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WO2011024892A1 - Colorant dichroïque, film anisotrope pouvant absorber la lumière, polariseur et son procédé de fabrication, et dispositif d'affichage - Google Patents

Colorant dichroïque, film anisotrope pouvant absorber la lumière, polariseur et son procédé de fabrication, et dispositif d'affichage Download PDF

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Publication number
WO2011024892A1
WO2011024892A1 PCT/JP2010/064469 JP2010064469W WO2011024892A1 WO 2011024892 A1 WO2011024892 A1 WO 2011024892A1 JP 2010064469 W JP2010064469 W JP 2010064469W WO 2011024892 A1 WO2011024892 A1 WO 2011024892A1
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group
general formula
represented
substituent
anisotropic film
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English (en)
Japanese (ja)
Inventor
伸卓 岩橋
亮司 後藤
慎一 森嶌
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Fujifilm Corp
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Fujifilm Corp
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    • G—PHYSICS
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B31/00—Disazo and polyazo dyes of the type A->B->C, A->B->C->D, or the like, prepared by diazotising and coupling
    • C09B31/16—Trisazo dyes
    • C09B31/26—Trisazo dyes from other coupling components "D"
    • C09B31/28—Heterocyclic compounds
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments

Definitions

  • the present invention relates to a novel dichroic dye and a light absorption anisotropic film.
  • the present invention also relates to a polarizer and a display device using the light absorption anisotropic film.
  • the present invention also relates to a method for manufacturing a polarizer.
  • iodine has a high sublimation property, when used for a polarizer, its heat resistance and light resistance are not sufficient.
  • the extinction color is deep blue, which is not an ideal achromatic polarizer over the entire visible spectrum region.
  • polarizers are an important component in LCDs that use optical rotation and birefringence as the display principle.
  • new polarizers have been developed for the purpose of improving display performance and the like. .
  • One method is to dissolve or adsorb an organic dye having a dichroism (dichroic dye) in a polymer material such as polyvinyl alcohol in the same way as a polarizer containing iodine, and film the film in one direction. And a method of orienting the dichroic dye by stretching it into a shape.
  • this method has a problem such that a process such as a stretching process is troublesome. Therefore, other methods have recently attracted attention.
  • a dichroic dye is oriented on a substrate such as glass or transparent film by utilizing intermolecular interaction of organic dye molecules, and a polarizing film (anisotropic dye film) is formed. Forming.
  • a polarizing film anisotropic dye film
  • orienting the dichroic dye on the substrate such as glass or transparent film by utilizing the intermolecular interaction of organic dye molecules can be achieved by a wet film forming method.
  • the dye used in this dye film is suitable for the process of the wet film formation method in addition to the high dichroism of the dye molecule. It is required to be a pigment.
  • the process in the wet film forming method include a method of depositing and orienting a dye on a substrate and a method of controlling the orientation. Accordingly, even a dye that can be used in a polarizer that has undergone the above-described conventional stretching treatment is often not suitable for the wet film-forming method.
  • Patent Documents 1 to 3 materials suitable for the above process are proposed. However, these materials have a problem that even if they are suitable for the process, they cannot exhibit high dichroism.
  • Patent Document 4 proposes a dye represented by (chromogen) (SO 3 M) n .
  • organic dye molecules are vapor-deposited from the gas phase and aligned on the alignment film.
  • Patent Document 6 discloses a method of spin-coating and aligning a liquid crystalline azo dye on a rubbed alignment film.
  • Patent Document 7 discloses a polarizer obtained by coating and aligning a dichroic molecule having a hydrophilic substituent such as a sulfonic acid group, an amino group, or a hydroxyl group on a layer having a photoactive molecule (so-called photo-alignment film). Has been.
  • Patent Documents 8 and 9 disclose a polarizer formed by coating and aligning a composition (so-called guest-host type) obtained by dissolving a black dichroic dye in an ultraviolet curable liquid crystal in a photo-alignment film. ing.
  • a composition so-called guest-host type
  • any of the polarizers obtained by these methods is considerably inferior in dichroism as compared with an iodine polarizer, and cannot be used for liquid crystal display devices.
  • Patent Document 10 proposes to suppress the depolarization of the color filter by providing a polarizing layer (so-called in-cell polarizing layer) between the color filter layer and the liquid crystal material layer.
  • a polarizing layer so-called in-cell polarizing layer
  • the polarizing layer disposed in the liquid crystal cell needs to achieve a desired degree of polarization with a thinner film thickness, and higher dichroism is required.
  • the present invention has been made in view of the background art described above, and includes a novel dichroic dye having high dichroism, a light absorption anisotropic film and a polarizer, and a display device having the light absorption anisotropic film. It is to provide.
  • Light absorption anisotropic film comprising the composition: Wherein the R 1 ⁇ R 5 each independently represents a hydrogen atom or a substituent; R 6 and R 7 each independently represent a hydrogen atom or an optionally substituted alkyl group; Q 1 is Represents an optionally substituted aromatic hydrocarbon group, aromatic heterocyclic group or cyclohexane ring group; L 1 represents a divalent linking group; A represents an oxygen atom or a sulfur atom; In the formula, each of R 8 and R 9 independently represents a hydrogen atom or an optionally substituted alkyl group; Q 2 represents an optionally substituted aromatic hydrocarbon group or aromatic group.
  • Q 3 represents an optionally substituted divalent aromatic hydrocarbon group or divalent aromatic heterocyclic group; n represents an integer of 1 to 4; When n is 2
  • liquid crystalline azo dye represented by the general formula (1) is represented by the following general formula (3)
  • liquid crystalline azo dye represented by the general formula (2) is represented by the following general formula (4).
  • R 10 to R 13 each independently represents a hydrogen atom or an alkyl group;
  • R 14 represents a hydrogen atom or a methyl group; and
  • R 15 and R 16 each independently have a substituent.
  • B 1 represents a nitrogen atom or an optionally substituted carbon atom;
  • L 2 represents an azo group, an acyloxy group (—C ( ⁇ O) O—), an oxycarbonyl group (— OC ( ⁇ O) —) or an imino group;
  • R 17 to R 20 each independently represents a hydrogen atom or a substituent;
  • R 21 and R 22 each independently represents an alkyl group which may have a substituent;
  • B 2 represents a nitrogen atom Or represents an optionally substituted carbon atom;
  • m represents 1 or 2, and when m is 2, two R 17 to R 20 may be the same or different.
  • a polarizer having a substrate and the light absorption anisotropic film of any one of [1] to [6] on the substrate.
  • the polarizer of [6] having an alignment film between the substrate and the light absorption anisotropic film.
  • a display device having the light absorption anisotropic film according to any one of [1] to [5], or the polarizer according to [7] or [8].
  • a highly dichroic light absorption anisotropic film and a polarizer, and a display device having the light absorption anisotropic film can be provided.
  • the present invention relates to a light absorption anisotropic film comprising a dichroic dye composition containing at least one selected from liquid crystalline azo dyes represented by the following general formulas (1) and (2).
  • the dichroic dye composition does not substantially contain a liquid crystal non-coloring compound. That is, in the dichroic composition of the present invention, the azo dye molecules are aligned by their own alignment ability, and the state is fixed, thereby functioning as an absorption anisotropic film such as a polarizing film.
  • the molecules of the dichroic dye are aligned along the alignment of the molecules of the liquid crystal compound, and a predetermined dichroic ratio is achieved.
  • the light absorption anisotropic film of the present invention is distinguished from the so-called guest host (GH) type.
  • GH guest host
  • the composition used for formation usually contains 80% by mass or more of a liquid crystal compound as a host in the total solid content, and the content of the guest dye is about 5 to 15% by mass.
  • a preferred embodiment of the present invention is a non-GH embodiment that does not substantially contain a liquid crystalline non-coloring compound.
  • the proportion of the liquid crystalline non-coloring compound in the composition is 30% by mass. % Is preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less. It is particularly preferred that no liquid crystalline non-coloring compound is contained.
  • Dichroic dye composition used for the production of the light-absorbing anisotropic film of the present invention has liquid crystallinity represented by the following general formulas (1) and (2). It contains at least one selected from azo dyes.
  • Liquid crystalline azo dyes Liquid crystalline azo dyes:
  • R 1 ⁇ R 5 each independently represents a hydrogen atom or a substituent
  • R 6 and R 7 each independently represent a hydrogen atom or an optionally substituted alkyl group
  • Q 1 is Represents an optionally substituted aromatic hydrocarbon group, aromatic heterocyclic group or cyclohexane ring group
  • L 1 represents a divalent linking group
  • A represents an oxygen atom or a sulfur atom.
  • each of R 8 and R 9 independently represents a hydrogen atom or an optionally substituted alkyl group;
  • Q 2 represents an optionally substituted aromatic hydrocarbon group or aromatic group.
  • Q 3 represents an optionally substituted divalent aromatic hydrocarbon group or divalent aromatic heterocyclic group;
  • n represents an integer of 1 to 4; When n is 2 or more, the plurality of Q 3 may be the same or different.
  • the liquid crystalline azo dye represented by the general formula (1) will be described in detail.
  • the substituent represented by R 1 to R 5 is an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms).
  • An alkyl group for example, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, an n-octyl group, an n-decyl group, an n-hexadecyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, etc.
  • An alkenyl group preferably an alkenyl group having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, such as a vinyl group, aryl group, 2-butenyl group, 3- A pentenyl group
  • an alkynyl group preferably an alkynyl group having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms.
  • phenyl group 2,6-diethylphenyl group, 3,5-ditrifluoromethylphenyl group, naphthyl group, biphenyl group and the like
  • substituted or unsubstituted amino group preferably having 0 to 20 carbon atoms, More preferably, it is an amino group having 0 to 10 carbon atoms, particularly preferably 0 to 6 carbon atoms, and examples thereof include an unsubstituted amino group, a methylamino group, a dimethylamino group, a diethylamino group, and an anilino group).
  • An alkoxy group (preferably having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, and a butoxy group), an oxycarbonyl group (Preferably having 2 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, particularly preferably 2 to 10 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, etc.), acyloxy group (preferably Has 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, particularly preferably 2 to 6 carbon atoms such as an acetoxy group and a benzoyloxy group), an acylamino group (preferably having 2 to 20 carbon atoms, More preferably, it has 2 to 10 carbon atoms, particularly preferably 2 to 6 carbon atoms.
  • alkoxycarbonylamino group preferably having 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, particularly preferably 2 to 6 carbon atoms, such as a methoxycarbonylamino group.
  • Aryloxycarbonylamino group preferably having 7 to 20 carbon atoms, more preferably having 7 to 16 carbon atoms, particularly preferably having 7 to 12 carbon atoms, and examples thereof include a phenyloxycarbonylamino group).
  • a sulfonylamino group (preferably having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms, such as a methanesulfonylamino group and a benzenesulfonylamino group), sulfamoyl Group (preferably having 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, particularly preferably The number of carbon atoms is 0 to 6, for example, sulfamoyl group, methylsulfamoyl group, dimethylsulfamoyl group, phenylsulfamoyl group, etc.), carbamoyl group (preferably having 1 to 20 carbon atoms, more preferably Having 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms, and examples thereof include an unsubstituted carbamoyl group, a methylcarbamoyl group, a diethylcar
  • An alkylthio group (preferably having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms, such as a methylthio group and an ethylthio group), an arylthio group (preferably a carbon atom) 6 to 20, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as a phenylthio group, and a sulfonyl group (preferably 1 to 20 carbon atoms, more preferably carbon atoms).
  • 1 to 10 particularly preferably 1 to 6 carbon atoms such as mesyl group and tosyl group
  • sulfinyl group preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, especially Preferably, it has 1 to 6 carbon atoms, and examples thereof include methanesulfinyl group and benzenesulfinyl group, and ureido group (preferably carbon number).
  • a phosphoric acid amide group (preferably Has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms, and examples thereof include a diethylphosphoric acid amide group and a phenylphosphoric acid amide group), a hydroxy group, a mercapto group Group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, azo group, heterocyclic group (preferably having 1 carbon atom) To 30 and more preferably 1 to 12, for example, a heterocyclic group having
  • silyl group preferably having 3 to 3 carbon atoms 40, more preferably a silyl group having 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, and examples thereof include a trimethylsilyl group and a triphenylsilyl group.
  • substituents may be further substituted with these substituents. Further, when two or more substituents are present, they may be the same or different. If possible, they may be bonded to each other to form a ring.
  • the group represented by R 1 to R 5 is preferably a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom, particularly preferably a hydrogen atom, an alkyl group or an alkoxy group, most preferably a hydrogen atom or methyl It is a group.
  • the alkyl group which may have a substituent represented by R 6 and R 7 preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably. Is an alkyl group having 1 to 8 carbon atoms, and examples thereof include a methyl group, an ethyl group, and an n-octyl group.
  • the substituent of the alkyl group represented by R 6 and R 7 has the same meaning as the substituent represented by R 1 to R 5 .
  • R 6 and R 7 represent an alkyl group, they may be linked to each other to form a ring structure.
  • R 6 or R 7 represents an alkyl group, it may be linked to R 2 or R 4 to form a ring structure.
  • the group represented by R 6 and R 7 is particularly preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom, a methyl group or an ethyl group.
  • Q 1 is an optionally substituted aromatic hydrocarbon group (preferably having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, such as a phenyl group, A naphthyl group and the like, and an aromatic heterocyclic group which may have a substituent or a cyclohexane ring group which may have a substituent.
  • the substituent that the group represented by Q 1 may have include a group introduced to enhance the solubility and nematic liquid crystal properties of the azo compound, and an electron introduced to adjust the color tone as a dye.
  • an alkyl group which may have a substituent an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an aryl group which may have a substituent
  • An aryl group which may have a substituent an alkoxy group which may have a substituent, an oxycarbonyl group which may have a substituent, an acyloxy group which may have a substituent, a nitro group, an imino group, An azo group.
  • substituents those having a carbon atom have the same preferable range of the number of carbon atoms as the preferable range of the number of carbon atoms for the substituents represented by R 1 to R 5 .
  • the aromatic hydrocarbon group, the aromatic heterocyclic group, or the cyclohexane ring group may have 1 to 5 and preferably 1 of these substituents.
  • Q 1 is a phenyl group, it preferably has one substituent at the para position with respect to L 1
  • Q 1 is a cyclohexane ring group
  • the trans configuration is at the 4-position with respect to L 1 It preferably has one substituent.
  • the aromatic heterocyclic group represented by Q 1, monocyclic or bicyclic heterocyclic ring from the group.
  • atoms other than carbon constituting the aromatic heterocyclic group include a nitrogen atom, a sulfur atom, and an oxygen atom.
  • the aromatic heterocyclic group has a plurality of atoms constituting a ring other than carbon, these may be the same or different.
  • Specific examples of the aromatic heterocyclic group include pyridyl group, quinolyl group, thiophenyl group, thiazolyl group, benzothiazolyl group, thiadiazolyl group, quinolonyl group, naphthalimidoyl group, and thienothiazolyl group.
  • a pyridyl group, a quinolyl group, a thiazolyl group, a benzothiazoly group, a thiadiazolyl group, or a thienotiazolyl group is preferable, and a pyridyl group, a benzothiazolyl group, a thiadiazolyl group, or a thienothiazolyl group is particularly preferable, and a pyridyl group, a benzothiazolyl group Or a thienothiazolyl group is most preferred.
  • the group represented by Q 1 is particularly preferably an optionally substituted phenyl group, naphthyl group, pyridyl group, benzothiazolyl group, thienothiazolyl group or cyclohexane ring group, more preferably a phenyl group, A pyridyl group, a benzothiazolyl group, or a cyclohexane ring group.
  • the linking group represented by L 1 is a single bond or an alkylene group (preferably having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms).
  • an alkylene group preferably having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms.
  • alkenylene group preferably having 2 to 20 carbon atoms, more preferably carbon number) 2 to 10, particularly preferably 2 to 6 carbon atoms such as ethenylene group
  • alkynylene group preferably 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, particularly preferably carbon number
  • an alkyleneoxy group preferably having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably Or an amide group, an ether group, an acyloxy group (—C ( ⁇ O) O
  • the group represented by L 1 is particularly preferably a single bond, an amide group, an acyloxy group, an oxycarbonyl group, an imino group, an azo group or an azoxy group, and more preferably an azo group, an acyloxy group or an oxycarbonyl group. Or an imino group.
  • A represents an oxygen atom or a sulfur atom, preferably a sulfur atom.
  • Q 2 is an optionally substituted aromatic hydrocarbon group (preferably having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, such as a phenyl group, A naphthyl group) or an aromatic heterocyclic group which may have a substituent.
  • the substituent that the group represented by Q 2 may have is the same as the substituent that the group represented by Q 1 in the general formula (1) may have, and the preferred range is also the same. It is.
  • the aromatic heterocyclic group represented by Q 2 is synonymous with the aromatic heterocyclic group represented by Q 1 in the general formula (1), and the preferred range is also the same.
  • the group represented by Q 2 is particularly preferably a phenyl group, a naphthyl group, a pyridyl group, a benzothiazolyl group or a thienothiazolyl group which may have a substituent, and most preferably a substituent.
  • n represents an integer of 1 to 4, preferably an integer of 1 to 3, more preferably 1 or 2, and particularly preferably 2.
  • Q 3 is a divalent aromatic hydrocarbon group which may have a substituent (preferably having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, A phenylene group, a naphthylene group, etc.) or a divalent aromatic heterocyclic group which may have a substituent, and when n represents an integer of 2 or more, a plurality of Q 3 are the same. May be different.
  • the aromatic hydrocarbon group represented by Q 3 is preferably a phenylene group or a naphthylene group, and more preferably a phenylene group.
  • the divalent aromatic heterocyclic group represented by Q 3 is preferably a monocyclic or bicyclic heterocyclic ring-derived group.
  • Examples of atoms other than carbon constituting the aromatic heterocyclic group include a nitrogen atom, a sulfur atom, and an oxygen atom.
  • the aromatic heterocyclic group has a plurality of atoms constituting a ring other than carbon, these may be the same or different.
  • Specific examples of the aromatic heterocyclic group include a pyridyl group, a quinolyl group, an isoquinolyl group, a benzothiadiazole group, a phthalimide group, and a thienothiazole group. Of these, a thienothiazole group is particularly preferable.
  • Examples of the substituent that the group represented by Q 3 may have include an alkyl group that may have a substituent, an alkoxy group that may have a substituent, a hydroxy group, a nitro group, and a halogen atom. Examples thereof include an atom, an amino group which may have a substituent, an acylamino group which may have a substituent, and a cyano group.
  • the substituent which the group represented by Q 3 may have, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a hydroxy group, a halogen atom And more preferably an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and a halogen atom, particularly preferably a methyl group and a halogen atom.
  • the group represented by Q 3 is particularly preferably a phenylene group or naphthylene group which may have a substituent, and more preferably a phenylene group which may have a substituent.
  • the compounds represented by the general formulas (1) and (2) may have a polymerizable group as a substituent. It is preferable to have a polymerizable group because the hardening property is improved.
  • the polymerizable group include an unsaturated polymerizable group, an epoxy group, and an aziridinyl group, preferably an unsaturated polymerizable group, and particularly preferably an ethylenically unsaturated polymerizable group.
  • the ethylenically unsaturated polymerizable group include acryloyl group and methacryloyl group.
  • the polymerizable group is preferably located at the end of the molecule, ie in formula (1) it is preferably present as a substituent for R 6 and / or R 7 and as a substituent for Q 1 ; In 2), it is preferably present as a substituent for R 8 and / or R 9 and as a substituent for Q 2 .
  • R 10 to R 13 each independently represents a hydrogen atom or an alkyl group
  • R 14 represents a hydrogen atom or a methyl group
  • R 15 and R 16 each independently have a substituent.
  • B 1 represents a nitrogen atom or an optionally substituted carbon atom
  • the alkyl group represented by R 10 to R 13 has the same meaning as the alkyl group represented by R 1 to R 4 in the general formula (1), and the preferred range is also the same.
  • the alkyl group represented by R 15 and R 16 has the same meaning as the alkyl group represented by R 6 and R 7 in the general formula (1), and the preferred range is also the same.
  • R 15 and R 16 , R 15 and R 11 , R 16 and R 13 may be linked to each other to form a ring structure.
  • R 14 represents a hydrogen atom or a methyl group, preferably a hydrogen atom.
  • the substituent that B 1 may have when it is a carbon atom is synonymous with the substituent that Q 1 may have in the general formula (1), and is preferable.
  • the range is also the same.
  • L 2 represents an azo group, an acyloxy group, an oxycarbonyl group, or an imino group, preferably an azo group, an acyloxy group, or an oxycarbonyl group, and more preferably an azo group.
  • R 17 to R 20 each independently represents a hydrogen atom or a substituent
  • R 21 and R 22 each independently represents an alkyl group which may have a substituent
  • B 2 represents a nitrogen atom Or represents an optionally substituted carbon atom
  • m represents 1 or 2, and when m is 2, two R 17 to R 20 may be the same or different.
  • the alkyl group represented by R 17 to R 20 has the same meaning as the substituent that the aromatic hydrocarbon group represented by Q 3 in the general formula (2) may have.
  • the preferred range is also the same.
  • the alkyl group represented by R 21 and R 22 has the same meaning as the alkyl group represented by R 8 and R 9 in the general formula (2), and the preferred range is also the same.
  • R 21 and R 22 may be linked to each other to form a ring structure.
  • m represents 1 or 2, preferably 2.
  • the substituent that B 2 may have when having a carbon atom is synonymous with the substituent that Q 2 may have in the general formula (2), and is preferable.
  • the range is also the same.
  • R 23 to R 30 each independently represents a hydrogen atom or a substituent;
  • R 31 and R 32 each independently represents an alkyl group which may have a substituent;
  • B 3 represents a nitrogen atom Or the carbon atom which may have a substituent is represented.
  • the alkyl group represented by R 23 to R 30 has the same meaning as the substituent that the aromatic hydrocarbon group represented by Q 3 in the general formula (2) may have.
  • the preferred range is also the same.
  • the alkyl group represented by R 31 and R 32 is synonymous with the alkyl group represented by R 8 and R 9 in the general formula (2), and the preferred range is also the same.
  • R 31 and R 32 may be to form a ring structure.
  • the range is also the same.
  • the compounds represented by the general formulas (1) and (3) according to the present invention are described in JP-A-58-38756, JP-A-1-70585, and JP-A-1-146960.
  • the compounds represented by the general formulas (2), (4) and (5) are Journal of Materials Chemistry (1999), 9 (11), 2755-2763, Tetrahedron (2005), 61, 903. According to the method described in -918 and Example 10 described later; it can be easily synthesized.
  • the nematic liquid crystal phase is preferably 10 to 300 ° C., more preferably 100 to 250 ° C. Indicates.
  • the liquid crystalline azo dyes represented by the general formulas (1), (2), (3), (4) and (5) have a flat molecular shape and a good linearity, as is apparent from the molecular structure. Since it has a rigid core portion and a flexible side chain portion and has a polar amino group at the end of the molecular long axis, it has the property of easily exhibiting liquid crystallinity, particularly nematic liquid crystallinity. Furthermore, since the planarity of the molecules is high, strong intermolecular interaction works, and the molecules tend to form an associated state.
  • the dichroic dye composition containing the liquid crystalline azo dye represented by the general formulas (1), (2), (3), (4), and (5) according to the present invention has a wide visible area due to association formation. Not only does it exhibit high absorbance in the wavelength region, but the composition containing this dye has nematic liquid crystal properties, so that, for example, through a lamination process such as coating on the rubbed alignment film surface, A molecular orientation state can be realized. Therefore, the dichroic dye composition containing the liquid crystalline azo dye represented by the general formulas (1), (2), (3), (4) and (5) is used as a light absorption anisotropic film. For example, a polarizer having high polarization characteristics can be produced.
  • one of the liquid crystalline azo dyes represented by the general formulas (1), (2), (3), (4) and (5) may be used alone, or two or more thereof may be used. You may use together.
  • other dye compounds may be used. Examples of other dye compounds include azo dyes other than liquid crystalline azo dyes represented by the general formulas (1), (2), (3), (4), and (5), cyanine dyes, and azo metals.
  • Examples include complexes, phthalocyanine dyes, pyrylium dyes, thiopyrylium dyes, azurenium dyes, squarylium dyes, naphthoquinone dyes, triphenylmethane dyes, and triallylmethane dyes.
  • Other dye compounds are also preferably liquid crystalline.
  • the dichroic dye composition according to the present invention is characterized by not containing a liquid crystalline non-coloring compound.
  • a so-called guest-host type polarizer composed of a liquid crystal compound and a dichroic dye blended therein is conventionally proposed.
  • the molecular orientation of a so-called guest-host type (GH) composition is the present invention. It is inferior compared with the dichroic dye composition which concerns on this, and only a polarizer with a low dichroic ratio is obtained.
  • the total content of the compounds represented by the general formulas (1), (2), (3), (4), and (5) is 80% by mass or more of the dye. It is preferably 90% by mass or more. The upper limit is 100% by mass, that is, all the dyes contained may of course be the predetermined liquid crystalline azo dyes.
  • the content of the compound represented by the general formulas (1), (2), (3), (4) and (5) in the total solid content excluding the solvent is preferably 20% by mass or more, It is particularly preferably 30% by mass or more.
  • the upper limit is not particularly limited, that is, it may be 100% by mass.
  • the dichroic dye is used.
  • the total content of the liquid crystalline azo dye in the total solid content excluding the solvent contained in the composition is preferably 95% by mass or less, and more preferably 90% by mass or less.
  • the composition used for formation usually contains 80% by mass or more of a liquid crystal compound as a host in the total solid content, and the content of the guest dye is 5 to 15% by mass. Degree.
  • Non-liquid crystalline polymer (binder polymer):
  • the dichroic dye composition may contain a non-liquid crystalline polymer.
  • the non-liquid crystalline polymer may be a polymer formed by applying the dichroic dye composition containing a monomer onto a substrate or an alignment film and then polymerizing the monomer.
  • non-liquid crystalline binder polymer an acrylic polymer (a resin having an acrylic copolymer or a styrene copolymer as a main chain) is particularly preferable, and it is particularly preferable that the non-liquid crystalline binder polymer is soluble in an organic solvent.
  • a known radical polymerization method can be applied.
  • Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. in the production by the radical polymerization method can be easily set by those skilled in the art, and the conditions should be determined experimentally. You can also.
  • unsaturated carboxylic acid eg, (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid and fumaric acid
  • aromatic vinyl compound eg, styrene, ⁇ -methylstyrene, vinyltoluene, 2-vinylpyridine, 4-vinylpyridine, N-vinylimidazole, etc.
  • acrylic acid alkyl esters eg, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl) (Meth) acrylate, i-butyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, dodecyl (meth) acrylate, etc.
  • acrylic acid alkyl aryl ester eg, benzyl (meth) acrylate, etc.
  • unsaturated carboxylic acids aromatic vinyl compounds, (meth) acrylic acid alkyl esters, (meth) acrylic acid alkyl aryl esters and carboxylic acid vinyl esters are preferred.
  • (meth) acrylic acid is a general term that combines acrylic acid and methacrylic acid
  • (meth) acrylate is also a general term for acrylate and methacrylate.
  • an acrylic polymer having a (meth) acryloyl group in the side chain or a macromonomer for example, a polystyrene macromonomer, a polymethyl methacrylate macromonomer, a polyethylene glycol mono (meth) acrylate, a polypropylene glycol mono (meth) acrylate, a polyethylene as a copolymerization component
  • An acrylic graft polymer containing glycol polypropylene glycol mono (meth) acrylate and the like is also preferable. These can be used alone or in combination of two or more.
  • the content of the non-liquid crystalline polymer in the total solid content excluding the solvent is preferably 0.5 to 90% by mass, and more preferably 1 to 80% by mass. Preferably, it is 5 to 70% by mass.
  • Non-liquid crystalline polyfunctional monomer having radical polymerizable group The dichroic dye composition used for forming the light absorption anisotropic film of the present invention preferably contains a non-liquid crystalline polyfunctional monomer having a radical polymerizable group.
  • the “non-liquid crystalline polyfunctional monomer having a radical polymerizable group” refers to a non-liquid crystalline monomer which is a polyfunctional monomer in which a growth active species undergoes a radical polymerization reaction.
  • This polyfunctional monomer is preferably a polyfunctional monomer having two or more double bonds in the molecule, particularly preferably an ethylenic (aliphatic) unsaturated double bond, specifically, Polyfunctional monomers having functional groups such as alkenes, dienes, acrylates, methacrylates, diesters of unsaturated polycarboxylic acids, amides of ⁇ , ⁇ -unsaturated carboxylic acids, unsaturated nitriles, styrene and derivatives thereof, vinyl esters, vinyl ethers, etc. Can be mentioned.
  • the number of double bonds in the molecule is preferably 2-20, more preferably 2-15, and even more preferably 2-6.
  • the polyfunctional monomer is preferably an ester of a polyol having two or more hydroxyl groups in the molecule and an unsaturated fatty acid.
  • unsaturated fatty acids include acrylic acid, methacrylic acid, maleic acid and itaconic acid, with acrylic acid and methacrylic acid being preferred.
  • the polyol having 4 or more hydroxyl groups in the molecule is preferably a tetrahydric or higher alcohol or a trihydric or higher alcohol oligomer.
  • the oligomer has a molecular structure in which polyhydric alcohols are linked by an ether bond, an ester bond or a urethane bond. Oligomers having a molecular structure in which polyhydric alcohols are linked by ether bonds are preferred.
  • the polyfunctional monomer is particularly preferably soluble in an organic solvent.
  • An example of such a monomer is a compound having a boiling point of 100 ° C. or higher at normal pressure.
  • examples of the bifunctional (meth) acrylate include ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, Polypropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, bisphenoxyethanol full orange acrylate and the like are listed, and commercially available products thereof include, for example, Aronix M-210, M-240, M-6200 (Toa Synthetic Chemical Industry Co., Ltd.), KAYARAD HDDA, HX-220, R-604 (Nippon Kayaku Co., Ltd.), Biscote 260, 312 and 335HP (Osaka Organic Chemical Co., Ltd.), etc. Is mentioned.
  • Examples of the trifunctional or higher functional (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, pentaerythritol tetra (meth) acrylate, Examples thereof include dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate, and examples of commercially available products thereof include Aronix M-309, M-400, M-405, M-450, and the like.
  • M-7100, M-8030, M-8060 all trade names, manufactured by Toa Gosei Chemical Industry Co., Ltd.
  • KAYARAD TMPTA, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120 both Product name, manufactured by Nippon Kayaku Co., Ltd.
  • BISCOAT 295, the 300, the 360, the same GPT, the same 3PA, the 400 (trade name, manufactured by Osaka Organic Chemical Industry Co., Ltd.), and the like.
  • bifunctional or trifunctional or higher (meth) acrylates include, for example, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolethane triacrylate, trimethylolpropane diacrylate.
  • Monomers composed of an ester of polyol and acrylic acid are commercially available from Mitsubishi Rayon Co., Ltd. (trade name: Diabeam UK-4154) and Nippon Kayaku Co., Ltd. (trade name: KYARAD / DPHA, SR355).
  • bifunctional or trifunctional or higher functional (meth) acrylates may be used alone or in combination, and may be used in combination with monofunctional (meth) acrylate.
  • Examples of monofunctional (meth) acrylates include 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, and 2- (meth) acryloyloxyethyl.
  • 2-Hydroxypropyl phthalate polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) acrylate, ethylene glycol (meth) acrylate, and the like.
  • the polymerization reaction includes a thermal polymerization reaction using a thermal polymerization initiator and a photopolymerization reaction using a photopolymerization initiator.
  • the total content of the liquid crystalline azo dye and the non-liquid crystalline polymerizable polyfunctional monomer in the total solid content excluding the solvent is preferably 50% by mass or more, and 70% by mass or more. Is particularly preferred.
  • Polymerization initiator In order to cure the composition containing the radical polymerizable polyfunctional monomer, it is preferable to contain a polymerization initiator.
  • a polymerization initiator known ones can be suitably used according to photopolymerization and thermal polymerization.
  • ⁇ -carbonyl compounds US Pat. Nos. 2,367,661 and 2,367,670
  • Acyloin ether described in U.S. Pat. No. 2,448,828
  • ⁇ -hydrocarbon-substituted aromatic acyloin compound described in U.S. Pat. No. 2,722,512
  • polynuclear quinone compound U.S. Pat.
  • the amount of the photopolymerization initiator used is preferably 0.01 to 20% by mass, and more preferably 1 to 10% by mass, based on the total solid content excluding the solvent.
  • Examples of the photopolymerization initiator, the amount of the photopolymerization initiator used, and the value of the light irradiation energy for polymerization are also described in paragraphs [0050] to [0051] of JP-A No. 2001-91741. Applicable to the invention.
  • additives In the dichroic dye composition used in the present invention, in addition to the liquid crystalline azo dye and a non-liquid crystalline polyfunctional monomer, a polymerization initiator, and a non-liquid crystalline binder polymer that are optionally added, An organic solvent and arbitrary additives can be blended and used in combination.
  • additives include wind unevenness inhibitors, anti-repellent agents, additives for controlling the tilt angle of the alignment film (tilt angle of the liquid crystalline dye at the light absorption anisotropic film / alignment film interface), air An additive for controlling the tilt angle of the interface (light absorption anisotropic film / pigment tilt angle at the air interface), a saccharide, a drug having at least one of antifungal, antibacterial and antibacterial functions.
  • wind unevenness inhibitors such as wind unevenness of the alignment film, anti-repellent agents, additives for controlling the tilt angle of the alignment film (tilt angle of the liquid crystalline dye at the light absorption anisotropic film / alignment film interface), air An additive for controlling the tilt angle of the interface (light absorption anisotropic film / pigment tilt angle at the air interface), a saccharide, a drug having at least one of antifungal, antibacterial and antibacterial functions.
  • each additive will be described.
  • the dichroic dye composition used in the present invention may contain a surfactant.
  • the surfactant will be added for the purpose of preventing wind unevenness and the like during application when the composition is prepared as an application liquid and applied.
  • a fluorine-type polymer can be used conveniently. There is no restriction
  • fluoropolymers that can be used as surfactants include JP-A No. 2004-198511, JP-A No. 4190275, JP-A No. 2004-333852, JP-A No.
  • the amount of the surfactant used for the purpose of preventing wind unevenness is generally about 0.1 to 10% by mass with respect to the liquid crystalline azo dye. It is preferably about 0.5 to 10% by mass, more preferably about 0.5 to 5% by mass.
  • a polymer compound can be added as a material for preventing repelling during coating.
  • the polymer compound used for this purpose is not particularly limited as long as it is compatible with the liquid crystalline azo dye and does not significantly inhibit the tilt angle change or orientation of the dye.
  • Examples of polymers that can be used as repellency inhibitors are described in JP-A-8-95030, and specific examples of particularly preferred polymers include cellulose esters. Examples of cellulose esters include cellulose acetate, cellulose acetate propionate, hydroxypropyl cellulose, and cellulose acetate butyrate.
  • the amount of the polymer used for the purpose of preventing repellency is preferably in the range of generally 0.1 to 10% by mass with respect to the liquid crystalline azo dye. It is more preferably in the range of 0.1 to 8% by mass, and still more preferably in the range of 0.1 to 5% by mass.
  • Alignment film tilt angle control agent An additive for controlling the tilt angle of the liquid crystalline azo dye molecules on the alignment film side may be added to the dichroic dye composition.
  • the additive having such an action include compounds having both a polar group and a nonpolar group in the molecule.
  • Compounds having both polar and nonpolar groups in the molecule include P O —OH, P O —COOH, P O —O—P O , P O —NH 2 , P O —NH—P O , P O -SH, P O -S-P O, P O -CO-P O, P O -COO-P O, P O -CONH-P O, P O -CONHCO-P O, P O -SO 3 H , P O —SO 3 —P O , P O —SO 2 NH—P O , P O —SO 2 NHSO 2 —P O , P O —C ⁇ N—P O , HO—P (—OP O ) 2 , (HO-) 2 PO-OP O , P (-OP O ) 3 , HO-PO (-OP O ) 2 , (HO-) 2 PO-OP O , PO (-OP O ) 3 , P O- Preferred examples include NO 2 and P O
  • organic salt in addition to the organic salt of the above compound (for example, ammonium salt, carboxylate, sulfonate, etc.), pyridinium salt and the like can be preferably employed.
  • organic salt in addition to the organic salt of the above compound (for example, ammonium salt, carboxylate, sulfonate, etc.), pyridinium salt and the like can be preferably employed.
  • P O —OH, P O —COOH, P O —O—P O , P O —NH 2 , P O —SO 3 H, HO -PO (-OP O ) 2 , (HO-) 2 PO-OP O , PO (-OP O ) 3 or an organic salt thereof is preferable.
  • each P O represents a nonpolar group, and when there are a plurality of P O , they may be the same or different.
  • an alkyl group preferably a linear, branched or cyclic substituted or unsubstituted alkyl group having 1 to 30 carbon atoms
  • an alkenyl group preferably a linear or branched chain having 1 to 30 carbon atoms, Cyclic substituted or unsubstituted alkenyl groups
  • alkynyl groups preferably linear, branched, cyclic substituted or unsubstituted alkenyl groups having 1 to 30 carbon atoms
  • aryl groups preferably having 6 to 30 carbon atoms.
  • Examples thereof include substituted or unsubstituted aryl groups) and silyl groups (preferably substituted or unsubstituted silyl groups having 3 to 30 carbon atoms). These nonpolar groups may further have a substituent.
  • substituent include a halogen atom, an alkyl group (including a cycloalkyl group and a bicycloalkyl group), an alkenyl group (a cycloalkenyl group and a bicycloalkenyl group).
  • the addition amount of the alignment film tilt angle controlling agent is preferably about 0.0001% by mass to 30% by mass, and preferably 0.001% by mass to 20% by mass with respect to the mass of the liquid crystalline azo dye. More preferably, it is about mass%, more preferably about 0.005 mass% to 10 mass%.
  • the alignment film tilt control agent described in JP-A-2006-58801 can be used.
  • Air interface tilt angle control agent (horizontal alignment agent):
  • the dichroic dye composition used in the present invention preferably contains a horizontal alignment agent as an air interface tilt angle control agent.
  • the horizontal alignment agent used in the present invention is preferably (1) a fluoroaliphatic group-containing compound represented by the following general formula (III); or (2) selected from the group consisting of polymerized units of fluoroaliphatic group-containing monomers represented by general formula (IV) or general formula (V) and polymerized units of amide group-containing monomers represented by general formula (VI) A fluoroaliphatic group-containing copolymer comprising at least one polymerized unit.
  • general formula (III) a fluoroaliphatic group-containing compound represented by the following general formula (III)
  • a fluoroaliphatic group-containing compound represented by the following general formula (III) or (2) selected from the group consisting of polymerized units of fluoroaliphatic group-containing monomers represented by general formula (IV) or general formula (V) and polymerized
  • R 11 , R 22 and R 33 each independently represents an alkoxy group having a CF 3 group or a CF 2 H group at the terminal, and X 11 , X 22 and X 33 each independently represent —NH—, —O— or —S—, and each of m11, m22 and m33 independently represents an integer of 1 to 3.
  • the substituent represented by each of R 11 , R 22 and R 33 is an alkoxy group having a CF 3 group or a CF 2 H group at the terminal, and may be linear or branched. Preferably, it has 4 to 20 carbon atoms, more preferably 4 to 16 carbon atoms, and particularly preferably 6 to 16 carbon atoms.
  • the alkoxy group having a CF 3 group or a CF 2 H group at the terminal is an alkoxy group in which part or all of the hydrogen atoms contained in the alkoxy group are substituted with fluorine atoms.
  • 50% or more of the hydrogen atoms in the alkoxy group are preferably substituted with fluorine atoms, more preferably 60% or more are substituted, and particularly preferably 70% or more are substituted.
  • alkoxy groups having a CF 3 group or a CF 2 H group at the ends represented by R 11 , R 22 and R 33 are shown below.
  • X 11 , X 22 and X 33 each preferably represent —NH— or —O—, and most preferably represents —NH—.
  • m 11 , m 22 and m 33 are each preferably 2.
  • R 1 represents a hydrogen atom, a halogen atom, or a methyl group
  • L 1 represents a divalent linking group
  • m1 represents an integer of 1 to 18.
  • R 2 represents a hydrogen atom, a halogen atom or a methyl group
  • L 2 represents a divalent linking group
  • n1 represents an integer of 1 to 18.
  • R 3 represents a hydrogen atom, a halogen atom or a methyl group
  • R 10 and R 11 are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aromatic group having 6 to 20 carbon atoms or a carbon number. 1 to 20 heterocyclic groups are represented. R 10 and R 11 may be connected to each other to form a heterocyclic ring.
  • R 1 represents a hydrogen atom, a halogen atom or a methyl group, and more preferably a hydrogen atom or a methyl group.
  • L 1 represents a divalent linking group
  • m1 represents an integer of 1 to 18, more preferably 2 to 12, further preferably 4 to 8, and more preferably 4 or 6.
  • R 2 represents a hydrogen atom, a halogen atom or a methyl group, and more preferably a hydrogen atom or a methyl group.
  • L 2 represents a divalent linking group
  • n1 represents an integer of 1 to 18, more preferably 2 to 12, still more preferably 4 to 8, and most preferably 4 or 6.
  • L 1 and L 2 are not limited as long as they are each independently a divalent substituent, but a structure represented by the following general formula (VII) is more preferable.
  • VI general formula
  • (a) shows the position bonded to the double bond side
  • (b) shows the position bonded to the fluoroaliphatic group side.
  • Formula (VII) (A) -X 10 -R 20 - (b)
  • X 10 is a single bond, or * -COO-**, * -COS-**, * -OCO-**, * -CON (R 21 )-**, * -O-.
  • R 20 represents an optionally substituted polymethylene group (eg, methylene group, ethylene group, trimethylene group), an optionally substituted phenylene group (eg, o-phenylene group, m-phenylene group).
  • R 21 represents a hydrogen atom or an alkyl group which may have a substituent having 1 to 8 carbon atoms, or an aryl group which may have a substituent having 6 to 20 carbon atoms.
  • a 1-6 alkyl group is more preferable, and a hydrogen atom or an alkyl group having 1 to 4 carbon atoms is still more preferable.
  • the fluoroaliphatic group-containing monomer represented by the general formula (IV) is more preferably a monomer represented by the following general formula (VIII).
  • X 1 represents a divalent group represented by —O—, —S— or —N (R 222 ) —, and p represents an integer of 1 to 8.
  • X 1 is more preferably —O— or —N (R 222 ) —, and most preferably —O—.
  • p is more preferably from 1 to 6, and still more preferably from 1 to 3.
  • R 1 and m1 have the same meanings as described in the general formula (IV), and preferred ranges are also the same.
  • R 222 represents a hydrogen atom, an alkyl group which may have a substituent having 1 to 8 carbon atoms, or an aryl group which may have a substituent having 6 to 20 carbon atoms.
  • X 2 represents a substituent represented by —O—, —S— or —N (R 222 ) —, and q represents an integer of 1 to 8.
  • X 2 is more preferably —O— or —N (R 222 ) —, and most preferably —O—.
  • p is more preferably from 1 to 6, and still more preferably from 1 to 3.
  • R 2 and n1 have the same meanings as described in the general formula (V), and the preferred ranges are also the same.
  • R 222 has the same meaning as that described in formula (VIII).
  • R 3 represents a hydrogen atom, a halogen atom or a methyl group, more preferably a hydrogen atom or a methyl group.
  • R 10 and R 11 each independently represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aromatic group having 6 to 20 carbon atoms or a heterocyclic group having 1 to 20 carbon atoms, and these substituents are further substituted It may have a group.
  • R 10 and R 11 may be linked to each other to form a heterocyclic ring.
  • the formed heterocyclic ring include a pyrrolidine ring, a piperidine ring, and a morpholine ring.
  • the fluoroaliphatic group-containing copolymer used as the horizontal alignment agent includes both a fluoroaliphatic group-containing monomer and an amide group-containing monomer as polymerized units, and each monomer may include two or more kinds of polymerized units.
  • the copolymer may include one or more other copolymerizable monomers as polymerized units.
  • Other types of such copolymerizable monomers include Polymer Handbook 2nd ed. , J .; Brandrup, Wiley Interscience (1975) Chapter 2, Pages 1-483 can be used. Examples thereof include compounds having one addition polymerizable unsaturated bond selected from acrylic esters, methacrylic esters, methacrylamides, allyl compounds, vinyl ethers, vinyl esters and the like.
  • a preferred mass average molecular weight of the fluoroaliphatic group-containing copolymer used as the horizontal alignment agent is 2000 to 100,000, more preferably 3000 to 80,000, and still more preferably 4,000 to 60,000. 000.
  • the mass average molecular weight and the molecular weight are converted to polystyrene by GTH analyzer using a column of TSKgel GMHxL, TSKgel G4000HxL, TSKgel G2000HxL (both are trade names manufactured by Tosoh Corporation) and detected by a solvent THF and a differential refractometer. Is the molecular weight.
  • the fluoroaliphatic group-containing copolymer that can be used in the present invention as the horizontal alignment agent will be shown, but the present invention is not limited to the following specific examples.
  • the number in a formula shows the mass ratio of each monomer component. Mw represents a mass average molecular weight.
  • horizontal alignment agents described in JP-A-2005-99248, JP-A-2005-134484, JP-A-2006-126768, and JP-A-2006-267183 may be selected.
  • the addition amount of the horizontal alignment agent in the dichroic dye composition is preferably 0.1% by mass to 10% by mass, and 0.5% by mass with respect to the addition amount of the liquid crystalline azo dye. More preferably, it is ⁇ 10% by mass, and particularly preferably 0.5% by mass to 5% by mass.
  • Saccharides may be added to the dichroic dye composition used in the present invention. By adding saccharides, the association degree of the dye aggregate can be improved, and as a result, the molecular orientation of the dye can be increased.
  • saccharides that can be used include monosaccharides, disaccharides, polysaccharides, and sugar derivatives such as sugar alcohols.
  • saccharides in order to achieve the effects of the present invention, those having a hydroxyl group of usually 2 or more, preferably 3 or more, preferably 18 or less, and more preferably 12 or less are preferable from the viewpoint of molecular association.
  • the molecular weight of the saccharide used is preferably 1,000 or less, more preferably 700 or less. If the molecular weight of the saccharide is too large, it is not preferred because it may cause phase separation from the dye and impair the orientation of the dye film.
  • the carbon number of the saccharide used is usually 36 or less, preferably 24 or less. If the saccharide has too many carbon atoms, the molecular weight of the saccharide increases, which causes phase separation from the azo dye, which may impair the orientation of the dye film.
  • monosaccharides include xylose, ribose, glucose, fructose, mannose, sorbose, and galactose.
  • oligosaccharide examples include trehalose, kojibiose, nigerose, maltose, maltotriose, isomaltotriose, maltotetraose, isomaltose, sophorose, laminaribiose, cellobiose, gentiobiose, lactose, sucrose, melibiose, lutinose, primiverose, Examples include turanose, panose, isopanose, cellotriose, manninotriose, soratriose, melezitose, planteose, gentianose, umbelliferose, raffinose, and stachyose.
  • sugar alcohol examples include compounds obtained by reducing the above monosaccharides and oligosaccharides such as threitol, xylitol, ribitol, arabitol, sorbitol, and mannitol.
  • saccharide xylose, mannose, maltose, maltotriose and arabitol are particularly preferable.
  • saccharides and sugar alcohols each have optical isomers, but each of them may be used alone or both may be included in the composition used in the present invention. Moreover, saccharides may be used individually by 1 type in the composition of this invention, and 2 or more types may be used in combination.
  • the saccharide content relative to the liquid crystalline azo dye is preferably in the range of 0.1 or more and 1 or less in terms of mass ratio. More preferably, it is 0.2 or more, particularly preferably 0.3 or more, further preferably 0.7 or less, and particularly preferably 0.6 or less.
  • the association degree of the dye aggregate can be increased without decreasing the degree of orientation of the aggregate.
  • Antifungal, antibacterial and fungicides You may add the chemical
  • a drug having at least one of antifungal, antibacterial, and sterilization functions refers to an antifungal ability that suppresses the generation / growth / growth of mold, a sterilizing ability that kills microorganisms, and a microorganism It means a drug having at least one function of antibacterial ability that suppresses the generation, growth and proliferation of sucrose.
  • Known antifungal agents, bactericides, and antibacterial agents can be used.
  • the optical property of the polarizer formed from the composition is not deteriorated.
  • the drug having at least one of antifungal, antibacterial and bactericidal functions include conventional phenols such as 2,4,4′-trichloro-2′-hydroxydiphenyl, chlorine dioxide and the like. And quaternary ammonium salt systems such as benzalkonium chloride.
  • Proxel BDN Proxel BD20
  • Proxel GXL Proxel LV
  • Proxel XL Proxel XL2
  • Proxel Ultra 10 above, product name
  • Polyhexametylene biguanide hydrochloride as an active ingredient
  • Proxel IB Avecia, trade name
  • Dithio-2,2'-bis (benzmethylamide) as an active ingredient
  • Densil P Avecia, trade name
  • Densil P Avecia, trade name
  • medical agent which has at least any one function of antifungal, antibacterial, and disinfection which can be used by this invention can also be used individually or in combination of 2 or more types.
  • the content of the agent having at least one of antifungal, antibacterial and bactericidal functions in the composition is not particularly limited, but is usually 0.01% by mass or more, preferably 0.001% by mass or more. On the other hand, it is usually 0.5% by mass or less, preferably 0.3% by mass or less.
  • the content of the drug having at least one of antifungal, antibacterial and sterilizing functions is within the above range, sufficient antifungal and antibacterial can be achieved without causing the precipitation of the drug or phase separation during film formation. Or the bactericidal effect is acquired.
  • Electron-Deficient lamellar compounds and Electron-Rich compounds Since the polarizer obtained by the method of the present invention has a high degree of polarization, the composition contains an electron-deficient discotic compound and an electron-rich compound. Is preferred.
  • the electron-deficient discotic compound and the electron-rich compound for example, those described in JP-A-2006-323377 can be used.
  • the ratio of the electron-deficient discotic compound in the composition is usually 0.1 parts by mass or more, preferably 0.2 parts by mass or more, when the total composition is 100 parts by mass. Moreover, it is 50 mass parts or less normally, Preferably it is the range of 40 mass parts or less. When the ratio of the compound is within this range, the effect of addition can be obtained without excessively increasing the viscosity of the composition as a solution. Moreover, the ratio of the electron-rich compound in the composition is usually 50 parts by mass or less, preferably 40 parts by mass or less when the entire composition is 100 parts by mass. When the ratio of the compound is within this range, the effect of addition can be obtained without excessively increasing the viscosity of the composition as a solution.
  • the dichroic dye composition is preferably prepared as a coating solution.
  • the solvent used for preparing the coating solution is preferably an organic solvent.
  • organic solvents include amides (eg, N, N-dimethylformamide), sulfoxides (eg, dimethyl sulfoxide), heterocyclic compounds (eg, pyridine), hydrocarbons (eg, benzene, toluene, hexane) , Alkyl halides (eg, chloroform, dichloromethane), esters (eg, methyl acetate, butyl acetate), ketones (eg, acetone, methyl ethyl ketone), ethers (eg, tetrahydrofuran, 1,2-dimethoxyethane). Hydrocarbons, alkyl halides and ketones are preferred. Two or more organic solvents may be used in combination.
  • the method for preparing the coating solution for the dichroic dye composition is not particularly limited. It is prepared by dissolving the one or more liquid crystalline azo dyes and one or more of the above-mentioned additives (for example, a surfactant, a horizontal alignment agent, etc.) added as desired with a solvent.
  • the coating liquid may not be completely dissolved but may be dispersed.
  • the dichroic dye composition is preferably prepared as a coating solution having a total solid concentration of about 0.1 to 10% by mass, and more preferably about 0.5 to 5% by mass.
  • the coating liquid is prepared in this concentration range, the polarizing layer can be stably formed by a wet film forming method.
  • the dichroic dye composition prepared as a coating solution is applied to the surface to form a coating film.
  • a known and commonly used method such as a spin coating method, a gravure printing method, a flexographic printing method, an ink jet method, a die coating method, a slit die coating method, a cap coating method, or a dipping method can be performed.
  • the solution diluted with the organic solvent is applied, it is dried after application to obtain a coating film.
  • the dichroic dye composition is oriented by evaporating a solute such as an organic solvent from the coating film of the dichroic dye composition.
  • a solute such as an organic solvent from the coating film of the dichroic dye composition.
  • it is naturally dried at room temperature. It is preferable not to disturb the orientation state of the azo dye molecules formed by coating (avoid thermal relaxation or the like). In the pressure reduction treatment, it is also preferable to evaporate the solvent and dry at a lower temperature.
  • depressurization treatment refers to removing a solvent by evaporating a substrate having a coating film under reduced pressure conditions. At this time, it is preferable that the substrate having the film is kept horizontal so that it does not flow from the high part to the bottom part. The shorter the time it takes for the coating film to start the decompression treatment after coating, the better, and it is preferably 1 second to 30 seconds.
  • Examples of the decompression method include the following methods. The coating film obtained by applying the coating solution is put together with the substrate in a reduced pressure processing apparatus and subjected to reduced pressure processing. For example, a decompression processing apparatus as shown in FIGS. 9 and 10 of JP-A-2006-201759 can be used. Details of the decompression processing apparatus are described in JP-A No. 2004-169975.
  • the pressure in the system where the coating film exists is preferably 2 ⁇ 10 4 Pa or less, more preferably 1 ⁇ 10 4 Pa or less, and particularly preferably 1 ⁇ 10 3 Pa or less. Further, it is preferably 1 Pa or more, more preferably 1 ⁇ 10 1 Pa or more.
  • the pressure finally reached in the system is preferably as described above. If the upper limit is exceeded, drying may not be possible and the orientation may be disturbed. If the lower limit is not reached, drying may be too rapid and defects may occur.
  • the decompression time is preferably 5 seconds or more and 180 seconds or less. If it exceeds the upper limit, the coating film cannot be dried rapidly before the orientation relaxation, and the orientation may be disturbed. If it falls below the lower limit, it may not be dried and the orientation may be disturbed.
  • the temperature in the system during the decompression treatment is preferably 10 ° C. or more and 60 ° C. or less. If the upper limit is exceeded, convection may occur during drying, and non-uniformity may occur in the coating film. If the lower limit is not reached, drying may not be possible and orientation may be disturbed.
  • the coating film and orienting the dichroic dye composition When drying the coating film and orienting the dichroic dye composition, it may be heated to promote the orientation.
  • the temperature is preferably 50 ° C. or higher and 200 ° C. or lower, and particularly preferably 70 ° C. or higher and 180 ° C. or lower.
  • an additive such as a plasticizer may be used in combination with the dichroic dye composition.
  • tilt angle means an angle formed between the major axis direction of an azo dye molecule and an interface (alignment film interface or air interface).
  • the preferred tilt angle on the alignment film side is 0 ° to 10 °, more preferably 0 ° to 5 °, particularly preferably 0 ° to 2 °, and still more preferably 0 ° to 1 °.
  • the tilt angle on the air interface side is preferably 0 ° to 10 °, more preferably 0 to 5 °, and particularly preferably 0 to 2 °.
  • the composition comprises (1) a fluoroaliphatic group-containing compound represented by the general formula (III); 2) At least selected from the group consisting of polymerized units of fluoroaliphatic group-containing monomers represented by general formula (IV) or (V) and polymerized units of amide group-containing monomers represented by general formula (VI) It preferably contains a fluoroaliphatic group-containing copolymer containing one kind of polymerized units.
  • the alignment film side tilt angle tends to be reduced by the action of the alignment film as compared with the air interface side tilt angle, but by adding the above-described alignment film tilt control agent to the composition, The tilt angle on the alignment film side can be further reduced, and the azo dye molecules can be stably in a horizontal alignment state.
  • the dichroic dye composition contains a curable component such as the non-liquid crystalline radical polymerizable polyfunctional monomer and the polymerization initiator
  • a curable component such as the non-liquid crystalline radical polymerizable polyfunctional monomer and the polymerization initiator
  • light irradiation preferably ultraviolet irradiation
  • the description in paragraphs [0050] to [0051] of JP-A-2001-91741 can be referred to.
  • the polarizing layer can be formed as described above.
  • the thickness of the polarizing layer is preferably from 0.01 to 2 ⁇ m, more preferably from 0.05 to 2 ⁇ m.
  • an alignment film is preferably used.
  • the alignment film used in the present invention may be any layer as long as the molecules of the liquid crystalline azo dye can be brought into a desired alignment state on the alignment film.
  • Organic compound eg, ⁇ -tricosanoic acid
  • rubbing treatment of organic compound (preferably polymer) film surface oblique deposition of inorganic compound, formation of layer having microgroove, or Langmuir-Blodgett method (LB film) , Dioctadecylmethylammonium chloride, methyl stearylate).
  • an alignment film in which an alignment function is generated by application of an electric field, application of a magnetic field, or light irradiation is also known.
  • an alignment film formed by rubbing treatment is preferable from the viewpoint of easy control of the pretilt angle of the alignment film, and a photo alignment film formed by light irradiation is preferable from the viewpoint of uniformity of alignment.
  • the polymer material used for the alignment film formed by the rubbing treatment is described in a large number of documents, and a large number of commercially available products can be obtained.
  • polyvinyl alcohol or polyimide and derivatives thereof are preferably used.
  • the thickness of the alignment film is preferably 0.01 to 10 ⁇ m, and more preferably 0.01 to 1 ⁇ m.
  • the rubbing treatment can be generally carried out by rubbing the surface of the polymer layer several times with paper or cloth in a certain direction.
  • “Liquid Crystal Handbook” (published by Maruzensha, October 30, 2000). It is preferable to carry out by the method described in (1).
  • a method for changing the rubbing density a method described in “Liquid Crystal Handbook” (published by Maruzen) can be used.
  • the rubbing density (L) is quantified by the following formula (A).
  • N Nl (1 + 2 ⁇ rn / 60v)
  • N is the number of rubbing
  • l is the contact length of the rubbing roller
  • r is the radius of the roller
  • n is the number of rotations (rpm) of the roller
  • v is the stage moving speed (second speed).
  • the rubbing frequency should be increased, the contact length of the rubbing roller should be increased, the radius of the roller should be increased, the rotation speed of the roller should be increased, and the stage moving speed should be decreased, while the rubbing density should be decreased. To do this, you can do the reverse. Between the rubbing density and the pretilt angle of the alignment film, there is a relationship in which the pretilt angle decreases as the rubbing density increases and the pretilt angle increases as the rubbing density decreases.
  • the photo-alignment material used for the alignment film formed by light irradiation has description in many literatures.
  • JP 2006-285197 A, JP 2007-76839 A, JP 2007-138138 A, JP 2007-94071 A, JP 2007-121721 A The azo compounds described in JP-A-2007-140465, JP-A-2007-156439, JP-A-2007-133184, JP-A-2009-109831, JP-A-3888848, and JP-A-4151746, No.
  • the photo-alignment film formed from the above material is irradiated with linearly polarized light or non-polarized light to produce a photo-alignment film.
  • linearly polarized light irradiation is an operation for causing a photoreaction in the photo-alignment material.
  • the wavelength of light used varies depending on the photo-alignment material used, and is not particularly limited as long as it is a wavelength necessary for the photoreaction.
  • the peak wavelength of light used for light irradiation is 200 nm to 700 nm, and more preferably ultraviolet light having a peak wavelength of light of 400 nm or less.
  • the light source used for light irradiation is a commonly used light source such as a tungsten lamp, a halogen lamp, a xenon lamp, a xenon flash lamp, a mercury lamp, a mercury xenon lamp, a carbon arc lamp, or various lasers (eg, semiconductor laser, helium). Neon laser, argon ion laser, helium cadmium laser, YAG laser), light emitting diode, cathode ray tube, and the like.
  • a method using a polarizing plate eg, iodine polarizing plate, dichroic dye polarizing plate, wire grid polarizing plate
  • reflection using a prism-based element eg, Glan-Thompson prism
  • a prism-based element eg, Glan-Thompson prism
  • Brewster angle A method using a type polarizer or a method using light emitted from a laser light source having polarization can be employed.
  • a method of irradiating light from the top surface or the back surface to the alignment film surface perpendicularly or obliquely with respect to the alignment film is employed.
  • the incident angle of the light varies depending on the photo-alignment material, but is, for example, 0 to 90 ° (vertical), preferably 40 to 90.
  • the non-polarized light is irradiated obliquely.
  • the incident angle is 10 to 80 °, preferably 20 to 60, particularly preferably 30 to 50 °.
  • the irradiation time is preferably 1 minute to 60 minutes, more preferably 1 minute to 10 minutes.
  • a method of performing light irradiation using a photomask as many times as necessary for pattern creation or a method of writing a pattern by laser beam scanning can be employed.
  • the light absorption anisotropic film of the present invention may have a transparent resin cured layer on it in order to impart physical strength, durability, or optical properties.
  • the thickness of the transparent resin cured layer is preferably in the range of 1 to 30 ⁇ m, and particularly preferably 1 to 10 ⁇ m.
  • the transparent resin cured layer is preferably formed by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable compound.
  • the transparent resin cured layer in the present invention is obtained by applying a coating composition containing an ionizing radiation-curable polyfunctional monomer or polyfunctional oligomer to the surface of the light absorption anisotropic film, and crosslinking reaction of the polyfunctional monomer or polyfunctional oligomer.
  • the functional group of the ionizing radiation-curable polyfunctional monomer or polyfunctional oligomer is preferably a light, electron beam, or radiation polymerizable group, and among them, a photopolymerizable functional group is preferable.
  • the photopolymerizable functional group include unsaturated polymerizable functional groups such as a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group. Among them, a (meth) acryloyl group is preferable.
  • inorganic fine particles can also be contained.
  • (Meth) acrylic acid diesters of alkylene glycol such as neopentyl glycol acrylate, 1,6-hexanediol (meth) acrylate, propylene glycol di (meth) acrylate
  • (Meth) acrylic acid diesters of polyoxyalkylene glycols such as triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate
  • (Meth) acrylic acid diesters of polyhydric alcohols such as pentaerythritol di (meth) acrylate
  • (Meth) acrylic acid diesters of ethylene oxide or propylene oxide adducts such as 2,2-bis ⁇ 4- (acryloxy-diethoxy) phenyl ⁇ propane and 2-2bis
  • epoxy (meth) acrylates, urethane (meth) acrylates, and polyester (meth) acrylates are also preferably used as the photopolymerizable polyfunctional monomer.
  • esters of polyhydric alcohol and (meth) acrylic acid are preferred. More preferably, a polyfunctional monomer having 3 or more (meth) acryloyl groups in one molecule is preferable.
  • a polymerization initiator used for forming the transparent resin cured layer it is preferable to use a photopolymerization initiator.
  • a photopolymerization initiator a photoradical polymerization initiator and a photocationic polymerization initiator are preferable, and a photoradical polymerization initiator is particularly preferable.
  • the photo radical polymerization initiator include acetophenones, benzophenones, Michler's benzoylbenzoate, ⁇ -amyloxime ester, tetramethylthiuram monosulfide, and thioxanthones.
  • photo radical polymerization initiators include Kayacure (DETX-S, BP-100, BDDK, CTX, BMS, 2-EAQ, ABQ, CPTX, EPD, ITX, QTX, BTC, manufactured by Nippon Kayaku Co., Ltd.
  • Irgacure (651, 184, 127, 500, 907, 369, 1173, 2959, 4265, 4263, etc., all of which are trade names) manufactured by Ciba Specialty Chemicals Co., Ltd.
  • Sartomer Examples include Esacure (KIP100F, KB1, EB3, BP, X33, KT046, KT37, KIP150, TZT, all of which are trade names).
  • photocleavable photoradical polymerization initiators are preferred.
  • the photocleavable photoradical polymerization initiator is described in the latest UV curing technology (P.159, issuer; Kazuhiro Takasawa, publisher; Technical Information Association, published in 1991).
  • Examples of commercially available photocleavable photoradical polymerization initiators include Irgacure (651, 184, 127, 907, trade names) manufactured by Ciba Specialty Chemicals.
  • the photopolymerization initiator is preferably used in the range of 0.1 to 15 parts by mass, more preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the curable resin.
  • a photosensitizer may be used.
  • Specific examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone.
  • Examples of commercially available photosensitizers include KAYACURE (DMBI, EPA, both trade names) manufactured by Nippon Kayaku Co., Ltd.
  • the photopolymerization reaction is preferably carried out by UV irradiation after the application of the high refractive index layer and drying.
  • the transparent resin cured layer may be added with an oligomer or polymer having a mass average molecular weight of 500 or more, or both.
  • the oligomer and polymer include (meth) acrylate-based, cellulose-based, and styrene-based polymers, urethane acrylate, and polyester acrylate.
  • Preferable examples include poly (glycidyl (meth) acrylate) and poly (allyl (meth) acrylate) having a functional group in the side chain.
  • the total amount of oligomer and polymer in the transparent resin cured layer is preferably 5 to 80% by mass, more preferably 25 to 70% by mass, and particularly preferably 35 to 65% by mass with respect to the total mass of the resin layer. is there.
  • the strength of the transparent resin cured layer is preferably H or more, more preferably 2H or more, and even more preferably 3H or more in a pencil hardness test according to JIS K5400. Further, in the Taber test according to JIS K5400, the smaller the wear amount of the test piece before and after the test, the better.
  • the crosslinking reaction or the polymerization reaction is preferably performed in an atmosphere having an oxygen concentration of 10% by volume or less. . By forming in an atmosphere having an oxygen concentration of 10% by volume or less, a transparent resin cured layer excellent in physical strength and durability can be formed, which is preferable.
  • it is formed by a crosslinking reaction or polymerization reaction of an ionizing radiation curable compound in an atmosphere having an oxygen concentration of 6% by volume or less, more preferably an oxygen concentration of 4% by volume or less, particularly preferably an oxygen concentration of 2 It is not more than volume%, more preferably not more than 1 volume%.
  • the transparent resin cured layer may further have a function of optical anisotropy.
  • the transparent resin cured layer can be produced by the following method. First, a curable transparent resin composition containing the above materials is prepared. As a solvent used for preparing the composition, a liquid having a boiling point of 60 to 170 ° C. is preferably used.
  • water eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol
  • ketone eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone
  • ester eg, methyl acetate, ethyl acetate, propyl acetate
  • aliphatic hydrocarbons eg, hexane, cyclohexane
  • halogenated hydrocarbons eg, methylene chloride, chloroform, carbon tetrachloride
  • aromatic hydrocarbons Eg, benzene, toluene, xylene
  • amide eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone
  • ether eg, diethyl
  • toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethanol and butanol are preferred, and particularly preferred dispersion media are methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and ethanol.
  • the amount of the solvent used is preferably such that the solid content concentration of the curable transparent resin composition is 2 to 50% by mass, and more preferably 3 to 40% by mass.
  • the coating method of the light absorption anisotropic film is suitably used, but the following coating method may be used.
  • Specific wet deposition methods include Yuji Harasaki, “Coating Engineering”, Asakura Shoten Co., Ltd., published March 20, 1971, pages 253-277 and “Creation and Application of Molecularly Cooperative Materials” supervised by Kunihiro Ichimura. Company CMC Publishing, published on March 3, 1998, pages 118 to 149, etc., such as spin coating method, spray coating method, slit and spin method, wire bar coating method, roll coating method , Blade coating method, free span coating method, extrusion coating method, direct gravure coating method, reverse gravure coating method, die coating method, and inkjet method.
  • curing is preferably performed by ultraviolet irradiation.
  • the light absorption anisotropic film of the present invention can also be formed on various substrates using a transfer material. Specifically, using a transfer material having a light-absorbing anisotropic film, the light-absorbing anisotropic film may be transferred onto a liquid crystal cell substrate using the transfer material.
  • a transfer material useful for forming the light absorption anisotropic film in a liquid crystal display device, particularly in a liquid crystal cell will be described.
  • the transfer material that can be used in the present invention has at least a support and a film that functions as a light absorption anisotropic film. Furthermore, it is preferable to have at least one photosensitive resin layer on the light absorption anisotropic film.
  • the photosensitive resin layer is useful for facilitating the transfer of the light-absorbing anisotropic film even when the patterning process is not performed.
  • a layer functioning as an alignment layer for controlling the alignment of the dye of the light absorption anisotropic film may be disposed, or both layers may be provided.
  • the support used for the above transfer material may be transparent or opaque and is not particularly limited.
  • the polymer constituting the support include cellulose ester (eg, cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, cellulose acetate butyrate), polyolefin (eg, norbornene-based polymer), poly (Meth) acrylic acid esters (eg, polymethyl methacrylate), polycarbonate, polyester and polysulfone are included.
  • the transparent support is preferably a transparent and low birefringent material, and cellulose ester and norbornene are preferred from the viewpoint of low birefringence.
  • the light absorption anisotropic film is formed on the support or an alignment film formed thereon using the coating method. Note that the light absorption anisotropic film included in the transfer material does not need to satisfy the optical characteristics sufficient for the polarization performance. For example, the polarization performance is manifested or changed through the exposure process performed in the transfer process. And finally, the polarizing performance necessary for the polarizing film may be exhibited.
  • the transfer material preferably has a photosensitive resin layer.
  • the photosensitive resin layer is made of a photosensitive resin composition, and the photosensitive resin layer includes at least (1) an alkali-soluble resin, (2) a monomer or an oligomer, and (3) a photopolymerization initiator or photopolymerization. It is preferable to form from the resin composition containing an initiator system.
  • Alkali-soluble resin (hereinafter sometimes simply referred to as “binder”) is preferably a polymer having a polar group such as a carboxylic acid group or a carboxylic acid group in the side chain. Examples thereof include JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836, and JP-A-57-36.
  • Methacrylic acid copolymer acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer as described in JP-A-59-71048 Etc.
  • the cellulose derivative which has a carboxylic acid group in a side chain can also be mentioned, In addition to this, what added the cyclic acid anhydride to the polymer which has a hydroxyl group can also be used preferably.
  • the binder polymer having these polar groups may be used alone or in the state of a composition used in combination with a normal film-forming polymer, and contained in the total solid content of the photosensitive resin composition.
  • the amount is generally 20 to 50% by mass, preferably 25 to 45% by mass.
  • the monomer or oligomer used in the photosensitive resin layer is preferably a monomer or oligomer that has two or more ethylenically unsaturated double bonds and undergoes addition polymerization by light irradiation.
  • Examples of such monomers and oligomers include compounds having at least one addition-polymerizable ethylenically unsaturated group in the molecule and having a boiling point of 100 ° C. or higher at normal pressure.
  • Examples include monofunctional acrylates and monofunctional methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) ) Acrylate, trimethylolethane triacrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexane All di (meth) acrylate, trimethylolpropane tri (acryloyloxy
  • urethane acrylates described in JP-B-48-41708, JP-B-50-6034 and JP-A-51-37193; JP-A-48-64183, JP-B-49-43191 And polyester acrylates described in Japanese Patent Publication No. 52-30490; polyfunctional acrylates such as epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid, and methacrylates.
  • trimethylolpropane tri (meth) acrylate pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are preferable.
  • polymerizable compound B described in JP-A-11-133600 can also be mentioned as a preferable example. These monomers or oligomers may be used alone or in admixture of two or more.
  • the content of the photosensitive resin composition with respect to the total solid content is generally 5 to 50% by mass, and 10 to 40% by mass. % Is preferred.
  • Photopolymerization initiator or photopolymerization initiator system As the photopolymerization initiator or photopolymerization initiator system used in the photosensitive resin layer, a vicinal poly disclosed in US Pat. No. 2,367,660 is used. Ketaldonyl compounds, acyloin ether compounds described in US Pat. No. 2,448,828, aromatic acyloin compounds substituted with ⁇ -hydrocarbons described in US Pat. No. 2,722,512, US Pat. No. 3,046,127 And a polynuclear quinone compound described in U.S. Pat. No. 2,951,758, a combination of a triarylimidazole dimer described in U.S. Pat. No.
  • photopolymerization initiators or photopolymerization initiator systems may be used singly or as a mixture of two or more, but it is particularly preferable to use two or more. When at least two kinds of photopolymerization initiators are used, display characteristics, particularly display unevenness, can be reduced.
  • the content of the photopolymerization initiator or photopolymerization initiator system with respect to the total solid content of the photosensitive resin composition is generally 0.5 to 20% by mass, and preferably 1 to 15% by mass.
  • thermoplastic resin layer between the support and the alignment film or between the alignment film and the light absorption anisotropic film of the transfer material in order to control the mechanical properties and the unevenness followability.
  • the component used in the thermoplastic resin layer is preferably an organic polymer substance described in JP-A-5-72724, and is a polymer softening point according to the Viker Vicat method (specifically, American Material Testing Method ASTM D1 ASTM D1235). It is particularly preferable that the softening point by the measurement method is selected from organic polymer substances having a temperature of about 80 ° C. or less.
  • polyolefins such as polyethylene and polypropylene, ethylene copolymers such as ethylene and vinyl acetate or saponified products thereof, ethylene and acrylic acid esters or saponified products thereof, polyvinyl chloride, vinyl chloride and vinyl acetate and saponified products thereof.
  • Vinyl chloride copolymer such as fluoride, polyvinylidene chloride, vinylidene chloride copolymer, polystyrene, styrene copolymer such as styrene and (meth) acrylic acid ester or saponified product thereof, polyvinyl toluene, vinyl toluene and (meta ) Vinyl toluene copolymer such as acrylic ester or saponified product thereof, poly (meth) acrylic ester, (meth) acrylic ester copolymer such as butyl (meth) acrylate and vinyl acetate, vinyl acetate copolymer Combined nylon, copolymer nylon, N-alkoxyme Le nylon, and organic polymeric polyamide resins such as N- dimethylamino nylon.
  • an intermediate layer for the purpose of preventing mixing of components during application of a plurality of application layers and during storage after application.
  • an oxygen-blocking film having an oxygen-blocking function described as “separation layer” in JP-A-5-72724. This reduces the time load and improves productivity.
  • the oxygen barrier film is preferably one that exhibits low oxygen permeability and is dispersed or dissolved in water or an aqueous alkali solution, and can be appropriately selected from known ones. Among these, a combination of polyvinyl alcohol and polyvinyl pyrrolidone is particularly preferable.
  • thermoplastic resin layer and the intermediate layer can also be used as the alignment layer.
  • polyvinyl alcohol and polyvinyl pyrrolidone preferably used for the intermediate layer are also effective as an alignment layer, and it is preferable that the intermediate layer and the alignment layer are made into one layer.
  • the protective film may be made of the same or similar material as the temporary support, but must be easily separated from the resin layer.
  • the protective film material for example, silicon paper, polyolefin or polytetrafluoroethylene sheet is suitable.
  • the light absorption anisotropic film, the photosensitive resin layer, the predetermined photo-alignment film, and the thermoplastic resin layer and the intermediate layer formed as desired are the same methods as the method for forming the light absorption anisotropic film. Can be formed. Two or more layers may be applied simultaneously. The methods of simultaneous application are described in US Pat. Nos. 2,761,791, 2,941,898, 3,508,947, and 3,526,528 and Yuji Harasaki, Coating Engineering, page 253, Asakura Shoten (1973).
  • the method for transferring the transfer material to the substrate in the present invention is not particularly limited, and the method is not particularly limited as long as the light absorption anisotropic film and the photosensitive resin layer can be simultaneously transferred onto the substrate.
  • the transfer material referred to in the present invention formed in a film shape is attached by pressing or thermocompression bonding with a roller or flat plate heated and / or pressurized using a laminator with the photosensitive resin layer side facing the substrate surface side. be able to.
  • laminators and laminating methods described in JP-A-7-110575 JP-A-11-77942, JP-A-2000-334836, and JP-A-2002-148794. From this point of view, it is preferable to use the method described in JP-A-7-110575. Thereafter, the support may be peeled off, and another layer such as an electrode layer may be formed on the surface of the light absorption anisotropic film exposed by peeling.
  • the substrate that is a transfer material to which the transfer material is transferred.
  • a soda glass plate having a silicon oxide film on the surface a known glass plate such as a low expansion glass, a non-alkali glass, a quartz glass plate, or a plastic film can be used.
  • the material to be transferred may be one in which a layer such as a color filter is provided on a transparent substrate.
  • the material to be transferred can be well adhered to the photosensitive resin layer by performing a coupling treatment in advance.
  • a method described in JP 2000-39033 A is preferably used.
  • the thickness of the substrate is generally preferably 700 to 1200 ⁇ m.
  • an adhesive layer may be provided on the transfer material.
  • Polarizer Display Device
  • the present invention also relates to a polarizer having a substrate and the light absorption anisotropic film of the present invention on the substrate.
  • substrate The substrate that can be used in the present invention will be selected depending on the application of the polarizer. For example, alkali-free glass, soda glass, Pyrex (registered trademark) glass, quartz glass used for liquid crystal display elements, OLED elements, etc .; photoelectric conversion element substrate used for solid-state imaging elements, etc .; silicon substrate; plastic substrate; And a substrate on which a functional layer such as a transparent conductive film, a color filter film, an electrode and a TFT is formed.
  • a functional layer such as a transparent conductive film, a color filter film, an electrode and a TFT is formed.
  • a black matrix for isolating each pixel may be formed, or a transparent resin layer may be provided for promoting adhesion. It is also preferable that the plastic substrate has a gas barrier layer and / or a solvent resistant layer on the surface thereof.
  • the light transmittance of the substrate used in the present invention is preferably 80% or more.
  • the plastic substrate is preferably an optically isotropic polymer film.
  • the description in paragraph [0013] of JP-A-2002-22294 can be applied.
  • a conventionally known polymer such as polycarbonate or polysulfone that easily develops birefringence is used by reducing the expression by modifying the molecule described in International Publication WO00 / 26705. You can also.
  • the polarizer of the present invention may have an alignment film between the substrate and the light absorption anisotropic film. Examples of alignment films, materials used for formation, and formation methods are as described above.
  • the polarizer of the present invention preferably has a color filter layer between the substrate and the light absorption anisotropic film. In addition to the color filter layer, other functional layers such as a transparent conductive film, a color filter film, an electrode, and a TFT may be included. Further, a black matrix for isolating each pixel may be formed.
  • the polarizer of the present invention may have a transparent resin cured layer on the light absorption anisotropic film. The material used for forming the transparent resin cured layer and the forming method are as described above.
  • the present invention also relates to a display device including at least one light absorption anisotropic film of the present invention.
  • a display device including at least one light absorption anisotropic film of the present invention There is no particular limitation on the configuration and the like. Specifically, transmissive, reflective, or transflective liquid crystal display devices of various modes such as TN, STN, VA, ECB, IPS, and OCB, OLED, and the like can be given.
  • Particularly preferable is a display device having the light absorption anisotropic film of the present invention as a so-called in-cell polarizer formed on the inner surface side of the substrate, and more preferably a color filter substrate of the present invention.
  • This is a display device in which a light absorption anisotropic film is laminated. With such a configuration, it is possible to reduce a decrease in contrast due to scattered light caused by depolarization by the color filter layer.
  • Dichroic ratio was calculated by the following equation after measuring the absorbance of the light-absorbing anisotropic film with a spectrophotometer in which an iodine-based polarizer was arranged in the incident optical system.
  • Dichroic ratio: D Az / Ay Az: Absorbance with respect to polarized light in the direction of the absorption axis of the dye film Ay: Absorbance with respect to polarized light in the direction of the polarization axis of the dye film
  • Example 1 2 parts by mass of azo dye A-1 having the following structure was added to 98 parts by mass of chloroform, dissolved by stirring, and then filtered to obtain a dichroic dye composition coating solution. Next, the coating solution was applied onto the alignment film formed and rubbed on the glass substrate, and then chloroform was naturally dried at room temperature.
  • As the alignment film polyimide (SE-150 manufactured by Nissan Chemical Co., Ltd.) was used. From the absorbance (Az) for polarized light having a vibration plane in the absorption axis direction in the film plane and the absorbance (Ay) for polarized light having a vibration plane in the polarization axis direction in the film plane in the obtained light absorption anisotropic film.
  • Table 1 shows the obtained dichroic ratio (D), the maximum absorption wavelength ( ⁇ max) of the azo dye used, and the phase transition temperature.
  • the azo dye used had nematic liquid crystal properties, and the obtained light absorption anisotropic film had a high dichroic ratio capable of functioning sufficiently as a polarizing film.
  • Example 2 A light absorption anisotropic film was prepared in the same manner as in Example 1 except that the azo dye A-1 was changed to A-2 having the following structure.
  • Table 1 shows the dichroic ratio of the obtained light absorption anisotropic film, and the maximum absorption wavelength and phase transition temperature of the azo dye used.
  • the azo dye used had nematic liquid crystal properties, and the obtained light absorption anisotropic film had a high dichroic ratio capable of functioning sufficiently as a polarizing film.
  • Example 3 A light absorption anisotropic film was prepared in the same manner as in Example 1 except that the azo dye A-1 was changed to A-3 having the following structure.
  • Table 1 shows the dichroic ratio, maximum absorption wavelength, and phase transition temperature of the azo dye used in the obtained light absorption anisotropic film.
  • the azo dye used had nematic liquid crystal properties, and the obtained light absorption anisotropic film had a high dichroic ratio capable of functioning sufficiently as a polarizing film.
  • Example 4 A light absorption anisotropic film was produced in the same manner as in Example 1 except that the azo dye A-1 was changed to A-4 having the following structure.
  • Table 1 shows the dichroic ratio of the obtained light absorption anisotropic film, and the maximum absorption wavelength and phase transition temperature of the azo dye used.
  • the azo dye used had nematic liquid crystal properties, and the obtained light absorption anisotropic film had a high dichroic ratio capable of functioning sufficiently as a polarizing film.
  • Example 5 A light absorption anisotropic film was produced in the same manner as in Example 1 except that the azo dye A-1 was changed to A-14 having the following structure.
  • Table 1 shows the dichroic ratio of the obtained light absorption anisotropic film, and the maximum absorption wavelength and phase transition temperature of the azo dye used.
  • the azo dye used had nematic liquid crystal properties, and the obtained light absorption anisotropic film had a high dichroic ratio capable of functioning sufficiently as a polarizing film.
  • Example 6 A light absorption anisotropic film was prepared in the same manner as in Example 1 except that the azo dye A-1 was changed to A-20 having the following structure. Table 1 shows the dichroic ratio of the obtained light absorption anisotropic film, and the maximum absorption wavelength and phase transition temperature of the azo dye used.
  • the azo dye used had nematic liquid crystal properties, and the obtained light absorption anisotropic film had a high dichroic ratio capable of functioning sufficiently as a polarizing film.
  • Example 7 A light absorption anisotropic film was produced in the same manner as in Example 1 except that the azo dye A-1 was changed to A-27 having the following structure.
  • Table 1 shows the dichroic ratio of the obtained light absorption anisotropic film, and the maximum absorption wavelength and phase transition temperature of the azo dye used.
  • the azo dye used had nematic liquid crystal properties, and the obtained light absorption anisotropic film had a high dichroic ratio capable of functioning sufficiently as a polarizing film.
  • Example 8 A light absorption anisotropic film was produced in the same manner as in Example 1 except that the azo dye A-1 was changed to B-3 having the following structure. Table 1 shows the dichroic ratio of the obtained light absorption anisotropic film, and the maximum absorption wavelength and phase transition temperature of the azo dye used.
  • the azo dye used had nematic liquid crystal properties, and the obtained light absorption anisotropic film had a high dichroic ratio capable of functioning sufficiently as a polarizing film.
  • Example 9 1 part by mass of azo dye A-1 and 1 part by mass of dipentaerythritol hexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) are added to 98 parts by mass of chloroform, and after stirring and dissolving, the mixture is filtered to obtain a dichroic dye composition. A product coating solution was obtained. Next, the coating solution is applied to the rubbing treated surface of the alignment film formed on the glass substrate, and then chloroform is naturally dried at room temperature, and an ultraviolet irradiation device (Execure 3000-w, HOYA). -UV light of 1.8 J / cm 2 was irradiated for 20 seconds using -SCHOTT.
  • KAYARAD DPHA dipentaerythritol hexaacrylate
  • polyimide SE-150 manufactured by Nissan Chemical Co., Ltd.
  • Table 1 shows the obtained dichroic ratio (D), maximum absorption wavelength ( ⁇ max), and phase transition temperature.
  • the azo dye used had nematic liquid crystal properties, and the obtained light absorption anisotropic film had a high dichroic ratio capable of functioning sufficiently as a polarizing film.
  • Example 1 A light-absorbing anisotropic film was prepared in the same manner as in Example 1 except that the azo dye was changed to the compound represented by the following chemical formula C-1 (azo dye No. 6 described in JP-A-11-305036). Table 1 shows the dichroic ratio of the obtained light absorption anisotropic film, and the maximum absorption wavelength and phase transition temperature of the azo dye used. Although the composition had nematic liquid crystallinity, crystallization occurred on the alignment film and no anisotropy was exhibited.
  • Example 10 A dichroic dye B-3 having the following structure was synthesized according to the following synthesis scheme.
  • the compounds represented by the general formulas (2), (4) and (5) can be synthesized by the same method.
  • reaction solution was warmed to room temperature, and the reaction solution was neutralized with sodium bicarbonate, and then the precipitated crystals were filtered and washed with water and methanol. After drying, 5.05 parts of compound 2 were obtained.
  • reaction solution was warmed to room temperature, and the reaction solution was neutralized with sodium bicarbonate, and then the precipitated crystals were filtered and washed with water and methanol. After purification by column chromatography, 0.50 part of azo dye B-3 was obtained. ⁇ max of B-3 in N-methylpyrrolidone solvent was 606.2 nm.
  • Example 11 A dichroic dye B-21 was synthesized according to the same synthesis scheme as in Example 10 except that pyrrolidine was replaced with N- (2-methoxyethyl) methylamine. ⁇ max of B-21 in N-methylpyrrolidone solvent was 584.8 nm.
  • dichroic dye B-23 was synthesized by replacing 4-butylaniline with 4-aminopyridine and pyrrolidine with 2- (methylamino) ethanol. ⁇ max of B-23 in an N-methylpyrrolidone solvent was 618.6 nm.
  • the details of 1 H-NMR (CDCl 3 ) are 8.04 (d, 4H), 7.85 (d, 2H), 7.80 (d, 1H), 7.60 (m, 2H), 7.51 (d, 1H), 7.33 (d, 2H), 6.13 (d, 1H), 3.95 (m, 2H), 3.62 (m, 2H), 3.23 (s , 3H), 2.80 (s, 3H).

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polarising Elements (AREA)
  • Liquid Crystal (AREA)

Abstract

L'invention concerne un film anisotrope pouvant absorber la lumière ayant un rapport dichroïque élevé. Le film anisotrope pouvant absorber la lumière comprend une composition de colorant dichroïque, la composition de colorant dichroïque contenant au moins un composant choisi parmi des colorants azoïques cristallins liquides représentés respectivement par les formules générales (1) et (2), et ne contenant sensiblement pas de composé non-colorant cristallin liquide.
PCT/JP2010/064469 2009-08-28 2010-08-26 Colorant dichroïque, film anisotrope pouvant absorber la lumière, polariseur et son procédé de fabrication, et dispositif d'affichage Ceased WO2011024892A1 (fr)

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JP2013101328A (ja) * 2011-10-12 2013-05-23 Sumitomo Chemical Co Ltd 偏光膜、円偏光板及びそれらの製造方法
CN103360787A (zh) * 2012-03-26 2013-10-23 住友化学株式会社 用于制造偏振膜的组合物及偏振膜
EP2881385A4 (fr) * 2012-08-02 2016-06-29 Bioneer Corp Nouveau composé azo, son utilisation et son procédé de préparation
CN107312124A (zh) * 2016-04-26 2017-11-03 住友化学株式会社 组合物和包含该组合物的光学膜
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JP2024116854A (ja) 2023-02-16 2024-08-28 住友化学株式会社 化合物、組成物、膜、積層体および表示装置

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JP2013101328A (ja) * 2011-10-12 2013-05-23 Sumitomo Chemical Co Ltd 偏光膜、円偏光板及びそれらの製造方法
CN103360787A (zh) * 2012-03-26 2013-10-23 住友化学株式会社 用于制造偏振膜的组合物及偏振膜
CN103360787B (zh) * 2012-03-26 2017-04-26 住友化学株式会社 用于制造偏振膜的组合物及偏振膜
US10167391B2 (en) 2012-08-02 2019-01-01 Bioneer Corporation Azo compound, use thereof and method for preparing same
EP2881385A4 (fr) * 2012-08-02 2016-06-29 Bioneer Corp Nouveau composé azo, son utilisation et son procédé de préparation
CN107312124A (zh) * 2016-04-26 2017-11-03 住友化学株式会社 组合物和包含该组合物的光学膜
WO2019203192A1 (fr) * 2018-04-17 2019-10-24 富士フイルム株式会社 Polariseur, plaque de polarisation circulaire, et dispositif d'affichage d'image
JPWO2019203192A1 (ja) * 2018-04-17 2021-04-22 富士フイルム株式会社 偏光素子、円偏光板および画像表示装置
JP7027531B2 (ja) 2018-04-17 2022-03-01 富士フイルム株式会社 偏光素子、円偏光板および画像表示装置
JP2022078095A (ja) * 2018-04-17 2022-05-24 富士フイルム株式会社 偏光素子、円偏光板および画像表示装置
US11703708B2 (en) 2018-04-17 2023-07-18 Fujifilm Corporation Polarizing element, circularly polarizing plate, and image display device
JP7457739B2 (ja) 2018-04-17 2024-03-28 富士フイルム株式会社 偏光素子、円偏光板および画像表示装置

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