di (meth) acrylate; ethylene glycol di (meth) acrylate; diethylene glycol di (Meth) acrylate; neopentyl glycol di (meth) acrylate; triethylene glycol di (meth) acrylate; tetraethylene glycol di (meth) acrylate; polyethylene glycol diacrylate; bis (acryloyloxyethyl) ether of bisphenol A; ethoxy Bisphenol A di (meth) acrylate; propoxylated neopentyl glycol di (meth) acrylate; ethoxylated neopentyl glycol di (meth) acrylate and 3-methylpen Such Njioruji (meth) acrylate.
- (meth) acrylate means an acrylate or a methacrylate.
- the caprolactone modification means that a ring-opened product of caprolactone or a ring-opened polymer is introduced between the alcohol-derived site of the (meth) acrylate compound and the (meth) acryloyloxy group.
- a commercial item can also be used for this polyfunctional acrylate.
- Such commercial products include A-DOD-N, A-HD-N, A-NOD-N, APG-100, APG-200, APG-400, A-GLY-9E, A-GLY-20E, A- TMM-3, A-TMPT, AD-TMP, ATM-35E, A-TMMT, A-9550, A-DPH, HD-N, NOD-N, NPG, TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.), “ARONIX "M-220", “M-325", “M-240", “M-270", “M-309", “M-310", “M-321”, “M-350”"M-360”,”M-305","M-306",”M-450”,”M-451”,”M-408”,"M-400”"M-402",”M-403”,”M-404",”M-4" 5 ”,“ M-406 ”(manufactured by To
- the width of the convex portion is preferably 0.05 to 5 ⁇ m
- the width of the concave portion is preferably 0.1 to 5 ⁇ m
- the depth of the uneven step is preferably 2 ⁇ m or less. Is preferably 0.01 to 1 ⁇ m or less. Within this range, it is possible to obtain liquid crystal alignment with little alignment disturbance.
- the thickness of the alignment film is usually 10 nm to 10000 nm, preferably 10 nm to 1000 nm, more preferably 10 nm to 500 nm.
- Examples of the method for applying the composition of the present invention include the same methods as those exemplified as the method for applying the alignment polymer composition to the substrate.
- composition of the present invention contains a solvent
- the solvent is usually removed from the formed coating film.
- the method for removing the solvent include a natural drying method, a ventilation drying method, a heat drying method and a vacuum drying method.
- the polymerizable liquid crystal compound contained in the formed coating film is usually heated to a temperature higher than the temperature at which it transitions to a solution state and then cooled to a temperature at which the liquid crystal is aligned to form a liquid crystal phase.
- the temperature at which the polymerizable liquid crystal compound contained in the formed coating film is aligned may be obtained in advance by texture observation using a composition containing the polymerizable liquid crystal compound. Further, the removal of the solvent and the liquid crystal alignment may be performed simultaneously. The temperature at this time depends on the solvent to be removed and the type of the polymerizable liquid crystal compound, but is preferably in the range of 50 to 200 ° C., and more preferably in the range of 80 to 130 ° C. when the substrate is a resin substrate. preferable.
- the orientation direction of the polymerizable liquid crystal compound is determined by the polarizing film obtained.
- the slow axis (optical axis) of the substrate may be substantially 45 °.
- the polymerizable liquid crystal compound is polymerized by irradiating the aligned polymerizable liquid crystal compound with active energy rays.
- a polarizing film including the polymerizable liquid crystal compound polymerized in the aligned state and the compound (1) aligned with the polymerizable liquid crystal compound is obtained.
- a polarizing film containing a polymerizable liquid crystal compound polymerized while retaining a smectic liquid crystal phase is a conventional host-guest type polarizing film, that is, a polarizing film obtained by polymerizing a polymerizable liquid crystal compound or the like while retaining a nematic liquid crystal phase.
- the polarizing performance is higher than that of the dichroic dye, and the polarizing performance and strength are excellent as compared with the case where only the dichroic dye or the lyotropic liquid crystal type liquid crystal compound is applied.
- the light source for the active energy ray may be any light source that generates ultraviolet rays, electron beams, X-rays, or the like.
- the light source has a light emission distribution at a wavelength of 400 nm or less, such as a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, a black light lamp, a microwave excitation mercury lamp, or a metal halide lamp.
- Irradiation energy of the active energy ray is preferably the irradiation intensity of the wavelength region effective for activation of the polymerization initiator is set to be 10 ⁇ 5000mJ / cm 2, more preferably at 100 ⁇ 2000mJ / cm 2 .
- the irradiation energy is lower than 10 mJ / cm 2 , the polymerizable liquid crystal compound tends to be insufficiently cured.
- the thickness of the polarizing film of the present invention thus formed is preferably in the range of 0.5 ⁇ m to 10 ⁇ m, more preferably 1 ⁇ m to 5 ⁇ m.
- the thickness of the polarizing film of the present invention can be determined by measurement with an interference film thickness meter, a laser microscope or a stylus thickness meter.
- the polarizing film of the present invention is particularly preferably a Bragg peak obtained in X-ray diffraction measurement.
- Examples of the polarizing film of the present invention from which such a Bragg peak is obtained include those showing a diffraction peak derived from a hexatic phase or a crystal phase.
- the maximum absorption ( ⁇ max1 ) of the polarizing film of the present invention is preferably in the range of 350 to 550 nm, more preferably in the range of 410 to 540 nm, and still more preferably in the range of 430 to 530 nm.
- ⁇ max1 is shifted by a long wavelength as compared with the maximum absorption ( ⁇ max2 ) measured by dissolving the compound (1) contained in the polarizing film of the present invention in an applicable solvent.
- a long wavelength shift is manifested when the compound (1) is dispersed between molecular chains formed by the polymerized polymerizable liquid crystal compound, and the compound (1) strongly interacts with the molecular chain. It shows that.
- Long wavelength shift means that the difference in absorption maximum ( ⁇ max1 ⁇ max2 ) is a positive value, and the difference is preferably 15 nm or more, and more preferably 30 nm or more.
- the dichroic ratio exhibited by the polarizing film of the present invention is preferably 15 or more, more preferably 25 or more.
- a circularly polarizing plate can be obtained by laminating the obtained polarizing film of the present invention and a quarter wavelength plate.
- the lamination is preferably performed so that the transmission axis of the polarizing film of the present invention and the slow axis (optical axis) of the quarter-wave plate are substantially 45 °.
- the polarizing plate which functions as an optical compensation film can also be obtained by making the transmission axis of the polarizing film of this invention and the optical axis of retardation films, such as a quarter wavelength plate, correspond or make orthogonal.
- Lamination of the polarizing film of the present invention and the quarter wavelength plate may be performed together with the base material on which the polarizing film of the present invention is formed, or the base material on which the alignment film is formed. Alternatively, the alignment film may be removed.
- the lamination of the polarizing film of the present invention formed on the surface of the base material or the base material on which the alignment film is formed and the quarter wavelength plate is, for example, the surface on which the polarizing film of the present invention is formed, After bonding the four-wave plate with an adhesive, the substrate or the substrate on which the alignment film is formed can be removed. Under the present circumstances, an adhesive agent may be apply
- the continuous manufacturing method of the polarizing film of this invention is preferably manufactured continuously by the Roll to Roll format.
- FIG. 1 an example of the main part of the method for continuously producing the polarizing film of the present invention in the Roll to Roll format will be described.
- the first roll 210 in which the base material is wound around the first core 210A can be easily obtained from the market, for example.
- a base material which can be obtained from the market in the form of such a roll the film etc. which consist of a cellulose ester, cyclic olefin resin, a polycarbonate, a polyethylene terephthalate, or a polymethacrylic acid ester are mentioned among the base materials already illustrated.
- the base material is unwound from the first roll 210.
- the method for unwinding the substrate is performed by installing an appropriate rotating means on the core 210A of the first roll 210 and rotating the first roll 210 by the rotating means.
- an appropriate auxiliary roll 300 may be installed in the direction of transporting the base material from the first roll 210 and the base material may be unwound by the rotating means of the auxiliary roll 300.
- the first winding core 210A and the auxiliary roll 300 may be provided with a rotating means so that the substrate is unwound while applying an appropriate tension to the substrate.
- the composition for forming a photo-alignment film is applied onto the surface of the base material by the coating device 211A.
- a gravure coating method, a die coating method, and a flexo method are preferable.
- the base material that has passed through the coating apparatus 211A is conveyed to the drying furnace 212A and dried by the drying furnace 212A, so that a first coating film is continuously formed on the surface of the base material.
- the drying furnace 212A for example, a hot-air drying furnace that combines a ventilation drying method and a heating drying method is used.
- the preset temperature of the drying furnace 212A is determined according to the type of solvent contained in the composition for forming a photo-alignment film.
- the drying furnace 212A may be composed of a plurality of zones having different set temperatures, or may be a series of a plurality of drying furnaces having different set temperatures.
- a photo-alignment film is obtained by irradiating the obtained first coating film with polarized light by the polarized UV irradiation device 213A.
- the base material on which the photo-alignment film is formed passes through the coating device 211B.
- the composition of the present invention containing the solvent is applied onto the photo-alignment film by the coating device 211B
- the second liquid crystal compound contained in the composition of the present invention is aligned by passing through a drying furnace 212B.
- a coating film is obtained.
- the drying oven 212B has a role of removing the solvent from the composition of the present invention containing the solvent applied on the photo-alignment film, and a role of giving thermal energy so that the polymerizable liquid crystal compound contained in the composition is aligned. Take on.
- the drying furnace 212B may be composed of a plurality of zones having different set temperatures, or may be a series of a plurality of drying furnaces having different set temperatures. .
- the active energy ray irradiation device 213B In the state in which the polymerizable liquid crystal compound contained in the second coating film is aligned, it is conveyed to the active energy ray irradiation device 213B. In the active energy ray irradiation device 213B, the active energy ray is further irradiated. By irradiating the active energy ray by the active energy ray irradiating device 213B, the polymerizable liquid crystal compound is polymerized in an aligned state to obtain a polarizing film.
- the present polarizing plate manufactured continuously is wound around the second core 220 ⁇ / b> A to obtain the form of the second roll 220.
- the base material passes from the first roll 210 in the order of the coating apparatus 211A, the drying furnace 212A, the polarized UV irradiation apparatus 213A, the coating apparatus 211B, the drying furnace 212B, and the active energy ray irradiation apparatus 213B.
- the polarizing plate can be continuously produced in the Roll-to-Roll format.
- the base material is applied from the first roll to the coating device 211A, the drying furnace 212A, and the polarized UV irradiation device. 213A is passed in this order, and a roll-shaped base material and a photo-alignment film laminate are manufactured by winding this around a core, and further, the roll-like laminate is unwound, and a coating apparatus 211B, a drying furnace
- the polarizing film of this invention can also be continuously manufactured by letting 212B and the active energy ray irradiation apparatus 213B pass in order.
- the long polarizing film of the present invention is unwound from the second roll 220, cut into a predetermined dimension, and then the cut polarized light.
- a circularly polarizing plate can be produced by laminating a quarter wave plate to the film.
- a long circularly-polarizing plate can also be continuously manufactured by preparing the 3rd roll by which the long quarter wave plate is wound by the core.
- a method for continuously producing a long circularly polarizing plate will be described with reference to FIG.
- Such a manufacturing method is: The polarizing film of the present invention is continuously unwound from the second roll 220, and the long quarter-wave plate is continuously wound from the third roll 230 on which the long quarter-wave plate is wound. And a process of A step of continuously bonding the polarizing film of the present invention and the long quarter-wave plate to obtain a long circularly polarizing plate; The obtained long circularly polarizing plate is wound around a fourth core 240A to obtain a fourth roll 240.
- This method is so-called Roll to Roll bonding.
- a display device is a device having a display element, and includes a light-emitting element or a light-emitting device as a light-emitting source.
- Examples of the display device including the polarizing plate include a liquid crystal display device, an organic electroluminescence (EL) display device, an inorganic electroluminescence (EL) display device, an electron emission display device (for example, a field emission display device (FED), a surface electric field).
- EL organic electroluminescence
- EL inorganic electroluminescence
- FED field emission display device
- Emission display device SED
- electronic paper display device using electronic ink or electrophoretic element
- plasma display device projection display device (for example, grating light valve (GLV) display device, digital micromirror device (DMD))
- Liquid crystal display devices such as transmissive liquid crystal display devices, transflective liquid crystal display devices, reflective liquid crystal display devices, direct view liquid crystal display devices, and projection liquid crystal display devices.
- These display devices include a display for displaying a two-dimensional image. May be a location, it may be a stereoscopic display apparatus for displaying a three-dimensional image.
- the polarizing film of the present invention can be effectively used particularly for a liquid crystal display device, an organic electroluminescence (EL) display device and an inorganic electroluminescence (EL) display device.
- the circularly polarizing plate having the polarizing film and the quarter-wave plate of the present invention can be effectively used particularly for an organic electroluminescence (EL) display device and an inorganic electroluminescence (EL) display device.
- the polarizing film of the present invention When the polarizing film of the present invention is used in a liquid crystal display device, the polarizing film of the present invention may be provided outside the liquid crystal cell or inside the liquid crystal cell.
- the display device 30 includes a first substrate 31, a polarizing film 32 of the first invention, a color filter layer 33, a planarizing layer 34, an ITO electrode layer 35, a first alignment film 36, a liquid crystal layer 37, a second The alignment film 38, the polarizing film 39 of the second invention, the TFT layer 40 including the thin film transistor circuit and the pixel electrode, and the second substrate 41.
- the color filter layer refers to a layer that extracts light having a desired wavelength from incident light from the substrate 41 side. For example, light having a wavelength other than the desired wavelength is absorbed from white light and only light having the desired wavelength is transmitted. It may be a layer, or a layer that converts the wavelength of incident light to emit light having a desired wavelength.
- an alignment film may be included on the first and second substrate sides, respectively.
- the alignment film may be a rubbing alignment film or a photo-alignment film.
- the polarizing film of the first aspect of the present invention may include a retardation layer.
- the display device 60 includes a first base 61, a polarizing film 62 of the first invention, a color filter layer 63, a planarizing layer 64, an ITO electrode layer 65, a first alignment film 66, a liquid crystal layer 67, a second.
- the second polarizing film 72 positioned on the opposite side of the TFT layer 70 of the second substrate 71 may be the polarizing film of the present invention, or polarized light produced by dyeing polyvinyl alcohol with iodine and stretching it. It may be a membrane.
- the display device 80 includes a first substrate 81, a color filter layer 82, a polarizing film 83 of the first invention, a planarization layer 84, an ITO electrode layer 85, a first alignment film 86, a liquid crystal layer 87, and a second.
- the alignment film 88, the TFT layer 90 including the thin film transistor circuit and the pixel electrode, the second base 91, and the second polarizing film 92 are included.
- the second polarizing film 92 may be the polarizing film of the present invention, or may be a polarizing film prepared by dyeing polyvinyl alcohol with iodine and stretching it.
- the second polarizing film 92 is a polarizing film according to the present invention, the second polarizing film may be located between the second base 91 and the TFT layer 90, as in the first configuration.
- the color filter layer 82 may be located on the side opposite to the liquid crystal layer of the first base 81.
- the polarized light is scattered by the particles included in the color filter layer, and the depolarization can occur. Therefore, among the first to third configurations, the third configuration in which the first polarizing film according to the present invention is located closer to the liquid crystal layer than the color filter layer is more preferable.
- Example 1 0.15 g of the compound represented by the formula (2A), 0.10 g of the compound represented by the formula (3A), 0.50 g of potassium phosphate, 0.0087 g of tris (dibenzylideneacetone) dipalladium (0), tri- 0.011 g of tert-butylphosphonium tetrafluoroborate and 3 g of 1,4-dioxane were mixed. The resulting mixture was stirred at 100 ° C. for 18 hours under a nitrogen atmosphere. The resulting reaction mixture was concentrated and purified by silica gel column chromatography (eluent: chloroform).
- Example 3 0.40 g of the compound represented by the formula (2C), 0.25 g of the compound represented by the formula (3A), 0.45 g of potassium acetate, [1,1′-bis (diphenylphosphino) ferrocene] dichloropalladium (II ) 0.150 g and 24.0 g of diethylene glycol dimethyl ether were mixed. The resulting mixture was stirred at 140 ° C. for 3 hours under a nitrogen atmosphere. The resulting reaction mixture was concentrated and purified by silica gel column chromatography (eluent: chloroform).
- a compound represented by the following formula (4-6) [hereinafter referred to as compound (4-6)], a compound represented by the following formula (4-8) [hereinafter referred to as compound (4-8)], the following formula A compound represented by (4-14) [hereinafter referred to as compound (4-14)] and a compound represented by the following formula (4-17) [hereinafter referred to as compound (4-17)] were used.
- Compound (4-6) was prepared from Lub et al. Recl. Trav. Chim. It was synthesized by the method described in Pays-Bas, 115, 321-328 (1996).
- Compound (4-8) was produced according to this method.
- Compound (4-14) and Compound (4-17) were produced according to the method described in Japanese Patent No. 4719156.
- phase transition temperature of the compound (4-6) was confirmed by determining the phase transition temperature of the film made of the compound (4-6).
- the operation is as follows. A film composed of the compound (4-6) was formed on the glass substrate on which the alignment film was formed, and the phase transition temperature was confirmed by texture observation with a polarizing microscope (BX-51, Olympus) while heating. Compound (4-6) was heated to 120 ° C., and when the temperature was lowered, the phase transitioned to the nematic phase at 112 ° C., the phase transition to the smectic A phase at 110 ° C., and the phase transition to the smectic B phase at 94 ° C. .
- phase transition temperature The phase transition temperature of compound (4-8) was confirmed in the same manner as in the measurement of the phase transition temperature of compound (4-6).
- Compound (4-8) was heated to 140 ° C., and at the time of temperature decrease, the phase transitioned to the nematic phase at 131 ° C., the phase transition to the smectic A phase at 80 ° C., and the phase transition to the smectic B phase at 68 ° C.
- phase transition temperature The phase transition temperature of compound (4-14) was confirmed in the same manner as in the measurement of the phase transition temperature of compound (4-6).
- Compound (4-14) was heated to 140 ° C., and at the time of temperature decrease, the phase transitioned to the nematic phase at 106 ° C., the phase transition to the smectic A phase at 103 ° C., and the phase transition to the smectic B phase at 86 ° C.
- phase transition temperature The phase transition temperature of compound (4-17) was confirmed in the same manner as in the measurement of the phase transition temperature of compound (4-6).
- Compound (4-17) was heated to 140 ° C., and at the time of cooling, the phase transitioned to the nematic phase at 119 ° C., the phase transition to the smectic A phase at 100 ° C., and the phase transition to the smectic B phase at 77 ° C.
- Example 4 (Preparation of composition) The following components were mixed and stirred at 80 ° C. for 1 hour to obtain a composition (1).
- phase transition temperature Similarly to the compound (4-6), the phase transition temperature of the component contained in the composition (1) was determined. This component was heated to 140 ° C., and at the time of cooling, the phase transitioned to the nematic phase at 115 ° C., the phase transition to the smectic A phase at 105 ° C., and the phase transition to the smectic B phase at 75 ° C.
- the rubbing process uses a semi-automatic rubbing apparatus (trade name: LQ-008 type, manufactured by Joyo Engineering Co., Ltd.) and a push-in amount of 0.15 mm using a cloth (trade name: YA-20-RW, manufactured by Yoshikawa Chemical Co., Ltd.). , Under the conditions of 500 rpm and 16.7 mm / s. By such rubbing treatment, a laminate 1 having an alignment film formed on a glass substrate was obtained.
- the composition (1) is applied onto the alignment film of the laminate 1 by spin coating, dried by heating on a hot plate at 120 ° C. for 1 minute, and then quickly cooled to room temperature to perform the alignment. A dry film containing an aligned polymerizable liquid crystal compound was formed on the film. Next, by using a UV irradiation apparatus (SPOT CURE SP-7; manufactured by Ushio Electric Co., Ltd.), the ultraviolet ray is irradiated to the dry film with an exposure amount of 2000 mJ / cm 2 (365 nm standard), thereby polymerization contained in the dry film. The liquid crystalline compound was polymerized while maintaining the alignment state, and the polarizing film (1) was formed from the dried film to obtain a laminate 2. When the thickness of the polarizing film at this time was measured with a laser microscope (OLS3000 manufactured by Olympus Corporation), it was 1.7 ⁇ m.
- OLS3000 manufactured by Olympus Corporation
- a sharp diffraction peak (Bragg peak) having a peak half width (FWHM) of about 0.31 ° was obtained.
- the order period (d) obtained from the peak position is about 4.4 mm, and it was found that a structure reflecting a higher-order smectic phase was formed.
- the absorbance (A 1 ) in the transmission axis direction and the absorbance (A 2 ) in the absorption axis direction at the maximum absorption wavelength are provided in a spectrophotometer (UV-3150, manufactured by Shimadzu Corporation), and the laminate 2 is provided.
- the folder was measured by the double beam method using the set device.
- the folder was provided with a mesh that cuts the light amount by 50% on the reference side.
- the ratio (A 2 / A 1 ) was calculated from the measured values of absorbance (A 1 ) in the transmission axis direction and absorbance (A 2 ) in the absorption axis direction to obtain a dichroic ratio.
- the maximum absorption wavelength ( ⁇ max1 ) was 376 nm, and the dichroic ratio at this wavelength was as high as 38. It can be said that the higher the dichroic ratio, the more useful as a polarizing film. Since the maximum absorption wavelength ( ⁇ max2 ) of the compound (1A) was 360 nm, it was found that the compound was shifted by a long wavelength. As a result of this long wavelength shift, when the compound (1A) is dispersed between dense molecular chains formed by polymerization of the polymerizable liquid crystal compound in the polarizing film of the present invention, the compound (1A) It shows that it interacts strongly with the molecular chain.
- a protective film 40 ⁇ m TAC (“KC4UY” manufactured by Konica Minolta Co., Ltd.) is disposed on the surface of the formed polarizing film (1), and light resistance is evaluated by irradiating light under the following conditions.
- the formed polarizing film is excellent in light resistance.
- the light irradiation conditions in the light resistance test are as follows. Equipment used: Suntest XLS + manufactured by ATLAS Light source used: Xenon arc lamp Exposure condition: 250 mW / m 2 Test time: 120 hours Exposure: 108000 KJ / m 2 Temperature: 60 ° C
- Example 5 it carries out similarly to Example 4 except using a compound (1B) instead of a compound (1A), and the composition and polarizing film containing a compound (1B) are obtained.
- Example 6 In Example 4, a composition containing the compound (1C) and a polarizing film are obtained by carrying out in the same manner as in Example 4 except that the compound (1C) is used in place of the compound (1A).
- Example 7 The compound represented by the formula (1D) is carried out in the same manner as in Example 1 except that the compound represented by the formula (2D) is used in place of the compound represented by the formula (2A). Is obtained.
- Example 8 In Example 4, a composition containing the compound (1D) and a polarizing film are obtained by carrying out in the same manner as in Example 4 except that the compound (1D) is used in place of the compound (1A).
- Example 9 0.30 g of the compound represented by formula (2E), 0.25 g of the compound represented by formula (3A), 0.45 g of potassium acetate, [1,1′-bis (diphenylphosphino) ferrocene] dichloropalladium (II ) 0.15 g and diethylene glycol dimethyl ether 18 g were mixed. The resulting mixture was stirred at 140 ° C. for 3 hours under a nitrogen atmosphere. The resulting reaction mixture was concentrated and purified by silica gel column chromatography (eluent: tetrahydrofuran).
- Example 10 A polarizing film was produced in the same manner as in Example 4 except that the compound (1E) was used instead of the compound (1A). Similarly, when the maximum absorption wavelength and the dichroic ratio were measured, the maximum absorption wavelength ( ⁇ max1 ) was 392 nm, and the dichroic ratio was as high as 30. Moreover, since the maximum absorption wavelength ( ⁇ max2 ) was 363 nm as described in Example 9, it was found that there was a long wavelength shift. As a result, when the compound (1E) is dispersed between dense molecular chains formed by polymerization of the polymerizable liquid crystal compound in the polarizing film, the compound (1E) strongly interacts with the molecular chain. It shows that it is.
- Example 11 The compound represented by the formula (1F) is carried out in the same manner as in Example 1 except that the compound represented by the formula (2F) is used instead of the compound represented by the formula (2A). Is obtained.
- Example 12 In Example 4, a composition containing the compound (1F) and a polarizing film are obtained by carrying out in the same manner as in Example 4 except that the compound (1F) is used in place of the compound (1A).
- Example 13 0.30 g of the compound represented by the formula (2G), 0.22 g of the compound represented by the formula (3A), 0.39 g of potassium acetate, [1,1′-bis (diphenylphosphino) ferrocene] dichloropalladium (II ) 0.13 g and diethylene glycol dimethyl ether 18 g were mixed. The resulting mixture was stirred at 140 ° C. for 3 hours under a nitrogen atmosphere. The resulting reaction mixture was concentrated and purified by silica gel column chromatography (eluent: tetrahydrofuran).
- Example 14 A polarizing film was produced in the same manner as in Example 4 except that the compound (1G) was used instead of the compound (1A). Similarly, when the maximum absorption wavelength and the dichroic ratio were measured, the maximum absorption wavelength ( ⁇ max1 ) was 380 nm, and the dichroic ratio was as high as 60. Moreover, since the maximum absorption wavelength ( ⁇ max2 ) was 360 nm as described in Example 13, it was found that there was a long wavelength shift. As a result, when the compound (1G) is dispersed between dense molecular chains formed by polymerization of the polymerizable liquid crystal compound in the polarizing film, the compound (1G) strongly interacts with the molecular chain. It shows that it is.
- Example 15 0.30 g of the compound represented by the formula (2G), 0.30 g of the compound represented by the formula (3B), 0.85 g of potassium phosphate, 0.0147 g of tris (dibenzylideneacetone) dipalladium (0), tri- 0.0187 g of tert-butylphosphonium tetrafluoroborate and 6 g of 1,4-dioxane were mixed. The resulting mixture was stirred at 100 ° C. for 5 hours under a nitrogen atmosphere. The resulting reaction mixture was concentrated and purified by silica gel column chromatography (eluent: tetrahydrofuran).
- the novel compound of the present invention is a compound having a maximum absorption in the wavelength range of 350 nm to 550 nm and functioning as a dichroic dye, and the composition of the present invention containing the compound is a polarizing film having a high dichroic ratio. give.
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Abstract
Description
特許文献2には、波長350nm~550nmの範囲に極大吸収を有する二色性色素として1,4-ナフチル構造を有するビスアゾ系色素が記載されている。しかしながら、当該二色性色素を含む偏光膜の二色比は低かった。
[1]式(1):
[式中、R1は、炭素数1~20のアルキル基、炭素数1~20のアルコキシ基、炭素数1~20のアシル基、炭素数2~20のアルコキシカルボニル基、炭素数1~20のアシルオキシ基または-N(R10)(R11)を表し、R10は、炭素数1~20のアシル基、炭素数1~20のアルキルスルホニル基または炭素数6~20のアリールスルホニル基を表わし、R11は、水素原子または炭素数1~20のアルキル基を表し、R10とR11とが互いに結合して、それらが結合する窒素原子とともに、-N-CO-または-N-SO2-を含む環を形成してもよい。前記アルキル基、前記アルコキシ基、前記アシル基、前記アルコキシカルボニル基、前記アシルオキシ基、前記アルキルスルホニル基および前記アリールスルホニル基を構成する一つ以上の水素原子は、ハロゲン原子、ヒドロキシ基、アミノ基または置換基を有するアミノ基で置き換わっていてもよい。前記アルキル基および前記アルコキシ基を構成する炭素原子間には、-O-または-NR20-が挿入されていてもよく、R20は、水素原子または炭素数1~20のアルキル基を表わす。
R7およびR8は、水素原子以外の置換基であって、それぞれ独立して、炭素数1~4のアルキル基、炭素数1~4のアルコキシ基、ハロゲン原子、またはシアノ基を表し、上記炭素数1~4のアルキル基および上記炭素数1~4アルコキシ基を構成する少なくとも一つの水素原子は、ハロゲン原子またはヒドロキシ基で置換されていてもよく、p及びqは、それぞれ独立して0~2の整数である。
R2は炭素数1~20のアシル基、炭素数1~20のアルキルスルホニル基または炭素数6~20のアリールスルホニル基を表し、R3は水素原子または炭素数1~20のアルキル基を表し、R2とR3とが互いに結合して、それらが結合する窒素原子とともに、-N-CO-または-N-SO2-を含む環を形成してもよい。前記アシル基、前記アルキルスルホニル基および前記アリールスルホニル基を構成する一つ以上の水素原子は、ハロゲン原子、ヒドロキシ基、アミノ基または置換基を有するアミノ基で置き換わっていてもよい。前記アルキル基および前記アルコキシ基を構成する炭素原子間には、-O-または-NR21-が挿入されていてもよく、R21は、水素原子または炭素数1~20のアルキル基を表わす。
Yは、式(Y1):
(式中、*はNとの結合部位を表す。R9は、水素原子以外の置換基であって、それぞれ独立して、炭素数1~4のアルキル基、炭素数1~4のアルコキシ基、ハロゲン原子、またはシアノ基を表し、上記炭素数1~4のアルキル基および上記炭素数1~4アルコキシ基を構成する少なくとも一つの水素原子は、ハロゲン原子またはヒドロキシ基で置換されていてもよく、rは0~2の整数である。)
で示される基または式(Y2):
(式中、*はNとの結合部位を表し、P1およびP2は、それぞれ独立して、-S-、-O-または-N(R12)-を表し、R12は、水素原子または炭素数1~4のアルキル基を表し、Q1およびQ2は、それぞれ独立して、=N-または=CH-を表す。)
で示される基を表す。]
で表される化合物。
[2] p、qおよびrが0である[1]に記載の化合物。
[3]重合性液晶化合物と[1]または[2]に記載の化合物とを含む組成物。
[4]重合性液晶化合物が、スメクチック液晶相を示す[3]に記載の組成物。
[5]さらに重合開始剤を含む[3]または[4]に記載の組成物。
[6][1]または[2]に記載の化合物を含む偏光膜。
[7][3]~[5]のいずれかに記載の組成物から形成される偏光膜。
[8]偏光膜の極大吸収波長(λmax1)が、式(1)で表される化合物の極大吸収波長(λmax2)よりも長い[6]または[7]に記載の偏光膜。
[9]λmax1と、λmax2との差が15nm以上である[8]に記載の偏光膜。
[10]X線回折測定においてブラッグピークを示す[6]~[9]のいずれかに記載の偏光膜。
[11][6]~[10]のいずれかに記載の偏光膜を備える液晶表示装置。
[12][6]~[10]のいずれかに記載の偏光膜、液晶層および基体を備える液晶セル。
[13]偏光膜が、基体と液晶層との間に配置される[12]に記載の液晶セル。
[14]基体と液晶層との間に、カラーフィルタがさらに配置される[13]に記載の液晶セル。
[15][6]~[10]のいずれかに記載の偏光膜と1/4波長板とを有する円偏光板。
[16][6]~[10]のいずれかに記載の偏光膜と有機EL素子とを備える有機EL表示装置。
[17][15]に記載の円偏光板と有機EL素子とを備える有機EL表示装置。
[18]式(2):
[式中、Xは、塩素原子、臭素原子またはヨウ素原子を表す。
R1は、炭素数1~20のアルキル基、炭素数1~20のアルコキシ基、炭素数1~20のアシル基、炭素数2~20のアルコキシカルボニル基、炭素数1~20のアシルオキシ基または-N(R10)(R11)を表し、R10は、炭素数1~20のアシル基、炭素数1~20のアルキルスルホニル基または炭素数6~20のアリールスルホニル基を表わし、R11は、水素原子または炭素数1~20のアルキル基を表し、R10とR11とが互いに結合して、それらが結合する窒素原子とともに、-N-CO-または-N-SO2-を含む環を形成してもよい。前記アルキル基、前記アルコキシ基、前記アシル基、前記アルコキシカルボニル基、前記アシルオキシ基、前記アルキルスルホニル基および前記アリールスルホニル基を構成する一つ以上の水素原子は、ハロゲン原子、ヒドロキシ基、アミノ基または置換基を有するアミノ基で置き換わっていてもよい。前記アルキル基および前記アルコキシ基を構成する炭素原子間には、-O-または-NR20-が挿入されていてもよく、R20は、水素原子または炭素数1~20のアルキル基を表わす。
R7は、水素原子以外の置換基であって、それぞれ独立して、炭素数1~4のアルキル基、炭素数1~4のアルコキシ基、ハロゲン原子、またはシアノ基を表し、上記炭素数1~4のアルキル基および上記炭素数1~4のアルコキシ基を構成する少なくとも一つの水素原子は、ハロゲン原子またはヒドロキシ基で置換されていてもよく、pは0~2の整数である。
Yは、式(Y1):
(式中、*はNとの結合部位を表す。炭素数1~4のアルコキシ基、ハロゲン原子、またはシアノ基を表し、上記炭素数1~4のアルキル基および上記炭素数1~4アルコキシ基を構成する少なくとも一つの水素原子は、ハロゲン原子またはヒドロキシ基で置換されていてもよく、rは0~2の整数である。)
で示される基または式(Y2):
(式中、*はNとの結合部位を表し、P1およびP2は、それぞれ独立して、-S-、-O-または-N(R12)-を表し、R12は、水素原子または炭素数1~4のアルキル基を表し、Q1およびQ2は、それぞれ独立して、=N-または=CH-を表す。)
で示される基を表す。]
で表される化合物と式(3):
[式中、R2は炭素数1~20のアシル基、炭素数1~20のアルキルスルホニル基または炭素数6~20のアリールスルホニル基を表し、R3は水素原子または炭素数1~20のアルキル基を表し、R2とR3とが互いに結合して、それらが結合する窒素原子とともに、-N-CO-または-N-SO2-を含む環を形成してもよい。前記アシル基、前記アルキルスルホニル基および前記アリールスルホニル基を構成する一つ以上の水素原子は、ハロゲン原子、ヒドロキシ基、アミノ基または置換基を有するアミノ基で置き換わっていてもよい。前記アルキル基および前記アルコキシ基を構成する炭素原子間には、-O-または-NR21-が挿入されていてもよく、R21は、水素原子または炭素数1~20のアルキル基を表わす。
R8は、水素原子以外の置換基であって、それぞれ独立して、炭素数1~4のアルキル基、炭素数1~4のアルコキシ基、ハロゲン原子、またはシアノ基を表し、上記炭素数1~4のアルキル基および上記炭素数1~4アルコキシ基を構成する少なくとも一つの水素原子は、ハロゲン原子またはヒドロキシ基で置換されていてもよく、qは0~2の整数である。
R4およびR5は、それぞれ独立して、水素原子または炭素数1~10のアルキル基を表し、R4とR5とが互いに結合して、それらが結合する酸素原子およびホウ素原子とともに、-O-B-O-を含む環を形成してもよい。]
で表される化合物とを反応させる式(1):
[式中、R1、R2、R3、R7、R8およびYは、上記と同一の意味を表す。]
で表される化合物の製造方法。
本発明の式(1)で表される化合物(以下、化合物(1)ということがある)のアゾ基は、トランスのアゾ基であることが好ましい。
炭素数1~20のアルキルスルホニル基としては、メチルスルホニル基、エチルスルホニル基、n-プロピルスルホニル基等の無置換の炭素数1~20のアルキルスルホニル基が挙げられ、かかるアルキルスルホニル基を構成する一つ以上の水素原子が、ハロゲン原子等で置き換わった基としては、トリフルオロメチルスルホニル基、ペンタフルオロエチルスルホニル基、ヘプタフルオロ-n-プロピルスルホニル基等の炭素数1~20のハロアルキルスルホニル基が挙げられる。
炭素数6~20のアリールスルホニル基としては、ベンゼンスルホニル基、p-トルエンスルホニル基等が挙げられ、かかるアリールスルホニル基を構成する一つ以上の水素原子が、ハロゲン原子等で置き換わった基としては、p-トリフルオロメチルベンゼンスルホニル基等が挙げられる。
R11における炭素数1~20のアルキル基としては、上記のR1における炭素数1~20のアルキル基と同様のものが挙げられ、該アルキル基を構成する一つ以上の水素原子が、ハロゲン原子等で置き換わったアルキル基としては、上記R1における基と同様のものが挙げられる。
R10とR11とが互いに結合して、それらが結合する窒素原子とともに形成する-N-CO-または-N-SO2-を含む環は、4~10員環であることが好ましく、5~7員環であることがより好ましい。具体的には、2-ピロリドン-1-イル基等が挙げられる。
R1は、より好ましくは、フッ素原子を有していてもよい直鎖状の炭素数1~10のアルキル基または-N(R10)(R11)であり、R10は、より好ましくは、フッ素原子を有していてもよい炭素数1~10のアシル基であり、R11は、好ましくは、水素原子である。
R1は、特に好ましくは、フッ素原子を有していてもよい直鎖状の炭素数1~10のアルキル基である。
炭素数1~4のアルキル基としては、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、tert-ブチル基等の、置換基を有していない直鎖状または分枝鎖状のアルキル基が挙げられる。
かかる炭素数1~4のアルキル基を構成する少なくとも一つの水素原子は、フッ素原子等のハロゲン原子、またはヒドロキシ基で置換されていてもよい。これらの例としては、フルオロメチル基、トリフルオロメチル基、ペンタフルオロエチル基、ノナフルオロブチル基等の炭素数1~4のハロアルキル基;ヒドロキシメチル基、2-ヒドロキシエチル基等の炭素数1~4のヒドロキシアルキル基;が挙げられる。
かかる炭素数1~4のアルコキシ基を構成する少なくとも一つの水素原子は、フッ素原子等のハロゲン原子、またはヒドロキシ基で置換されていてもよい。これらの例としては、フルオロメトキシ基、トリフルオロメトキシ基、ペンタフルオロエトキシ基、ノナフルオロブトキシ基等の炭素数1~4のハロアルコキシ基;ヒドロキシメトキシ基、2-ヒドロキシエトキシ基等の炭素数1~4のヒドロキシアルコキシ基が挙げられる。
R2における炭素数1~20のアルキルスルホニル基および炭素数6~20のアリールスルホニル基としては、それぞれ、上記のR10における炭素数1~20のアルキルスルホニル基および炭素数6~20のアリールスルホニル基と同様のものが挙げられる。
R2とR3とが互いに結合して、それらが結合する窒素原子とともに形成する-N-CO-または-N-SO2-を含む環は、4~10員環であることが好ましく、5~7員環であることがより好ましい。具体的には、2-ピロリドン-1-イル基等が挙げられる。
R21における、炭素数1~20のアルキル基としては、上記と同様の基が挙げられる。
R3は、好ましくは、水素原子である。
(式中、*はNとの結合部位を表す。R9は、水素原子以外の置換基であって、それぞれ独立して、炭素数1~4のアルキル基、炭素数1~4のアルコキシ基、ハロゲン原子、またはシアノ基を表し、上記炭素数1~4のアルキル基および上記炭素数1~4アルコキシ基を構成する少なくとも一つの水素原子は、ハロゲン原子またはヒドロキシ基で置換されていてもよく、rは0~2の整数である。)
で示される基または式(Y2):
(式中、*はNとの結合部位を表し、P1およびP2は、それぞれ独立して、-S-、-O-または-N(R12)-を表し、R12は、水素原子または炭素数1~4のアルキル基を表し、Q1およびQ2は、それぞれ独立して、=N-または=CH-を表す。)
で示される基を表す。
P1は、好ましくは、-S-である。
P2は、好ましくは、-S-である。
R12における炭素数1~4のアルキル基としては、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基及びtert-ブチル基が挙げられる。
Q1は、好ましくは、=CH-である。
Q2は、好ましくは、=N-である。
[式中、Xは、塩素原子、臭素原子またはヨウ素原子を表す。
R1、R7、p及びYは、それぞれ上記と同一の意味を表す。]
で表される化合物(以下、化合物(2)ということがある)と、
式(3):
[式中、R2、R3、R8およびqは、それぞれ上記と同一の意味を表し、R4およびR5は、それぞれ独立して、水素原子または炭素数1~10のアルキル基を表し、R4とR5とが互いに結合して、それらが結合する酸素原子およびホウ素原子とともに、-O-B-O-を含む環を形成してもよい。)
で表される化合物(以下、化合物(3)ということがある)とを反応させることにより製造することができる。
化合物(3)におけるR4で表される炭素数1~10のアルキル基、及び、R5で表される炭素数1~10のアルキル基としては、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、tert-ブチル基、n-ペンチル基、イソペンチル基、ネオペンチル基、n-ヘキシル基、n-ヘプチル基、n-オクチル基、n-ノニル基、n-デシル基等の無置換の直鎖状又は分枝鎖状の炭素数1~10のアルキル基が挙げられる。
R4とR5とが互いに結合して、それらが結合する酸素原子およびホウ素原子とともに形成する-O-B-O-を含む環としては、下記の環が挙げられる。下記式中、*は、ベンゼン環との結合手を表す。
-B(OR4)(OR5)としては、下記基が挙げられ、-B(OH)2が好ましい。
下記式中、*は、ベンゼン環との結合手を表す。
化合物(1)は、反応終了後、再結晶、再沈殿、抽出、各種クロマトグラフィー等の通常の取り出し手段によって取り出すことができる。
形成された偏光膜表面に保護フィルムを配置し、その上から下記条件で光を照射する。試験前の偏光膜の極大吸収波長501nmの偏光膜の吸光度に対する、耐光性試験後の偏光膜の極大吸収波長501nmの偏光膜の吸光度の割合から、耐光性を判断する。
例えば、特開2013-101328号公報に記載の式(1-10)で示される二色性色素を使用し偏光膜を形成して耐光性試験を行うと、この偏光膜の極大吸収波長548nmにおける、耐光性試験後の該偏光膜の吸光度は、試験前の47%となる。
使用機器:ATLAS社製 サンテストXLS+
使用光源:キセノンアークランプ
露光条件:250mW/m2
試験時間:120時間
暴露量:108000KJ/m2
温度:60℃
本発明の組成物は、二種以上の化合物(1)を含んでもよい。
重合性液晶化合物とは、分子内に重合性基を有し、配向することによって液晶相を示すことができる化合物であり、好ましくは単独で配向することによって液晶相を示すことができる化合物である。
重合性液晶化合物は、サーモトロピック液晶型であってもよいし、リオトロピック液晶型であってもよい。
化合物(1)は、スメクチック液晶相を示す重合性液晶化合物から形成された、密な分子鎖間に分散した状態であっても、高い二色性を示すことができ、化合物(1)を含む組成物は、二色比の高い偏光膜を与えることができる。
U1-V1-W1-X1-Y1-X2-Y2-X3-W2-V2-U2 (4)
[式(4)中、
X1、X2及びX3は、互いに独立に、置換基を有していてもよい1,4-フェニレン基又は置換基を有していてもよいシクロヘキサン-1,4-ジイル基を表す。ただし、X1、X2及びX3のうち少なくとも1つは、置換基を有していてもよい1,4-フェニレン基である。シクロへキサン-1,4-ジイル基を構成する-CH2-は、-O-、-S-又は-NR-に置き換わっていてもよい。Rは、炭素数1~6のアルキル基又はフェニル基を表す。
Y1及びY2は、互いに独立に、-CH2CH2-、-CH2O-、-COO-、-OCOO-、単結合、-N=N-、-CRa=CRb-、-C≡C-又は-CRa=N-を表す。Ra及びRbは、互いに独立に、水素原子又は炭素数1~4のアルキル基を表す。
U1は、水素原子又は重合性基を表す。
U2は、重合性基を表す。
W1及びW2は、互いに独立に、単結合、-O-、-S-、-COO-又は-OCOO-を表す。
V1及びV2は、互いに独立に、置換基を有していてもよい炭素数1~20のアルカンジイル基を表し、該アルカンジイル基を構成する-CH2-は、-O-、-S-又は-NH-に置き換わっていてもよい。]
置換基を有していてもよい1,4-フェニレン基は、好ましくは、置換基を有していない1,4-フェニレン基である。置換基を有していてもよいシクロへキサン-1,4-ジイル基は、好ましくは、置換基を有していてもよいトランス-シクロへキサン-1,4-ジイル基である。置換基を有していてもよいトランス-シクロへキサン-1,4-ジイル基は、好ましくは、置換基を有していないトランス-シクロへキサン-1,4-ジイル基である。
置換基を有していてもよい炭素数1~20のアルカンジイル基が任意に有する置換基としては、シアノ基及びハロゲン原子が挙げられる。該アルカンジイル基は、好ましくは、置換基を有していないアルカンジイル基であり、より好ましくは、置換基を有しておらず、且つ直鎖状のアルカンジイル基である。
溶剤は、重合性液晶化合物及び化合物(1)を完全に溶解し得るものが好ましい。また、重合性液晶化合物の重合反応に不活性な溶剤であることが好ましい。
重合開始剤は、重合性液晶化合物の重合反応を開始し得る化合物である。重合開始剤としては、光の作用により活性ラジカルを発生する光重合開始剤が好ましい。
重合開始剤としては、市販のものを用いることができる。市販の重合開始剤としては、イルガキュア(Irgacure)(登録商標)907、184、651、819、250及び369(チバ・スペシャルティ・ケミカルズ株式会社製);セイクオール(登録商標)BZ、Z及びBEE(精工化学株式会社製);カヤキュアー(kayacure)(登録商標)BP100及びUVI-6992(ダウ・ケミカル株式会社製);アデカオプトマーSP-152及びSP-170(株式会社ADEKA製);TAZ-A及びTAZ-PP(日本シイベルヘグナー株式会社製);及び、TAZ-104(株式会社三和ケミカル製)が挙げられる。
本発明の組成物が光重合開始剤を含有する場合、本発明の組成物は、好ましくは光増感剤を含有する。本発明の組成物が、光重合開始剤及び光増感剤を含有することにより、重合性液晶化合物の重合反応がより促進される傾向がある。該光増感剤としては、キサントン及びチオキサントン等のキサントン化合物(例えば、2,4-ジエチルチオキサントン、2-イソプロピルチオキサントン);アントラセン及びアルコキシ基含有アントラセン(例えば、ジブトキシアントラセン)等のアントラセン化合物;フェノチアジン及びルブレンが挙げられる。
重合禁止剤としては、ハイドロキノン、アルコキシ基含有ハイドロキノン、アルコキシ基含有カテコール(例えば、ブチルカテコール)、ピロガロール、2,2,6,6-テトラメチル-1-ピペリジニルオキシラジカル等のラジカル捕捉剤;チオフェノール類;β-ナフチルアミン類及びβ-ナフトール類が挙げられる。
本発明の組成物が重合禁止剤を含む場合、本発明の組成物における重合禁止剤の含有量は、重合性液晶化合物100質量部に対して、好ましくは0.1~30質量部であり、より好ましくは0.5~10質量部であり、さらに好ましくは0.5~8質量部である。
レベリング剤とは、本発明の組成物の流動性を調整し、本発明の組成物を塗布して得られる塗布膜をより平坦にする機能を有するものであり、例えば、界面活性剤が挙げることができる。好ましいレベリング剤は、ポリアクリレート化合物を主成分とするレベリング剤及びフッ素原子含有化合物を主成分とするレベリング剤である。
レベリング剤の含有量が前記の範囲内であると、重合性液晶化合物を水平配向させることが容易であり、且つ、得られる偏光膜がより平滑となる傾向がある。重合性液晶化合物に対するレベリング剤の含有量が前記の範囲を超えると、得られる偏光膜にムラが生じやすい傾向がある。本発明の組成物は、二種以上のレベリング剤を含んでもよい。
化合物(1)を含む偏光膜は、例えば、本発明の組成物を塗布することにより得ることができる。好ましくは、下記工程(A)~(C)を含む製造方法によって製造することができる。
工程(A):基材又は配向膜が形成された基材の表面に、本発明の組成物を塗布する工程工程(B):形成された塗布膜に含まれる重合性液晶化合物及び化合物(1)を配向させる工程
工程(C):配向した重合性液晶化合物に活性エネルギー線を照射することにより重合性液晶化合物を重合する工程
<基材>
基材は、ガラス基材でも樹脂基材でもよいが、好ましくは、樹脂基材である。樹脂からなるフィルム基材を用いることで、薄い偏光板を得ることができる。
樹脂基材は、好ましくは、透明樹脂基材である。透明樹脂基材とは、光、特に可視光を透過し得る透光性を有する基材を意味し、透光性とは、波長380nm~780nmにわたる光線に対しての視感度補正透過率が80%以上となる特性をいう。
この際、偏光膜の透過軸と、1/4波長板の遅相軸(光軸)とが実質的に45°となるようにして積層するのが好ましい。実質的に45°とは、通常45±5°の範囲である。
また、偏光膜と1/4波長板の光軸を一致又は、直交させることで光学補償フィルムとして機能する偏光フィルムを得ることができる。
100nm<Re(550)<160nm (40)
130nm<Re(550)<150nm (40-1)
Re(550)は波長550nmの光に対する面内位相差値を表す。
Re(450)/Re(550)≦1.00 (50)
1.00≦Re(630)/Re(550) (51)
鎖状オレフィンとしては、エチレン及びプロピレン等が挙げられ、ビニル化芳香族化合物としては、スチレン、α-メチルスチレン及びアルキル置換スチレン等が挙げられる。
環状オレフィン系樹脂が、環状オレフィンと、鎖状オレフィンと、ビニル化芳香族化合物との三元共重合体である場合、鎖状オレフィンに由来する構造単位の含有量は、共重合体の全構造単位に対して、通常5~80モル%であり、ビニル化芳香族化合物に由来する構造単位の含有割合は、共重合体の全構造単位に対して、通常5~80モル%である。このような三元共重合体は、高価な環状オレフィンの使用量を比較的少なくすることができるという利点がある。
本発明における配向膜とは、重合性液晶化合物を所望の方向に配向させる、配向規制力を有するものである。
配向膜としては、本発明の組成物の塗布などにより溶解しない溶剤耐性を有し、また、溶剤の除去や重合性液晶化合物の配向のための加熱処理における耐熱性を有するものが好ましい。かかる配向膜としては、配向性ポリマーを含む配向膜、光配向膜及び表面に凹凸パターンや複数の溝を形成し配向させるグルブ配向膜等が挙げられる。
ラビングする方向を選択することにより、配向規制力の方向を任意に制御することができる。
単官能アクリレートとは、アクリロイルオキシ基(CH2=CH-COO-)及びメタクリロイルオキシ基(CH2=C(CH3)-COO-)からなる群より選ばれる基(以下、(メタ)アクリロイルオキシ基と記すこともある。)を分子内に1個有する化合物である。
トリメチロールプロパントリ(メタ)アクリレート;ペンタエリスリトールトリ(メタ)アクリレート;トリス(2-ヒドロキシエチル)イソシアヌレートトリ(メタ)アクリレート;エトキシ化トリメチロールプロパントリ(メタ)アクリレート;プロポキシ化トリメチロールプロパントリ(メタ)アクリレート;ペンタエリスリトールテトラ(メタ)アクリレート;ジペンタエリスリトールペンタ(メタ)アクリレート;ジペンタエリスリトールヘキサ(メタ)アクリレート;トリペンタエリスリトールテトラ(メタ)アクリレート;トリペンタエリスリトールペンタ(メタ)アクリレート;トリペンタエリスリトールヘキサ(メタ)アクリレート;トリペンタエリスリトールヘプタ(メタ)アクリレート;トリペンタエリスリトールオクタ(メタ)アクリレート;
ペンタエリスリトールトリ(メタ)アクリレートと酸無水物との反応物;ジペンタエリスリトールペンタ(メタ)アクリレートと酸無水物との反応物;
トリペンタエリスリトールヘプタ(メタ)アクリレートと酸無水物との反応物;
カプロラクトン変性トリメチロールプロパントリ(メタ)アクリレート;カプロラクトン変性ペンタエリスリトールトリ(メタ)アクリレート;カプロラクトン変性トリス(2-ヒドロキシエチル)イソシアヌレートトリ(メタ)アクリレート;カプロラクトン変性ペンタエリスリトールテトラ(メタ)アクリレート;カプロラクトン変性ジペンタエリスリトールペンタ(メタ)アクリレート;カプロラクトン変性ジペンタエリスリトールヘキサ(メタ)アクリレート;カプロラクトン変性トリペンタエリスリトールテトラ(メタ)アクリレート;カプロラクトン変性トリペンタエリスリトールペンタ(メタ)アクリレート;カプロラクトン変性トリペンタエリスリトールヘキサ(メタ)アクリレート;カプロラクトン変性トリペンタエリスリトールヘプタ(メタ)アクリレート;カプロラクトン変性トリペンタエリスリトールオクタ(メタ)アクリレート;カプロラクトン変性ペンタエリスリトールトリ(メタ)アクリレートと酸無水物との反応物;カプロラクトン変性ジペンタエリスリトールペンタ(メタ)アクリレートと酸無水物との反応物、及びカプロラクトン変性トリペンタエリスリトールヘプタ(メタ)アクリレートと酸無水物との反応物などが挙げられる。なお、ここに示した多官能アクリレートの具体例において、(メタ)アクリレートとは、アクリレート又はメタクリレートを意味する。また、カプロラクトン変性とは、(メタ)アクリレート化合物のアルコール由来部位と(メタ)アクリロイルオキシ基との間に、カプロラクトンの開環体、又は、開環重合体が導入されていることを意味する。
かかる市販品としては、A-DOD-N、A-HD-N、A-NOD-N、APG-100、APG-200、APG-400、A-GLY-9E、A-GLY-20E、A-TMM-3、A-TMPT、AD-TMP、ATM-35E、A-TMMT、A-9550、A-DPH、HD-N、NOD-N、NPG、TMPT(新中村化学株式会社製)、”ARONIX M-220”、同”M-325”、同”M-240”、同”M-270”同”M-309”同”M-310”、同”M-321”、同”M-350” 、同”M-360” 、同”M-305” 、同”M-306” 、同”M-450” 、同”M-451” 、同”M-408” 、同”M-400” 、同”M-402” 、同”M-403” 、同”M-404” 、同”M-405” 、同”M-406”(東亜合成株式会社製)、”EBECRYL11”、同”145” 、同”150” 、同”40” 、同”140” 、同”180” 、DPGDA、HDDA、TPGDA、HPNDA、PETIA、PETRA、TMPTA、TMPEOTA、DPHA、EBECRYLシリーズ(ダイセル・サイテック株式会社製)などを挙げることができる。
本発明の組成物が溶剤を含む場合には、通常、形成された塗布膜から溶剤を除去する。
溶剤の除去方法としては、自然乾燥法、通風乾燥法、加熱乾燥及び減圧乾燥法等が挙げられる。
配向した重合性液晶化合物に活性エネルギー線を照射することにより、重合性液晶化合物を重合する。
スメクチック液晶相を保持したまま重合した重合性液晶化合物を含む偏光膜は、従来のホストゲスト型偏光膜、すなわち、ネマチック液晶相を保持したままで重合性液晶化合物等を重合して得られる偏光膜と比較して偏光性能が高く、また、二色性色素又はリオトロピック液晶型の液晶化合物のみを塗布したものと比較して、偏光性能及び強度に優れる。
本発明の偏光膜は、好ましくは、Roll to Roll形式により連続的に製造される。図1を参照しながら、Roll to Roll形式により、本発明の偏光膜を連続的に製造する方法の要部の一例を説明する。
第2ロール220から連続的に本発明の偏光膜を巻き出すとともに、長尺の1/4波長板が巻き取られている第3ロール230から連続的に長尺の1/4波長板を巻き出す工程と、
本発明の偏光膜と、前記長尺の1/4波長板とを連続的に貼合して長尺の円偏光板を得る工程と、
得られた長尺の円偏光板を第4の巻芯240Aに巻き取り、第4ロール240を得る工程とからなる。この方法はいわゆるRoll to Roll貼合である。なお、貼合には接着剤を用いてもよい。
本発明の偏光膜、及び、本発明の偏光膜と1/4波長板とを有する円偏光板は、さまざまな表示装置に用いることができる。
表示装置とは、表示素子を有する装置であり、発光源として発光素子又は発光装置を含むものである。本偏光板を備える表示装置としては、例えば、液晶表示装置、有機エレクトロルミネッセンス(EL)表示装置、無機エレクトロルミネッセンス(EL)表示装置、電子放出表示装置(例えば電場放出表示装置(FED)、表面電界放出表示装置(SED))、電子ペーパー(電子インクや電気泳動素子を用いた表示装置、プラズマ表示装置、投射型表示装置(例えばグレーティングライトバルブ(GLV)表示装置、デジタルマイクロミラーデバイス(DMD)を有する表示装置)及び圧電セラミックディスプレイなどが挙げられる。液晶表示装置は、透過型液晶表示装置、半透過型液晶表示装置、反射型液晶表示装置、直視型液晶表示装置及び投写型液晶表示装置などのいずれをも含む。これらの表示装置は、2次元画像を表示する表示装置であってもよいし、3次元画像を表示する立体表示装置であってもよい。
本発明の偏光膜は、特に、液晶表示装置、有機エレクトロルミネッセンス(EL)表示装置及び無機エレクトロルミネッセンス(EL)表示装置に有効に用いることができる。
本発明の偏光膜と1/4波長板とを有する円偏光板は、特に、有機エレクトロルミネッセンス(EL)表示装置及び無機エレクトロルミネッセンス(EL)表示装置に有効に用いることができる。
また第一の本発明の偏光膜は位相差層を包含していてもよい。
式(2A)で表される化合物0.15g、式(3A)で表される化合物0.10g、リン酸カリウム0.50g、トリス(ジベンジリデンアセトン)ジパラジウム(0)0.0087g、トリ-tert-ブチルホスホニウムテトラフルオロボレート0.011g及び1,4-ジオキサン3gを混合した。得られた混合物を、窒素雰囲気下、100℃で18時間攪拌した。得られた反応混合物を濃縮した後、シリカゲルカラムクロマトグラフィー(溶出液:クロロホルム)で精製した。得られた固体をアセトニトリルで洗浄後、乾燥させることにより、橙色固体である式(1A)で表される化合物(以下、化合物(1A)という)0.03gを得た。
Mw:371(GC-MS)
極大吸収波長(λmax2)=360nm(クロロホルム溶液)
式(2B)で表される化合物0.30g、式(3A)で表される化合物0.21g、酢酸カリウム0.38g、[1,1’-ビス(ジフェニルホスフィノ)フェロセン]ジクロロパラジウム(II)0.129g及びジエチレングリコールジメチルエーテル18.0gを混合した。得られた混合物を、窒素雰囲気下、140℃で3時間攪拌した。得られた反応混合物を濃縮した後、シリカゲルカラムクロマトグラフィー(溶出液:クロロホルム)で精製した。得られた固体をアセトニトリルで洗浄後、乾燥させることにより、橙色固体である式(1B)で表される化合物(以下、化合物(1B)という)0.010gを得た。
Mw:434(LC-MS)
極大吸収波長(λmax2)=437nm(クロロホルム溶液)
式(2C)で表される化合物0.40g、式(3A)で表される化合物0.25g、酢酸カリウム0.45g、[1,1’-ビス(ジフェニルホスフィノ)フェロセン]ジクロロパラジウム(II)0.150g及びジエチレングリコールジメチルエーテル24.0gを混合した。得られた混合物を、窒素雰囲気下、140℃で3時間攪拌した。得られた反応混合物を濃縮した後、シリカゲルカラムクロマトグラフィー(溶出液:クロロホルム)で精製した。得られた固体をアセトニトリルで洗浄後、乾燥させることにより、橙色固体である式(1C)で表される化合物(以下、化合物(1C)という)0.032gを得た。
Mw:490(LC-MS)
極大吸収波長(λmax2)=438nm(クロロホルム溶液)
下記式(4-6)で表される化合物[以下、化合物(4-6)という]、下記式(4-8)で表される化合物[以下、化合物(4-8)という]、下記式(4-14)で表される化合物[以下、化合物(4-14)という]及び下記式(4-17)で表される化合物[以下、化合物(4-17)という]を用いた。
なお、化合物(4-6)は、Lub et al. Recl.Trav.Chim.Pays-Bas,115, 321-328(1996)記載の方法で合成した。また、この方法に準拠して、化合物(4-8)を製造した。
化合物(4-14)及び化合物(4-17)は、特許第4719156号記載の方法に準拠して製造した
化合物(4-6)の相転移温度は、化合物(4-6)からなる膜の相転移温度を求めることで確認した。その操作は以下のとおりである。
配向膜を形成したガラス基板上に、化合物(4-6)からなる膜を形成し、加熱しながら、偏光顕微鏡(BX-51、オリンパス社製)によるテクスチャー観察によって相転移温度を確認した。化合物(4-6)は、120℃まで昇温後、降温時において、112℃でネマチック相に相転移し、110℃でスメクチックA相に相転移し、94℃でスメクチックB相へ相転移した。
化合物(4-6)の相転移温度測定と同様にして、化合物(4-8)の相転移温度を確認した。化合物(4-8)は、140℃まで昇温後、降温時において、131℃でネマチック相に相転移し80℃でスメクチックA相に相転移し、68℃でスメクチックB相へ相転移した。
化合物(4-6)の相転移温度測定と同様にして、化合物(4-14)の相転移温度を確認した。化合物(4-14)は、140℃まで昇温後、降温時において、106℃でネマチック相に相転移し103℃でスメクチックA相に相転移し、86℃でスメクチックB相へ相転移した。
化合物(4-6)の相転移温度測定と同様にして、化合物(4-17)の相転移温度を確認した。化合物(4-17)は、140℃まで昇温後、降温時において、119℃でネマチック相に相転移し100℃でスメクチックA相に相転移し、77℃でスメクチックB相へ相転移した。
〔組成物の調製〕
下記の成分を混合し、80℃で1時間攪拌することで、組成物(1)を得た。
重合性液晶化合物;化合物(4-6) 75部
化合物(4-8) 25部
化合物(1); 化合物(1A) 2.5部
重合開始剤;
2-ジメチルアミノ-2-ベンジル-1-(4-モルホリノフェニル)ブタン-1-オン(イルガキュア369;チバ スペシャルティケミカルズ社製)
6部
レベリング剤;
ポリアクリレート化合物(BYK-361N;BYK-Chemie社製)
1.5部
溶剤;クロロホルム 250部
化合物(4-6)と同様に、組成物(1)に含まれる成分の相転移温度を求めた。かかる成分は、140℃まで昇温後、降温時において、115℃でネマチック相に相転移し105℃でスメクチックA相に相転移し、75℃でスメクチックB相へ相転移した。
1.配向膜の形成
ガラス基板上に、ポリビニルアルコール(ポリビニルアルコール1000完全ケン化型、和光純薬工業株式会社製)の2質量%水溶液をスピンコート法により塗布し、乾燥後、厚さ100nmの膜を形成した。続いて、得られた膜の表面にラビング処理を施すことにより配向膜を形成した。ラビング処理は、半自動ラビング装置(商品名:LQ-008型、常陽工学株式会社製)を用いて、布(商品名:YA-20-RW、吉川化工株式会社製)によって、押し込み量0.15mm、回転数500rpm、16.7mm/sの条件で行った。かかるラビング処理により、ガラス基板上に配向膜が形成された積層体1を得た。
積層体1の配向膜上に、組成物(1)をスピンコート法により塗布し、120℃のホットプレート上で1分間加熱乾燥した後、速やかに室温まで冷却して、前記配向膜上に配向した重合性液晶化合物を含む乾燥被膜を形成した。次いで、UV照射装置(SPOT CURE SP-7;ウシオ電機株式会社製)を用い、紫外線を、露光量2000mJ/cm2(365nm基準)で乾燥被膜に照射することにより、該乾燥被膜に含まれる重合性液晶化合物を、配向状態を保持したまま重合させ、該乾燥被膜から偏光膜(1)を形成し積層体2を得た。この際の偏光膜の厚みをレーザー顕微鏡(オリンパス株式会社社製 OLS3000)により測定したところ、1.7μmであった。
偏光膜(1)に対して、X線回折装置X’Pert PRO MPD(スペクトリス株式会社製)を用いてX線回折測定を行った。ターゲットとしてCuを用いてX線管電流40mA、X線管電圧45kVの条件で発生したX線を固定発散スリット1/2°を介してラビング方向(予め、偏光膜下にある配向膜のラビング方向を求めておく。)から入射させ、走査範囲2θ=4.0~40.0°の範囲で2θ=0.01671°ステップで走査して測定を行った結果、2θ=20.1°付近にピーク半価幅(FWHM)=約0.31°のシャープな回折ピーク(ブラッグピーク)が得られた。また、ラビング垂直方向からの入射でも同等な結果を得た。ピーク位置から求めた秩序周期(d)は約4.4Åであり、高次スメクチック相を反映した構造を形成していることがわかった。
極大吸収波長における透過軸方向の吸光度(A1)及び吸収軸方向の吸光度(A2)を、分光光度計(島津製作所株式会社製 UV-3150)に、積層体2を備えたフォルダーを、セットした装置を用いてダブルビーム法で測定した。該フォルダーは、リファレンス側は光量を50%カットするメッシュを設置した。測定された透過軸方向の吸光度(A1)及び吸収軸方向の吸光度(A2)の値から、比(A2/A1)を算出し、二色比とした。極大吸収波長(λmax1)は376nmであり、この波長での二色比は38と高い値を示した。二色比が高いほど、偏光膜として有用であるといえる。化合物(1A)の極大吸収波長(λmax2)は360nmであることから、長波長シフトしていることが判明した。この長波長シフトの結果は、本発明の偏光膜中において、重合性液晶化合物が重合してなる密な分子鎖間に、化合物(1A)が分散しているとき、該化合物(1A)がその分子鎖と強く相互作用していることを示すものである。
使用機器:ATLAS社製 サンテストXLS+
使用光源:キセノンアークランプ
露光条件:250mW/m2
試験時間:120時間
暴露量:108000KJ/m2
温度:60℃
実施例4において、化合物(1A)に代えて化合物(1B)を用いる以外は実施例4と同様に実施することにより、化合物(1B)を含む組成物および偏光膜が得られる。
実施例4において、化合物(1A)に代えて化合物(1C)を用いる以外は実施例4と同様に実施することにより、化合物(1C)を含む組成物および偏光膜が得られる。
実施例4において、化合物(1A)に代えて化合物(1D)を用いる以外は実施例4と同様に実施することにより、化合物(1D)を含む組成物および偏光膜が得られる。
式(2E)で表される化合物0.30g、式(3A)で表される化合物0.25g、酢酸カリウム0.45g、[1,1’-ビス(ジフェニルホスフィノ)フェロセン]ジクロロパラジウム(II)0.15g及びジエチレングリコールジメチルエーテル18gを混合した。得られた混合物を、窒素雰囲気下、140℃で3時間攪拌した。得られた反応混合物を濃縮した後、シリカゲルカラムクロマトグラフィー(溶出液:テトラヒドロフラン)で精製した。得られた固体をアセトニトリルで洗浄後、乾燥させることにより、橙色固体である式(1E)で表される化合物(以下、化合物(1E)という)0.14gを得た。収率は、化合物(2E)基準で40%であった。
M/Z:384(EI-MS)
極大吸収波長(λmax2)=363nm(クロロホルム溶液)
1H-NMR(DMSO-d6):δ(ppm) 2.06(s、3H)、7.73(m、4H)、7.95(m、4H)、8.03(m、4H)、10.1(s、1H)。
化合物(1A)の代わりに化合物(1E)を用いたこと以外は、実施例4と同様にして、偏光膜を作製した。同様に極大吸収波長ならびに二色比を測定したところ、極大吸収波長(λmax1)は392nmであり、二色比は30と高い値を示した。また、実施例9に記載したとおり極大吸収波長(λmax2)は363nmであるため、長波長シフトしていることが判明した。この結果は、偏光膜中において、重合性液晶化合物が重合してなる密な分子鎖間に、化合物(1E)が分散しているとき、該化合物(1E)がその分子鎖と強く相互作用していることを示すものである。
実施例4において、化合物(1A)に代えて化合物(1F)を用いる以外は実施例4と同様に実施することにより、化合物(1F)を含む組成物および偏光膜が得られる。
式(2G)で表される化合物0.30g、式(3A)で表される化合物0.22g、酢酸カリウム0.39g、[1,1’-ビス(ジフェニルホスフィノ)フェロセン]ジクロロパラジウム(II)0.13g及びジエチレングリコールジメチルエーテル18gを混合した。得られた混合物を、窒素雰囲気下、140℃で3時間攪拌した。得られた反応混合物を濃縮した後、シリカゲルカラムクロマトグラフィー(溶出液:テトラヒドロフラン)で精製した。得られた固体をアセトニトリルで洗浄後、乾燥させることにより、橙色固体である式(1G)で表される化合物(以下、化合物(1G)という)0.26gを得た。収率は、化合物(2G)基準で76%であった。
M/Z:428(EI-MS)
極大吸収波長(λmax2)=360nm(クロロホルム溶液)
1H-NMR(CDCl3):δ(ppm) 0.88(t、3H)、1.30(m、10H)、1.63(t、2H)、2.21(s、3H)、2.68(t、2H)、7.25(d、2H)、7.33(d、2H)、7.67(m、4H)、7.85(d、2H)、7.96(d、2H)。
化合物(1A)の代わりに化合物(1G)を用いたこと以外は、実施例4と同様にして、偏光膜を作製した。同様に極大吸収波長ならびに二色比を測定したところ、極大吸収波長(λmax1)は380nmであり、二色比は60と高い値を示した。また、実施例13に記載したとおり極大吸収波長(λmax2)は360nmであるため、長波長シフトしていることが判明した。この結果は、偏光膜中において、重合性液晶化合物が重合してなる密な分子鎖間に、化合物(1G)が分散しているとき、該化合物(1G)がその分子鎖と強く相互作用していることを示すものである。
式(2G)で表される化合物0.30g、式(3B)で表される化合物0.30g、リン酸カリウム0.85g、トリス(ジベンジリデンアセトン)ジパラジウム(0)0.0147g、トリ-tert-ブチルホスホニウムテトラフルオロボレート0.0187g及び1,4-ジオキサン6gを混合した。得られた混合物を、窒素雰囲気下、100℃で5時間攪拌した。得られた反応混合物を濃縮した後、シリカゲルカラムクロマトグラフィー(溶出液:テトラヒドロフラン)で精製した。得られた固体をアセトニトリルで洗浄後、乾燥させることにより、橙色固体である式(1H)で表される化合物(以下、化合物(1H)という)0.11gを得た。収率は、化合物(2G)基準で28%であった。
M/Z:482(EI-MS)
極大吸収波長(λmax2)=355nm(クロロホルム溶液)
210A 巻芯
220 第2ロール
220A 巻芯
211A,211B 塗布装置
212A,212B 乾燥炉
213A 偏光UV照射装置
213B 活性エネルギー線照射装置
300 補助ロール
230 第3ロール
230A 巻芯
240 第4ロール
240A 巻芯
300 補助ロール
Claims (18)
- 式(1):
[式中、R1は、炭素数1~20のアルキル基、炭素数1~20のアルコキシ基、炭素数1~20のアシル基、炭素数2~20のアルコキシカルボニル基、炭素数1~20のアシルオキシ基または-N(R10)(R11)を表し、R10は、炭素数1~20のアシル基、炭素数1~20のアルキルスルホニル基または炭素数6~20のアリールスルホニル基を表わし、R11は、水素原子または炭素数1~20のアルキル基を表し、R10とR11とが互いに結合して、それらが結合する窒素原子とともに、-N-CO-または-N-SO2-を含む環を形成してもよい。前記アルキル基、前記アルコキシ基、前記アシル基、前記アルコキシカルボニル基、前記アシルオキシ基、前記アルキルスルホニル基および前記アリールスルホニル基を構成する一つ以上の水素原子は、ハロゲン原子、ヒドロキシ基、アミノ基または置換基を有するアミノ基で置き換わっていてもよい。前記アルキル基および前記アルコキシ基を構成する炭素原子間には、-O-または-NR20-が挿入されていてもよく、R20は、水素原子または炭素数1~20のアルキル基を表わす。
R7およびR8は、水素原子以外の置換基であって、それぞれ独立して、炭素数1~4のアルキル基、炭素数1~4のアルコキシ基、ハロゲン原子、またはシアノ基を表し、上記炭素数1~4のアルキル基および上記炭素数1~4アルコキシ基を構成する少なくとも一つの水素原子は、ハロゲン原子またはヒドロキシ基で置換されていてもよく、p及びqは、それぞれ独立して0~2の整数である。
R2は炭素数1~20のアシル基、炭素数1~20のアルキルスルホニル基または炭素数6~20のアリールスルホニル基を表し、R3は水素原子または炭素数1~20のアルキル基を表し、R2とR3とが互いに結合して、それらが結合する窒素原子とともに、-N-CO-または-N-SO2-を含む環を形成してもよく、前記アシル基、前記アルキルスルホニル基および前記アリールスルホニル基を構成する一つ以上の水素原子は、ハロゲン原子、ヒドロキシ基、アミノ基または置換基を有するアミノ基で置き換わっていてもよい。前記アルキル基および前記アルコキシ基を構成する炭素原子間には、-O-または-NR21-が挿入されていてもよく、R21は、水素原子または炭素数1~20のアルキル基を表わす。
Yは、式(Y1):
(式中、*はNとの結合部位を表す。R9は、水素原子以外の置換基であって、それぞれ独立して、炭素数1~4のアルキル基、炭素数1~4のアルコキシ基、ハロゲン原子、またはシアノ基を表し、上記炭素数1~4のアルキル基および上記炭素数1~4アルコキシ基を構成する少なくとも一つの水素原子は、ハロゲン原子またはヒドロキシ基で置換されていてもよく、rは0~2の整数である。)
で示される基または式(Y2):
(式中、*はNとの結合部位を表し、P1およびP2は、それぞれ独立して、-S-、-O-または-N(R12)-を表し、R12は、水素原子または炭素数1~4のアルキル基を表し、Q1およびQ2は、それぞれ独立して、=N-または=CH-を表す。)
で示される基を表す。]
で表される化合物。 - p、qおよびrが0である請求項1に記載の化合物。
- 重合性液晶化合物と請求項1または2に記載の化合物とを含む組成物。
- 重合性液晶化合物が、スメクチック液晶相を示す請求項3に記載の組成物。
- さらに重合開始剤を含む請求項3または4に記載の組成物。
- 請求項1または2に記載の化合物を含む偏光膜。
- 請求項3~5のいずれかに記載の組成物から形成される偏光膜。
- 偏光膜の極大吸収波長(λmax1)が、式(1)で表される化合物の極大吸収波長(λmax2)よりも長い請求項6または7に記載の偏光膜。
- λmax1と、λmax2との差が15nm以上である請求項8に記載の偏光膜。
- X線回折測定においてブラッグピークを示す請求項6~9のいずれかに記載の偏光膜。
- 請求項6~10のいずれかに記載の偏光膜を備える液晶表示装置。
- 請求項6~10のいずれかに記載の偏光膜、液晶層および基体を備える液晶セル。
- 偏光膜が、基体と液晶層との間に配置される請求項12に記載の液晶セル。
- 基体と液晶層との間に、カラーフィルタがさらに配置される請求項13に記載の液晶セル。
- 請求項6~10のいずれかに記載の偏光膜と1/4波長板とを有する円偏光板。
- 請求項6~10のいずれかに記載の偏光膜と有機EL素子とを備える有機EL表示装置。
- 請求項15に記載の円偏光板と有機EL素子とを備える有機EL表示装置。
- 式(2):
[式中、Xは、塩素原子、臭素原子またはヨウ素原子を表す。
R1は、炭素数1~20のアルキル基、炭素数1~20のアルコキシ基、炭素数1~20のアシル基、炭素数2~20のアルコキシカルボニル基、炭素数1~20のアシルオキシ基または-N(R10)(R11)を表し、R10は、炭素数1~20のアシル基、炭素数1~20のアルキルスルホニル基または炭素数6~20のアリールスルホニル基を表わし、R11は、水素原子または炭素数1~20のアルキル基を表し、R10とR11とが互いに結合して、それらが結合する窒素原子とともに、-N-CO-または-N-SO2-を含む環を形成してもよい。前記アルキル基、前記アルコキシ基、前記アシル基、前記アルコキシカルボニル基、前記アシルオキシ基、前記アルキルスルホニル基および前記アリールスルホニル基を構成する一つ以上の水素原子は、ハロゲン原子、ヒドロキシ基、アミノ基または置換基を有するアミノ基で置き換わっていてもよい。前記アルキル基および前記アルコキシ基を構成する炭素原子間には、-O-または-NR20-が挿入されていてもよく、R20は、水素原子または炭素数1~20のアルキル基を表わす。
R7は、水素原子以外の置換基であって、それぞれ独立して、炭素数1~4のアルキル基、炭素数1~4のアルコキシ基、ハロゲン原子、またはシアノ基を表し、上記炭素数1~4のアルキル基および上記炭素数1~4のアルコキシ基を構成する少なくとも一つの水素原子は、ハロゲン原子またはヒドロキシ基で置換されていてもよく、pは0~2の整数である。
Yは、式(Y1):
(式中、*はNとの結合部位を表す。炭素数1~4のアルコキシ基、ハロゲン原子、またはシアノ基を表し、上記炭素数1~4のアルキル基および上記炭素数1~4アルコキシ基を構成する少なくとも一つの水素原子は、ハロゲン原子またはヒドロキシ基で置換されていてもよく、rは0~2の整数である。)
で示される基または式(Y2):
(式中、*はNとの結合部位を表し、P1およびP2は、それぞれ独立して、-S-、-O-または-N(R12)-を表し、R12は、水素原子または炭素数1~4のアルキル基を表し、Q1およびQ2は、それぞれ独立して、=N-または=CH-を表す。)
で示される基を表す。]
で表される化合物と式(3):
[式中、R2は炭素数1~20のアシル基、炭素数1~20のアルキルスルホニル基または炭素数6~20のアリールスルホニル基を表し、R3は水素原子または炭素数1~20のアルキル基を表し、R2とR3とが互いに結合して、それらが結合する窒素原子とともに、-N-CO-または-N-SO2-を含む環を形成してもよく、前記アシル基、前記アルキルスルホニル基および前記アリールスルホニル基を構成する一つ以上の水素原子は、ハロゲン原子、ヒドロキシ基、アミノ基または置換基を有するアミノ基で置き換わっていてもよい。前記アルキル基および前記アルコキシ基を構成する炭素原子間には、-O-または-NR21-が挿入されていてもよく、R21は、水素原子または炭素数1~20のアルキル基を表わす。
R8は、水素原子以外の置換基であって、それぞれ独立して、炭素数1~4のアルキル基、炭素数1~4のアルコキシ基、ハロゲン原子、またはシアノ基を表し、上記炭素数1~4のアルキル基および上記炭素数1~4アルコキシ基を構成する少なくとも一つの水素原子は、ハロゲン原子またはヒドロキシ基で置換されていてもよく、qは0~2の整数である。
R4およびR5は、それぞれ独立して、水素原子または炭素数1~10のアルキル基を表し、R4とR5とが互いに結合して、それらが結合する酸素原子およびホウ素原子とともに、-O-B-O-を含む環を形成してもよい。]
で表される化合物とを反応させる式(1):
[式中、R1、R2、R3、R7、R8およびYは、上記と同一の意味を表す。]
で表される化合物の製造方法。
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