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  • C09K19/00—Liquid crystal materials
  • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
  • C09K19/38—Polymers
  • C09K19/3833—Polymers with mesogenic groups in the side chain
  • C09K19/3842—Polyvinyl derivatives
  • C09K19/3852—Poly(meth)acrylate derivatives
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  • C09K19/00—Liquid crystal materials
  • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
  • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
  • C09K19/56—Aligning agents
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  • C09K19/00—Liquid crystal materials
  • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
  • C09K19/60—Pleochroic dyes
  • C09K19/601—Azoic
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/30—Polarising elements
  • G02B5/3016—Polarising elements involving passive liquid crystal elements
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
  • H05B33/00—Electroluminescent light sources
  • H05B33/02—Details
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  • C09K19/00—Liquid crystal materials
  • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
  • C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
  • C09K2019/0448—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
  • G02F1/133528—Polarisers
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
  • G02F1/13363—Birefringent elements, e.g. for optical compensation
  • G02F1/133638—Waveplates, i.e. plates with a retardation value of lambda/n
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F2413/00—Indexing scheme related to G02F1/13363, i.e. to birefringent elements, e.g. for optical compensation, characterised by the number, position, orientation or value of the compensation plates
  • G02F2413/01—Number of plates being 1
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K50/00—Organic light-emitting devices
  • H10K50/80—Constructional details
  • H10K50/86—Arrangements for improving contrast, e.g. preventing reflection of ambient light
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
  • H10K59/80—Constructional details
  • H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light

Definitions

• the present invention relates to a liquid crystal composition, a light absorption anisotropic film, a laminate, and an image display device.
• Patent Documents 1 and 2 disclose a light absorption anisotropic film formed by using a liquid crystal composition containing a polymer liquid crystal compound and a dichroic substance.
• the present invention provides a liquid crystal composition capable of forming a light absorption anisotropic film having low reflectance, a light absorption anisotropic film obtained by using the liquid crystal composition, a laminate, and an image display device. Make it an issue.
• the present inventors have made a liquid crystal composition containing a side-chain type polymer liquid crystal compound having a repeating unit containing a mesogen group and a repeating unit containing a fluorine atom together with a dichroic substance.
• a light absorption anisotropic film having a low reflectance can be formed by using the above, and have reached the present invention. That is, the present inventors have found that the above problems can be solved by the following configuration.
• a liquid crystal composition containing a side chain type polymer liquid crystal compound and a dichroic substance containing a side chain type polymer liquid crystal compound and a dichroic substance.
• a liquid crystal composition in which a side-chain type polymer liquid crystal compound is a copolymer having a repeating unit M containing a mesogen group and a repeating unit F containing a fluorine atom.
• P1 represents the main chain of the repeating unit
• L1 represents a single bond or a divalent linking group
• SP1 represents a spacer group
• M1 represents a mesogen group containing two or more cyclic structures.
• T1 represent a terminal group.
• P2 represents the main chain of the repeating unit
• L2 represents a single bond or a divalent linking group
• ma and na each independently represent an integer of 0 to 19. However, ma and na represent integers from 0 to 19 in total.
• X represents a hydrogen atom or a fluorine atom.
• a liquid crystal composition capable of forming a light absorption anisotropic film having low reflectance, a light absorption anisotropic film obtained by using the liquid crystal composition, a laminate, and an image display.
• Equipment can be provided.
• the present invention will be described in detail.
• the description of the constituent elements described below may be based on a typical embodiment of the present invention, but the present invention is not limited to such an embodiment.
• the numerical range represented by using “-” means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
• (meth) acrylic acid is a general term for "acrylic acid” and “methacrylic acid”
• (meth) acryloyl is a general term for "acryloyl” and "methacrylic acid”.
• the liquid crystal composition of the present invention is a liquid crystal composition containing a side chain type polymer liquid crystal compound and a dichroic substance. Further, the side chain type polymer liquid crystal compound contained in the liquid crystal composition of the present invention is a copolymer having a repeating unit M containing a mesogen group and a repeating unit F containing a fluorine atom.
• a liquid crystal composition containing a side chain type polymer liquid crystal compound having a repeating unit M containing an anisotropic group and a repeating unit F containing a fluorine atom is used together with a dichroic substance.
• a light absorption anisotropic film containing a dichroic substance often causes reflection at the interface of the film. Therefore, the present inventors tend to unevenly distribute the side-chain type polymer liquid crystal compound in the vicinity of the interface of the light absorption anisotropic film because it has the repeating unit M and the repeating unit F described above. It is also estimated that the reflection at the light absorption anisotropic film interface could be suppressed because the concentration of the dichroic substance existing near the interface decreased.
• each component of the liquid crystal composition of the present invention will be described in detail.
• the side-chain type polymer liquid crystal compound contained in the liquid crystal composition of the present invention is a copolymer having a repeating unit M containing a mesogen group and a repeating unit F containing a fluorine atom.
• the side chain type polymer liquid crystal compound means a polymer liquid crystal compound having a liquid crystal structure in the side chain.
• the side chain type polymer liquid crystal compound may be any polymer such as a block polymer, an alternating polymer, a random polymer, and a graft polymer.
• the side chain type polymer liquid crystal compound may be abbreviated as "polymer liquid crystal compound".
• the substituent W used in the description of the polymer liquid crystal compound represents the following group.
• Specific examples of the substituent W include a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkyl halide group having 1 to 20 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms.
• alkoxy groups alkenyl groups with 1 to 20 carbon atoms, alkynyl groups with 1 to 20 carbon atoms, aryl groups with 1 to 20 carbon atoms, heterocyclic groups (heterocyclic groups), cyano groups, hydroxy groups, nitro groups, Carboxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including anirino group; the same applies hereinafter), ammonio group, acylamino Group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group,
• the repeating unit M is a repeating unit containing a mesogen group.
• the mesogen group is a group showing the main skeleton of the liquid crystal molecule that contributes to the formation of the liquid crystal, and the details are as described by M1 in the formula (1) described later, and specific examples thereof are also the same.
• the repeating unit M is preferably a repeating unit represented by the following formula (1) because the degree of orientation of the light absorption anisotropic film is improved.
• P1 represents the main chain of the repeating unit
• L1 represents a single bond or a divalent linking group
• SP1 represents a spacer group
• M1 represents a mesogen group containing two or more cyclic structures.
• T1 represent a terminal group.
• the main chain of the repeating unit represented by P1 specifically includes, for example, the groups represented by the following formulas (P1-A) to (P1-D), and among them, From the viewpoint of the diversity of the monomer as a raw material and the ease of handling, the group represented by the following formula (P1-A) is preferable.
• R 1 , R 2 , R 3 and R 4 are independently hydrogen atoms, halogen atoms, cyano groups or alkyl groups having 1 to 10 carbon atoms. Represents an alkoxy group having 1 to 10 carbon atoms.
• the alkyl group may be a linear or branched alkyl group, or may be an alkyl group having a cyclic structure (cycloalkyl group).
• the alkyl group preferably has 1 to 5 carbon atoms.
• the group represented by the above formula (P1-A) is preferably one unit of the partial structure of the poly (meth) acrylic acid ester obtained by the polymerization of the (meth) acrylic acid ester.
• the group represented by the above formula (P1-B) is preferably an ethylene glycol unit formed by ring-opening polymerization of the epoxy group of the compound having an epoxy group.
• the group represented by the above formula (P1-C) is preferably a propylene glycol unit formed by ring-opening polymerization of the oxetane group of the compound having an oxetane group.
• the group represented by the above formula (P1-D) is preferably a siloxane unit of polysiloxane obtained by decomposing a compound having at least one of an alkoxysilyl group and a silanol group.
• examples of the compound having at least one of the alkoxysilyl group and the silanol group include a compound having a group represented by the formula SiR 14 (OR 15 ) 2-.
• R 14 is synonymous with R 14 in (P1-D), and the plurality of R 15s independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
• L1 is a single bond or a divalent linking group.
• the divalent linking groups represented by L1 are -C (O) O-, -OC (O)-, -O-, -S-, -C (O) NR 3- , -NR 3 C (O). -, - SO 2 -, and, -NR 3 R 4 -, and the like.
• R 3 and R 4 each independently represent a hydrogen atom and an alkyl group having 1 to 6 carbon atoms which may have a substituent (for example, the above-mentioned substituent W).
• L1 is preferably a group represented by ⁇ C (O) O— for the reason that the degree of orientation of the light absorption anisotropic film is improved. ..
• P1 is a group represented by the formulas (P1-B) to (P1-D)
• L1 is preferably a single bond because the degree of orientation of the light absorption anisotropic film is improved.
• the spacer group represented by SP1 is composed of an oxyethylene structure, an oxypropylene structure, a polysiloxane structure, and a fluorinated alkylene structure because of the tendency to exhibit liquid crystallinity and the availability of raw materials. It preferably contains at least one structure selected from the group.
• oxyethylene structure represented by SP1 is, * - (CH 2 -CH 2 O) n1 - * groups represented by are preferred.
• n1 represents an integer of 1 to 20, and * represents the coupling position with L1 or M1 in the above formula (1).
• n1 is preferably an integer of 2 to 10, more preferably an integer of 2 to 4, and most preferably 3 for the reason that the degree of orientation of the light absorption anisotropic film is improved.
• the oxypropylene structure represented by SP1 is preferably a group represented by *-(CH (CH 3 ) -CH 2 O) n2- * because the degree of orientation of the light absorption anisotropic film is improved.
• n2 represents an integer of 1 to 3
• * represents the connection position with L1 or M1.
• the polysiloxane structure represented by SP1 is preferably a group represented by *-(Si (CH 3 ) 2- O) n3- * because the degree of orientation of the light absorption anisotropic film is improved.
• n3 represents an integer of 6 to 10
• * represents the coupling position with L1 or M1.
• alkylene fluoride structure represented by SP1 because the orientation degree of the light absorption anisotropic film is improved, * - (CF 2 -CF 2 ) n4 - * groups represented by are preferred.
• n4 represents an integer of 6 to 10, and * represents the coupling position with L1 or M1.
• the mesogen group represented by M1 is a group showing the main skeleton of the liquid crystal molecule that contributes to the formation of the liquid crystal.
• the liquid crystal molecule exhibits liquid crystallinity, which is an intermediate state (mesophase) between the crystalline state and the isotropic liquid state.
• the mesogen group is not particularly limited, and for example, "Flusige Kristalle in Tabellen II” (VEB Manual Verlag fur Grundstoff Industrie, Leipzig, 1984), especially the description on pages 7 to 16 and the liquid crystal You can refer to the edition, LCD Handbook (Maruzen, 2000), especially the description in Chapter 3.
• the mesogen group for example, a group having at least one cyclic structure selected from the group consisting of an aromatic hydrocarbon group, a heterocyclic group, and an alicyclic group is preferable.
• the mesogen group preferably has an aromatic hydrocarbon group, more preferably 2 to 4 aromatic hydrocarbon groups, because the degree of orientation of the light absorption anisotropic film is improved. It is more preferable to have an aromatic hydrocarbon group.
• the mesogen group the following formula (M1-A) is used from the viewpoints of developing liquid crystallinity, adjusting the liquid crystal phase transition temperature, availability of raw materials and synthetic suitability, and improving the degree of orientation of the light absorption anisotropic film.
• a group represented by the following formula (M1-B) is preferable, and a group represented by the following formula (M1-B) is more preferable.
• A1 is a divalent group selected from the group consisting of aromatic hydrocarbon groups, heterocyclic groups and alicyclic groups. These groups may be substituted with an alkyl group, an alkyl fluoride group, an alkoxy group or a substituent (for example, the substituent W described above).
• the divalent group represented by A1 is preferably a 4- to 6-membered ring. Further, the divalent group represented by A1 may be a monocyclic ring or a condensed ring. * Represents the binding position with SP1 or T1.
• Examples of the divalent aromatic hydrocarbon group represented by A1 include a phenylene group, a naphthylene group, a fluorene-diyl group, an anthracene-diyl group and a tetracene-diyl group. From the viewpoint of properties and the like, a phenylene group or a naphthylene group is preferable, and a phenylene group is more preferable.
• the divalent heterocyclic group represented by A1 may be either aromatic or non-aromatic, but a divalent aromatic heterocyclic group is preferable from the viewpoint of further improving the degree of orientation. ..
• Examples of atoms other than carbon constituting the divalent aromatic heterocyclic group include nitrogen atom, sulfur atom and oxygen atom.
• the aromatic heterocyclic group has a plurality of atoms constituting a ring other than carbon, they may be the same or different.
• divalent aromatic heterocyclic group examples include a pyridylene group (pyridine-diyl group), a pyridazine-diyl group, an imidazole-diyl group, a thienylene (thiophene-diyl group), and a quinolinene group (quinolin-diyl group).
• Isoquinolylene group isoquinolin-diyl group
• oxazole-diyl group thiazole-diyl group
• oxadiazole-diyl group benzothiazole-diyl group
• benzothiazol-diyl group benzothiazol-diyl group
• phthalimide-diyl group thienothiazole-diyl group
• Thiazorothiazole-diyl group thienothiophene-diyl group
• thienooxazole-diyl group thienooxazole-diyl group and the like.
• divalent alicyclic group represented by A1 examples include a cyclopentylene group and a cyclohexylene group.
• a1 represents an integer of 1 to 10.
• the plurality of A1s may be the same or different.
• A2 and A3 are each independently a divalent group selected from the group consisting of an aromatic hydrocarbon group, a heterocyclic group and an alicyclic group. Specific examples and preferred embodiments of A2 and A3 are the same as those of A1 of the above formula (M1-A), and thus the description thereof will be omitted.
• a2 represents an integer of 1 to 10, and when a2 is 2 or more, a plurality of A2s may be the same or different, and a plurality of A3s may be the same or different.
• the plurality of LA1s may be the same or different.
• a2 is preferably an integer of 2 or more, and more preferably 2 for the reason that the degree of orientation of the light absorption anisotropic film is improved.
• LA1 is a divalent linking group.
• each of the plurality of LA1s is independently a single bond or a divalent linking group, and at least one of the plurality of LA1s is a divalent linking group.
• a2 is 2, it is preferable that one of the two LA1s is a divalent linking group and the other is a single bond because the degree of orientation of the light absorption anisotropic film is improved.
• M1 include the following structures.
• Ac represents an acetyl group.
• the terminal group represented by T1 includes a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxy group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a carbon number of carbon atoms.
• Examples thereof include a sulfinyl group of about 10 and a ureido group having 1 to 10 carbon atoms, a (meth) acryloyloxy group-containing group, and the like.
• Examples of the (meth) acryloyloxy group-containing group include -LA (L represents a single bond or a linking group. Specific examples of the linking group are the same as those of L1 and SP1 described above.
• A is (meth).
• a group represented by (representing an acryloyloxy group) can be mentioned.
• T1 is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 5 carbon atoms, and even more preferably a methoxy group, for the reason that the degree of orientation of the light absorption anisotropic film is improved.
• These terminal groups may be further substituted with these groups or the polymerizable group described in JP-A-2010-244038.
• the number of atoms in the main chain of T1 is preferably 1 to 20, more preferably 1 to 15, further preferably 1 to 10, and particularly preferably 1 to 7 because the degree of orientation of the light absorption anisotropic film is improved. ..
• the "main chain" in T1 means the longest molecular chain bonded to M1, and the hydrogen atom is not counted in the number of atoms in the main chain of T1.
• T1 is an n-butyl group
• the number of atoms in the main chain is 4, and when T1 is a sec-butyl group, the number of atoms in the main chain is 3.
• repeating unit M include a repeating unit represented by the following structural formula.
• the content of the repeating unit M is preferably 25 to 99% by mass, more preferably 50 to 98% by mass, based on the total mass (100% by mass) of the polymer liquid crystal compound.
• the content of each repeating unit contained in the polymer liquid crystal compound is based on the molar ratio of each repeating unit in the polymer measured using an NMR (Nuclear Magnetic Resonance) analyzer. , The calculated value.
• the repeating unit M may be contained alone or in combination of two or more in the polymer liquid crystal compound.
• the polymer liquid crystal compound contains two or more kinds of repeating units M, there are advantages that the solubility of the polymer liquid crystal compound in a solvent is improved and the liquid crystal phase transition temperature can be easily adjusted.
• the total amount thereof is preferably within the above range.
• the terminal group represented by T1 in one (repeating unit A) is an alkoxy group and the other (repeated unit A) is an alkoxy group because the degree of orientation of the light absorption anisotropic film is improved.
• the terminal group represented by T1 in the repeating unit B) is a group other than the alkoxy group.
• the terminal group represented by T1 in the repeating unit B is preferably an alkoxycarbonyl group, a cyano group, or a (meth) acryloyloxy group-containing group because the degree of orientation of the light absorption anisotropic film is improved. It is more preferably an alkoxycarbonyl group or a cyano group.
• the ratio (A / B) of the content of the repeating unit A in the polymer liquid crystal compound and the content of the repeating unit B in the polymer liquid crystal compound improves the degree of orientation of the light absorption anisotropic film. For this reason, it is preferably 50/50 to 95/5, more preferably 60/40 to 93/7, and even more preferably 70/30 to 90/10.
• the repeating unit F is a repeating unit containing a fluorine atom.
• the repeating unit F is preferably a repeating unit represented by the following formula (2) because the reflectance of the light absorption anisotropic film is further reduced, and is a repeating unit represented by the following formula (3). More preferably.
• P2 represents the main chain of the repeating unit
• L2 represents a single bond or a divalent linking group
• L3 represents a divalent hydrocarbon group which may have a substituent. .. However, one or more of -CH 2- constituting the divalent hydrocarbon group may be substituted with -O-, -S-, and -N (Q)-.
• Q represents a hydrogen atom or a substituent.
• X represents a hydrogen atom or a fluorine atom.
• P2 represents the main chain of the repeating unit
• L2 represents a single bond or a divalent linking group
• ma and na each independently represent an integer of 0 to 19. However, ma and na represent integers from 0 to 19 in total.
• X represents a hydrogen atom or a fluorine atom.
• a specific example of the main chain of the repeating unit represented by P2 is the same as that of P1 in the above formula (1), and the preferred embodiment is also the same, and thus the description thereof will be omitted.
• a specific example of the divalent linking group represented by L2 is the same as that of L1 in the above formula (1), and the preferred embodiment is also the same, and thus the description thereof will be omitted.
• a divalent hydrocarbon group represented by L3, which may have a substituent will be described.
• the substituent include the above-mentioned substituent W, and among them, an alkyl halide group is preferable.
• the divalent hydrocarbon group may have, for example, a linear alkylene group having 1 to 18 carbon atoms, a branched or cyclic alkylene group having 3 to 18 carbon atoms, or a substituent. Examples thereof include an arylene group having a number of 6 to 12.
• a linear alkylene group having 1 to 18 carbon atoms is preferable, a linear alkylene group having 1 to 12 carbon atoms is more preferable, and a linear alkylene group having 1 to 6 carbon atoms is preferable. It is more preferable that it is an alkylene group of 1 to 4, and it is particularly preferable that it is a linear alkylene group having 1 to 4 carbon atoms.
• ma and na each independently represent an integer of 0 to 19, but ma is preferably an integer of 1 to 8, and more preferably an integer of 1 to 5. Further, na is preferably an integer of 1 to 15, more preferably an integer of 1 to 12, further preferably an integer of 2 to 10, and most preferably an integer of 5 to 7. ..
• X represents a hydrogen atom or a fluorine atom, and is preferably fluorine.
• HFIPA hexafluoroisopropylacrylamide
• the monomer forming the repeating unit represented by the above formula (3) include 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3. -Pentafluoropropyl (meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, 2- (Perfluorodecyl) ethyl (meth) acrylate, 2- (perfluoro-3-methylbutyl) ethyl (meth) acrylate, 2- (perfluoro-5-methylhexyl) ethyl (meth) acrylate, 2- (perfluoro-) 7-Methyloctyl) ethyl (meth) acrylate, 1H, 1H, 3H-tetrafluor
• the content of the repeating unit F is 50% by mass or less with respect to the total mass of the side chain type polymer liquid crystal compound because the reflectance of the light absorption anisotropic film is further reduced while maintaining good liquid crystal property. It is preferably 40% by mass or less, and further preferably 2 to 40% by mass.
• the weight average molecular weight (Mw) of the polymer liquid crystal compound is preferably 1000 to 500,000, more preferably 2000 to 300,000.
• the handling of the polymer liquid crystal compound becomes easy.
• the weight average molecular weight (Mw) of the polymer liquid crystal compound is preferably 10,000 or more, and more preferably 10,000 to 300,000.
• the weight average molecular weight and the number average molecular weight in the present invention are values measured by a gel permeation chromatography (GPC) method.
• the liquid crystal property of the polymer liquid crystal compound may exhibit either nematic property or smectic property, but it is preferable to exhibit at least nematic property.
• the temperature range showing the nematic phase is preferably room temperature (23 ° C.) to 450 ° C., and more preferably 50 ° C. to 400 ° C. from the viewpoint of handling and manufacturing suitability.
• the content of the polymer liquid crystal compound is 0.5% by mass or more with respect to the total mass of the solid content of the liquid crystal composition because the degree of orientation of the light absorption anisotropic film is improved. It is preferably 1% by mass or more, more preferably 1 to 75% by mass, and particularly preferably 7 to 75% by mass.
• the bicolor substance contained in the liquid crystal composition of the present invention is not particularly limited, and is a visible light absorbing substance (bicolor dye), a luminescent substance (fluorescent substance, a phosphorescent substance), an ultraviolet absorbing substance, an infrared absorbing substance, and a non-linear substance.
• Examples thereof include optical substances, carbon nanotubes, inorganic substances (for example, quantum rods), and conventionally known bicolor substances (bicolor dyes) can be used.
• two or more kinds of dichroic substances may be used in combination.
• at least one kind having a maximum absorption wavelength in the wavelength range of 370 to 550 nm is preferable to use the above dye compound in combination with at least one dye compound having a maximum absorption wavelength in the wavelength range of 500 to 700 nm.
• the dichroic substance has a crosslinkable group for the reason that the pressing resistance is good.
• the crosslinkable group include (meth) acryloyl group, epoxy group, oxetanyl group, styryl group and the like, and among them, (meth) acryloyl group is preferable.
• the content of the dichroic substance is preferably 1 to 50% by mass, more preferably 3 to 45% by mass, and 5 to 40% by mass with respect to the total mass of the solid content of the liquid crystal composition. It is more preferable to have.
• the liquid crystal composition of the present invention contains two or more kinds of dichroic substances, the total amount thereof is preferably within the above range.
• the liquid crystal composition of the present invention is also abbreviated as a liquid crystal compound other than the above-mentioned side chain type polymer liquid crystal compound (hereinafter, also abbreviated as "other liquid crystal compound”) for the reason that the degree of orientation of the light absorption anisotropic film is improved. ) Is preferably contained.
• the other liquid crystal compound either a small molecule liquid crystal compound or a high molecular weight liquid crystal compound can be used.
• the "small molecule liquid crystal compound” refers to a liquid crystal compound having no repeating unit in its chemical structure.
• the "polymer liquid crystal compound” means a liquid crystal compound having a repeating unit in the chemical structure.
• Examples of the small molecule liquid crystal compound include the liquid crystal compound described in JP2013-228706.
• Examples of the polymer liquid crystal compound include thermotropic liquid crystal polymers described in Japanese Patent Application Laid-Open No. 2011-237513. Further, the polymer liquid crystal compound may have a crosslinkable group (for example, an acryloyl group and a methacryloyl group) at the terminal. Other liquid crystal compounds may be used alone or in combination of two or more.
• the difference in logP value ( ⁇ logP) from the side chain type polymer liquid crystal compound described above, which is calculated by the following formula, is ⁇ 5.0 to 5.0. It is preferably -4.0 to 4.0, more preferably -3.5 to 2.5, and particularly preferably -3.2 to 2.2.
• ⁇ logP (logP value of side chain type polymer liquid crystal)-(logP value of liquid crystal compound)
• the logP value is an index expressing the hydrophilic and hydrophobic properties of the chemical structure, and is sometimes called a prohydrophobic parameter.
• the logP value can be calculated using software such as ChemBioDrow Ultra or HSPiP (Ver. 4.1.07).
• a value calculated by inputting the structural formula of the compound into HSPiP (Ver. 4.1.07) is adopted as the logP value.
• the content of the other liquid crystal compound is preferably 1 to 98% by mass with respect to the total mass of the solid content of the liquid crystal composition. It is more preferably 3 to 95% by mass, further preferably 5 to 90% by mass.
• the liquid crystal composition of the present invention preferably contains a polymerization initiator.
• the polymerization initiator is not particularly limited, but a photosensitive compound, that is, a photopolymerization initiator is preferable.
• a photopolymerization initiator various compounds can be used without particular limitation. Examples of photopolymerization initiators include ⁇ -carbonyl compounds (US Pat. Nos. 2,376,661 and 236,670), acidoin ethers (US Pat. No. 2,448,828), and ⁇ -hydrogen-substituted aromatic acidoines. Compounds (US Pat. No. 2722512), polynuclear quinone compounds (US Pat. Nos.
• a photopolymerization initiator commercially available products can also be used, and examples thereof include IRGACURE 184, 907, 369, 651, 819, OXE-01 and OXE-02 manufactured by BASF.
• the content of the polymerization initiator is 100 parts by mass in total of the side chain type polymer liquid crystal compound and the bicolor substance in the liquid crystal composition.
• 0.01 to 30 parts by mass is preferable, and 0.1 to 15 parts by mass is more preferable.
• the content of the polymerization initiator is 0.01 parts by mass or more, the durability of the light absorption anisotropic film is good, and when it is 30 parts by mass or less, the orientation of the light absorption anisotropic film is good. It becomes.
• the liquid crystal composition of the present invention preferably contains a solvent from the viewpoint of workability and the like.
• a solvent for example, ketones (for example, acetone, 2-butanone, methylisobutylketone, cyclopentanone, cyclohexanone, etc.), ethers (for example, dioxane, tetrahydrofuran, 2-methyltetrahexyl, cyclopentylmethyl ether, tetrahydropyran, etc.
• Dioxolane, etc. Dioxolane, etc.), aliphatic hydrocarbons (eg, hexane, etc.), alicyclic hydrocarbons (eg, cyclohexane, etc.), aromatic hydrocarbons (eg, benzene, toluene, xylene, trimethylbenzene, etc.), halogenation Carbons (eg, dichloromethane, trichloromethane, dichloroethane, dichlorobenzene, chlorotoluene, etc.), esters (eg, methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, etc.), alcohols (eg, ethanol, isopropanol, butanol, etc.
• aliphatic hydrocarbons eg, hexane, etc.
• alicyclic hydrocarbons eg, cyclohexane, etc.
• aromatic hydrocarbons
• Cyclohexanol isopentyl alcohol, neopentyl alcohol, diacetone alcohol, benzyl alcohol, etc.
• cellosolves eg, methyl cellosolve, ethyl cellosolve, 1,2-dimethoxyethane, etc.
• cellosolve acetates eg, sulfoxides (eg, dimethyl)
• examples include organic solvents such as sulfoxides), amides (eg, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, etc.), and heterocyclic compounds (eg, pyridine), and water. These solvents may be used alone or in combination of two or more.
• the liquid crystal composition of the present invention contains a solvent
• the content of the solvent is preferably 80 to 99% by mass, more preferably 83 to 98% by mass, and 85 by mass, based on the total mass of the solid content of the liquid crystal composition. It is more preferably ⁇ 96% by mass.
• the liquid crystal composition of the present invention preferably contains an interface improver.
• the smoothness of the coated surface is improved, the degree of orientation is improved, repelling and unevenness are suppressed, and the in-plane uniformity is expected to be improved.
• the interface improver it is preferable to make the liquid crystal compound horizontal on the coated surface side, and the compound (horizontal alignment agent) described in paragraphs [0253] to [0293] of JP2011-237513A can be used. can.
• the fluorine (meth) acrylate-based polymers described in [0018] to [0043] of JP-A-2007-272185 can also be used. Compounds other than these may be used as the interface improver.
• the liquid crystal composition of the present invention contains an interface improver, and the content of the interface improver is 100 parts by mass in total of the side chain type polymer liquid crystal compound and the dichroic substance in the liquid crystal composition. Therefore, 0.001 to 5 parts by mass is preferable, and 0.01 to 3 parts by mass is more preferable.
• the side-chain type polymer liquid crystal compound of the present invention is a side-chain type polymer liquid crystal compound having a repeating unit represented by the above formula (1) and a repeating unit represented by the above formula (3). be.
• the light absorption anisotropic film of the present invention is a light absorption anisotropic film formed by using the liquid crystal composition of the present invention described above.
• Examples of the method for producing a light absorption anisotropic film of the present invention include a step of applying the above liquid crystal composition on a substrate to form a coating film (hereinafter, also referred to as a “coating film forming step”). Examples thereof include a step of orienting a bicolor substance contained in the coating film (hereinafter, also referred to as an “orientation step”) in this order.
• an orientation step a bicolor substance contained in the coating film
• the coating film forming step is a step of applying the above liquid crystal composition onto a substrate to form a coating film. It is easy to apply the liquid crystal composition on the substrate by using the liquid crystal composition containing the above-mentioned solvent or by using a liquid crystal composition such as a molten liquid by heating or the like. Become.
• the coating method of the liquid crystal composition includes a roll coating method, a gravure printing method, a spin coating method, a wire bar coating method, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, a die coating method, a spray method, and an inkjet. Known methods such as a method can be mentioned.
• the liquid crystal composition is applied on the base material, but the present invention is not limited to this, and for example, the liquid crystal composition may be applied on an alignment film provided on the base material. .. Details of the base material and the alignment film will be described later.
• the alignment step is a step of aligning the dichroic substance contained in the coating film. As a result, a light absorption anisotropic film is obtained.
• the orientation step may include a drying process. By the drying treatment, components such as a solvent can be removed from the coating film. The drying treatment may be carried out by a method of leaving the coating film at room temperature for a predetermined time (for example, natural drying), or by a method of heating and / or blowing air.
• the dichroic substance contained in the liquid crystal composition may be oriented by the coating film forming step or the drying treatment described above.
• the coating film is dried to remove the solvent from the coating film to have a light absorption anisotropy (that is, light absorption).
• Anisotropic film is obtained.
• the orientation step preferably includes heat treatment.
• the dichroic substance contained in the coating film can be oriented, so that the coating film after the heat treatment can be suitably used as the light absorption anisotropic film.
• the heat treatment is preferably 10 to 250 ° C., more preferably 25 to 190 ° C. from the viewpoint of manufacturing suitability and the like.
• the heating time is preferably 1 to 300 seconds, more preferably 1 to 60 seconds.
• the orientation step may include a cooling process performed after the heat treatment.
• the cooling treatment is a treatment for cooling the coated film after heating to about room temperature (20 to 25 ° C.).
• the cooling means is not particularly limited, and can be carried out by a known method. By the above steps, a light absorption anisotropic film can be obtained.
• a drying treatment, a heat treatment, and the like are mentioned, but the method is not limited to this, and a known orientation treatment can be used.
• the method for producing a light absorption anisotropic film may include a step of curing the light absorption anisotropic film (hereinafter, also referred to as “curing step”) after the alignment step.
• the curing step is carried out, for example, by heating and / or light irradiation (exposure). Among these, the curing step is preferably carried out by light irradiation.
• the light source used for curing various light sources such as infrared rays, visible light, and ultraviolet rays can be used, but ultraviolet rays are preferable.
• the ultraviolet rays may be irradiated while being heated at the time of curing, or the ultraviolet rays may be irradiated through a filter that transmits only a specific wavelength. Further, the exposure may be performed in a nitrogen atmosphere. When the curing of the light absorption anisotropic film proceeds by radical polymerization, the inhibition of polymerization by oxygen is reduced, so that exposure in a nitrogen atmosphere is preferable.
• the light absorption anisotropic film may have an absorption axis in-plane (hereinafter, also referred to as “horizontal orientation”) or out-of-plane.
• the absorption axis may substantially coincide with the normal of the light absorption anisotropic film plane (hereinafter, also referred to as “vertical orientation”), and 5 ° to 85 ° from the normal. It may be tilted (hereinafter, also referred to as "tilted orientation").
• the absorption axis when the light absorption anisotropic film is horizontally oriented is preferably larger than 85 ° from the normal of the membrane plane, and the absorption axis when the light absorption anisotropic film is vertically oriented is less than 5 ° from the normal of the membrane plane. Is preferable.
• the side-chain type polymer liquid crystal compound contained in the liquid crystal composition of the present invention is suitably used for the light absorption anisotropic film in these three orientation states.
• the degree of orientation of the light absorption anisotropic film is preferably 0.7 or more, more preferably 0.85 or more, and particularly preferably 0.93 or more.
• the degree of orientation is the absorption lightness (hereinafter, also referred to as “Ac”) in polarized light that vibrates in the same plane as the orientation direction of the dichroic substance and in the direction parallel to the long axis of the dichroic substance.
• the absorbed light intensity (hereinafter, also referred to as "Ap”) in polarized light vibrating in the same plane as the orientation direction of the chromatic substance can be measured and calculated from the following formula.
• Degree of orientation (Ap-Ac) / (2Ap + Ac) The measurement of the degree of orientation will be described by taking horizontal orientation as an example. First, a polarizing plate is set on the light source side of the device capable of measuring absorption in the visible region.
• the sample is set on the detection side of the polarizing plate so that the light source light is incident from the normal direction of the light absorption anisotropic membrane plane in the sample, and the absorption spectrum at the position where the absorbance is maximized while rotating the sample. Is measured (Ap). Similarly, the absorption spectrum at the position where the absorbance is minimized is measured (Ac). The degree of orientation is calculated from the above formula using the values of Ap and Ac at a desired wavelength.
• the film thickness of the light absorption anisotropic film is preferably 0.1 to 5.0 ⁇ m, more preferably 0.3 to 1.5 ⁇ m. Although it depends on the concentration of the dichroic substance in the liquid crystal composition, when the film thickness is 0.1 ⁇ m or more, a light absorption anisotropic film having excellent absorbance is obtained, and when the film thickness is 5.0 ⁇ m or less, it is said. A light absorption anisotropic film having excellent transmittance can be obtained.
• the laminate of the present invention has a base material and a light absorption anisotropic film of the present invention provided on the base material. Further, the laminate of the present invention may have a ⁇ / 4 plate on the light absorption anisotropic film. Further, the laminate of the present invention may have an alignment film between the base material and the light absorption anisotropic film. Further, the laminate of the present invention may have a barrier layer between the light absorption anisotropic film and the ⁇ / 4 plate.
• each layer constituting the laminated body of the present invention will be described.
• the base material can be selected according to the application of the light absorption anisotropic film, and examples thereof include glass and polymer films.
• the light transmittance of the base material is preferably 80% or more.
• a polymer film is used as the base material, it is preferable to use an optically isotropic polymer film.
• the description in paragraph [0013] of JP-A-2002-22942 can be applied.
• a polymer whose expression is reduced by modifying the molecule described in International Publication No. 2000/26705 is used. You can also do it.
• the " ⁇ / 4 plate” is a plate having a ⁇ / 4 function, and specifically, a plate having a function of converting linearly polarized light having a specific wavelength into circularly polarized light (or converting circularly polarized light into linearly polarized light).
• examples of the mode in which the ⁇ / 4 plate has a single-layer structure include a stretched polymer film and a retardation film in which an optically anisotropic layer having a ⁇ / 4 function is provided on a support.
• ⁇ / 4 plate has a multi-layer structure
• a wide band ⁇ / 4 plate formed by laminating a ⁇ / 4 plate and a ⁇ / 2 plate can be specifically mentioned.
• the ⁇ / 4 plate and the light absorption anisotropic film may be provided in contact with each other, or another layer may be provided between the ⁇ / 4 plate and the light absorption anisotropic film. .. Examples of such a layer include an adhesive layer or an adhesive layer for ensuring adhesion, and a barrier layer.
• the barrier layer is provided between the light absorption anisotropic film and the ⁇ / 4 plate.
• the barrier layer is, for example, light absorption anisotropic. It can be provided between the sex membrane and another layer.
• the barrier layer is also called a gas blocking layer (oxygen blocking layer), and has a function of protecting the light absorption anisotropic film from gas such as oxygen in the atmosphere, moisture, or a compound contained in an adjacent layer.
• paragraphs [0014] to [0054] of JP-A-2014-159124, paragraphs [0042]-[0075] of JP-A-2017-121721, and paragraphs [0042]-[0075] of JP-A-2017-121507 You can refer to paragraphs 0045] to [0054], paragraphs [0010] to [0061] of JP2012-213938, and paragraphs [0021] to [0031] of JP2005-169994.
• the laminate of the present invention may have an alignment film between the base material and the light absorption anisotropic film.
• the alignment film may be any layer as long as the dichroic substance contained in the liquid crystal composition of the present invention can be in a desired orientation state on the alignment film.
• an alignment film in which an alignment function is generated by applying an electric field, applying a magnetic field, or irradiating light is also known.
• the alignment film formed by the rubbing treatment is preferable from the viewpoint of easy control of the pre-tilt angle of the alignment film, and the photo-alignment film formed by light irradiation is also preferable from the viewpoint of the uniformity of orientation.
• ⁇ Rubbing treatment alignment film> The polymer material used for the alignment film formed by the rubbing treatment has been described in a large number of documents, and a large number of commercially available products can be obtained.
• polyvinyl alcohol or polyimide and its derivatives are preferably used.
• the thickness of the alignment film is preferably 0.01 to 10 ⁇ m, more preferably 0.01 to 1 ⁇ m.
• ⁇ Photo-alignment film> The photo-alignment material used for the alignment film formed by light irradiation is described in many documents.
• Preferred examples thereof include the photocrosslinkable silane derivative described in No. 2003-520878, JP-A-2004-522220, or the photocrosslinkable polyimide, polyamide or ester described in Japanese Patent No. 4162850. More preferably, it is an azo compound, a photocrosslinkable polyimide, a polyamide, or an ester.
• a photo-aligned film formed from the above material is irradiated with linearly polarized light or non-polarized light to produce a photo-aligned film.
• linearly polarized irradiation and “non-polarized irradiation” are operations for causing a photoreaction in a photoaligned material.
• the wavelength of light used varies depending on the photoalignment material used, and is not particularly limited as long as it is a wavelength required for the photoreaction.
• the peak wavelength of the light used for light irradiation is preferably 200 nm to 700 nm, and more preferably ultraviolet light having a peak wavelength of light of 400 nm or less.
• Light sources used for light irradiation are commonly used light sources such as tungsten lamps, halogen lamps, xenon lamps, xenon flash lamps, mercury lamps, mercury xenon lamps and carbon arc lamps, and various lasers [eg, semiconductor lasers, heliums]. Examples include neon lasers, argon ion lasers, helium cadmium lasers and YAG (itrium aluminum garnet) lasers], light emitting diodes, and cathode wire tubes.
• a method using a polarizing plate for example, an iodine polarizing plate, a two-color dye polarizing plate, and a wire grid polarizing plate
• a prism element for example, a Gran Thomson prism
• a Brewster angle is used.
• a method using a polarized reflector or a method using light emitted from a polarized laser light source can be adopted. Further, only light having a required wavelength may be selectively irradiated by using a filter, a wavelength conversion element, or the like.
• the alignment film is irradiated with non-polarized light at an angle.
• the incident angle is preferably 10 to 80 °, more preferably 20 to 60 °, and even more preferably 30 to 50 °.
• the irradiation time is preferably 1 minute to 60 minutes, more preferably 1 minute to 10 minutes.
• the laminate of the present invention can be used as a polarizing element (polarizing plate), for example, as a linear polarizing plate or a circular polarizing plate.
• polarizing plate polarizing plate
• the laminate of the present invention does not have an optically anisotropic layer such as the ⁇ / 4 plate
• the laminate can be used as a linear polarizing plate.
• the laminate of the present invention has the above-mentioned ⁇ / 4 plate
• the laminate can be used as a circularly polarizing plate.
• the image display device of the present invention has the above-mentioned light absorption anisotropic film or the above-mentioned laminate.
• the display element used in the image display device of the present invention is not particularly limited, and examples thereof include a liquid crystal cell, an organic electroluminescence (hereinafter abbreviated as “EL”) display panel, and a plasma display panel.
• EL organic electroluminescence
• a liquid crystal cell or an organic EL display panel is preferable, and a liquid crystal cell is more preferable.
• the image display device of the present invention is preferably a liquid crystal display device using a liquid crystal cell as a display element and an organic EL display device using an organic EL display panel as a display element, and the liquid crystal display device is preferable. More preferred.
• liquid crystal display device As the liquid crystal display device which is an example of the image display device of the present invention, an embodiment having the above-mentioned light absorption anisotropic film and a liquid crystal cell is preferably mentioned. More preferably, it is a liquid crystal display device having the above-mentioned laminate (however, not including the ⁇ / 4 plate) and a liquid crystal cell.
• the light absorption anisotropic films (laminates) provided on both sides of the liquid crystal cell the light absorption anisotropic films (laminates) of the present invention are used as the polarizing element on the front side. It is preferable to use the light absorption anisotropic film (laminated body) of the present invention as the front and rear polarizing elements.
• the liquid crystal cells constituting the liquid crystal display device will be described in detail below.
• the liquid crystal cell used in the liquid crystal display device is preferably a VA (Vertical Element) mode, an OCB (Optically Compensated Bend) mode, an IPS (In-Plane-Switching) mode, or a TN (Twisted Nematic) mode. It is not limited to these.
• the rod-shaped liquid crystal molecules are substantially horizontally oriented when no voltage is applied, and are further twisted to 60 to 120 °.
• the TN mode liquid crystal cell is most often used as a color TFT (Thin Film Transistor) liquid crystal display device, and has been described in many documents.
• the rod-shaped liquid crystal molecules are substantially vertically oriented when no voltage is applied.
• VA mode liquid crystal cell In the VA mode liquid crystal cell, (1) a VA mode liquid crystal cell in a narrow sense in which rod-shaped liquid crystal molecules are oriented substantially vertically when no voltage is applied and substantially horizontally when a voltage is applied (Japanese Patent Laid-Open No. 2-). In addition to (described in Japanese Patent Application Laid-Open No. 176625), (2) a liquid crystal cell (SID97, Digital of technique. Papers (Proceedings) 28 (1997) 845 in which the VA mode is multi-domainized for expanding the viewing angle). ), (3) Liquid crystal cells in a mode (n-ASM mode) in which rod-shaped liquid crystal molecules are substantially vertically oriented when no voltage is applied and twisted and multi-domain oriented when a voltage is applied.
• n-ASM mode Liquid crystal cells in a mode in which rod-shaped liquid crystal molecules are substantially vertically oriented when no voltage is applied and twisted and multi-domain oriented when a voltage is applied.
• SURVIVAL mode liquid crystal cells presented at LCD International 98. Further, it may be any of PVA (Patternized Vertical Alignment) type, optical alignment type (Optical Alignment), and PSA (Polymer-Sustained Alignment). Details of these modes are described in Japanese Patent Application Laid-Open No. 2006-215326 and Japanese Patent Application Laid-Open No. 2008-538819.
• the rod-shaped liquid crystal molecules are oriented substantially parallel to the substrate, and the liquid crystal molecules respond in a plane by applying an electric field parallel to the substrate surface.
• the display In the IPS mode, the display is black when no electric field is applied, and the absorption axes of the pair of upper and lower polarizing plates are orthogonal to each other.
• Methods for reducing leakage light when displaying black in an oblique direction and improving the viewing angle by using an optical compensation sheet are described in JP-A-10-54982, JP-A-11-202323, and JP-A-9-292522. It is disclosed in JP-A-11-133408, JP-A-11-305217, JP-A-10-307291, and the like.
• the organic EL display device which is an example of the image display device of the present invention, includes, for example, a light absorption anisotropic film, a ⁇ / 4 plate, and an organic EL display panel in this order from the viewing side.
• a light absorption anisotropic film e.g., a ⁇ / 4 plate
• an organic EL display panel e.g., a ⁇ / 4 plate
• the above-mentioned laminate having a ⁇ / 4 plate and the organic EL display panel are provided in this order.
• the laminate is arranged in the order of the base material, the alignment film provided as needed, the light absorption anisotropic film, the barrier layer provided as needed, and the ⁇ / 4 plate from the visual side. Has been done.
• the organic EL display panel is a display panel configured by using an organic EL element having an organic light emitting layer (organic electroluminescence layer) sandwiched between electrodes (between a cathode and an anode).
• the configuration of the organic EL display panel is not particularly limited, and a known configuration is adopted.
• FP4 polymer liquid crystal compound represented by the following formula (FP4) was synthesized according to the following scheme.
• 1,3- which contains 10.0 g of a high molecular weight liquid crystal compound (FP4A), 3.2 g of 1-hydroxybenzotriazole (HOBt), and 20.82 ml of N, N-diisopropylethylamine (DIPEA).
• FP4A high molecular weight liquid crystal compound
• HOBt 1-hydroxybenzotriazole
• DIPEA N, N-diisopropylethylamine
• the reaction solution was added to a mixed solvent of hexane and acetone (185 ml), filtered, and the residue was washed with hexane and acetone to obtain 8.6 g of the polymer liquid crystal compound (FP4) as a white solid.
• the weight average molecular weight (Mw) of the obtained polymer liquid crystal compound (FP4) was 21,700.
• Example 1 [Preparation of alignment film]
• the glass substrate manufactured by Central Glass Co., Ltd., blue plate glass, size 300 mm ⁇ 300 mm, thickness 1.1 mm
• the following alignment film forming composition 1 is applied onto a glass substrate after drying using a bar # 12, and the applied alignment film forming composition 1 is dried at 110 ° C. for 2 minutes to form a glass substrate.
• a coating film was formed on top.
• the obtained coating film was subjected to a rubbing treatment (roller rotation speed: 1000 rotations / spacer thickness 2.9 mm, stage speed 1.8 m / min) once to prepare an alignment film 1 on a glass substrate.
• the numerical value in the repeating unit represents the molar% of each repeating unit with respect to all the repeating units in the modified vinyl alcohol.
• a liquid crystal composition 1 having the following composition was spin-coated on the obtained alignment film 1 at 1000 rpm to form a coating film.
• the coating film was heated at 140 ° C. for 40 seconds, and the coating film 1 was cooled to room temperature (23 ° C.). It was then heated at 85 ° C. for 10 seconds and cooled again to room temperature.
• a polarizer (light absorption anisotropic film) 1A was produced on the alignment film A by irradiating with a high-pressure mercury lamp under an irradiation condition of an illuminance of 28 mW / cm 2 for 60 seconds.
• Examples 2 to 8 and Comparative Example 1 A circularly polarizing plate was produced in the same manner as in Example 1 except that the composition of the liquid crystal composition 1 was changed to the composition shown in Table 1 below.
• Example 9 to 15 A polarizer (light absorption anisotropic film) was produced in the same manner as in Example 1 except that the composition of the liquid crystal composition 1 was changed to the composition shown in Table 2 below. Next, the polarizer was further heated at 45 ° C. for 15 minutes and allowed to stand at room temperature for 1 hour to prepare light absorption anisotropic films 9A to 15A. Further, a circularly polarizing plate was produced by the same method as in Example 1 except that the polarizer 1A was changed to the light absorption anisotropic films 9A to 15A.
• Example 16 The optical film B of Example 16 was manufactured as follows.
• Example 17 to 22, Comparative Example 2 Each optical film of Examples 17 to 22 and Comparative Example 2 was prepared in the same manner as the optical film B of Example 16 except that the liquid crystal composition was changed to the liquid crystal composition having the composition shown in Table 3 below. did. In each of the light absorption anisotropic films contained in the optical films of Examples 16 to 22 and Comparative Example 2, the polymer liquid crystal compound and the dichroic substance were vertically oriented.
• Example 23 The light absorption anisotropic film C of Example 23 was produced as follows.
• the surface of the cellulose acylate film 1 (TAC base material having a thickness of 40 ⁇ m; TG40; manufactured by Fuji Film Co., Ltd.) was saponified with an alkaline solution, and the above-mentioned alignment film forming composition 1 was applied thereto with a wire bar.
• the support on which the coating film was formed was dried with warm air at 60 ° C. for 60 seconds and further with warm air at 100 ° C. for 120 seconds to obtain a TAC film with an alignment layer.
• the film thickness was 0.5 ⁇ m.
• the prepared TAC film with an alignment layer was used by rubbing the alignment film surface.
• composition liquid 4 for forming a photo-alignment layer was prepared with the following composition, dissolved for 1 hour with stirring, and filtered through a 0.45 ⁇ m filter.
• composition liquid 4 for forming a photo-alignment layer was applied onto the alignment film and dried at 60 ° C. for 2 minutes to obtain a TAC film with a photo-alignment film.
• the obtained coating film was irradiated with ultraviolet rays (irradiation amount 2000 mJ / cm 2 ) from a polar angle of 30 ° using an ultraviolet exposure device to prepare a transparent support with a photoalignment layer having a thickness of 0.03 ⁇ m.
• ⁇ Preparation of light absorption anisotropic film> The following composition 5 for forming a light absorption anisotropic film was applied to the prepared TAC film with an alignment layer with a wire bar. Next, the coating layer C was heated at 120 ° C. for 30 seconds, and the coating layer P1 was cooled to 100 ° C. Then, a light absorption anisotropic film C was prepared on the alignment layer 1 by irradiating the alignment layer 1 with an LED lamp (center wavelength 365 nm) at room temperature (25 ° C.) under an irradiation condition of 200 mW / cm 2 for 2 seconds. The polymer liquid crystal compound and the dichroic substance contained in the produced light absorption anisotropic film were inclined or oriented with respect to the film thickness direction.
• Composition of Composition 5 for Forming Light Absorption Anisotropy Film ⁇ ⁇ Liquid compound (FP1) 3.382 parts by mass ⁇ Liquid compound L1 3.382 parts by mass ⁇ Bicolor substance Y1 0.370 parts by mass ⁇ Bicolor substance M1 0.089 parts by mass ⁇ Two Color substance C1 0.665 parts by mass, polymerization initiator I1 0.122 parts by mass, interface improver F2 0.003 parts by mass, cyclopentanone 82.800 parts by mass, tetrahydrofuran 9.200 parts by mass --- ⁇
• Examples 24-28 and Comparative Example 3 The light of Examples 24 to 28 and Comparative Example 3 was carried out in the same manner as the photo-orientation anisotropic film C of Example 23 except that the liquid crystal composition was changed to the liquid crystal composition having the composition shown in Table 4 below. An orientation anisotropic film was prepared.
• An adhesive (SK-2057, manufactured by Soken Chemical Co., Ltd.) is applied to the opposite side of the coated surface of each of the light absorption anisotropic films of Examples and Comparative Examples to form an adhesive layer, and Pure Ace WR (Teijin) is formed. (Made by Co., Ltd.) was pasted together. Next, the surface on the Pure Ace WR side was roughened with sandpaper and then treated with black ink to eliminate backside reflection, and the adapter ARV-474 was applied to the spectrophotometer V-550 (manufactured by JASCO Corporation).

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