Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K19/00—Liquid crystal materials
  • C09K19/52—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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/10—Esters
  • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F20/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K19/00—Liquid crystal materials
  • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K19/00—Liquid crystal materials
  • C09K19/52—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
• • 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
• • 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
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
  • G02F1/13363—Birefringent elements, e.g. for optical compensation
• • 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
  • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers

Definitions

• the present invention relates to a polymerizable liquid crystal composition, a polarizing film, a method for producing the same, a polarizing plate, and a display device including the same.
• polarizing plates have been used by being bonded to image display elements such as liquid crystal cells and organic EL display elements in various image display panels such as liquid crystal display panels and organic electroluminescence (organic EL) display panels.
• image display elements such as liquid crystal cells and organic EL display elements
• organic electroluminescence (organic EL) display panels As such a polarizing plate, at least one surface of a polarizer obtained by adsorbing and orienting a dichroic compound such as iodine or a dichroic dye on a polyvinyl alcohol-based resin film, a triacetyl cellulose is bonded via an adhesive layer.
• a polarizing plate having a configuration in which a protective layer such as a film is laminated is known.
• Patent Document 1 and Patent Document 2 a thin host-guest type polarizer composed of a polymerizable liquid crystal compound and a dichroic compound.
• the present invention forms a polarizing film (polarizer) that has a high inhibitory effect on the modification of the dichroic dye when exposed to sunlight and can suppress a decrease in polarization performance over time.
• polarizer polarizing film
• a polymerizable liquid crystal composition comprising a polymerizable liquid crystal compound having at least one polymerizable group and exhibiting smectic liquid crystallinity, a dichroic dye and an antioxidant,
• the polymerizable group possessed by the polymerizable liquid crystal compound is a radical polymerizable group
• the antioxidant is represented by the formula (1) in relation to the polymerizable liquid crystal compound: 0.8 °C ⁇ T1-T2 (1)
• T1 is a liquid crystal that appears on the lowest temperature side when the phase transition temperature is measured while the polymerizable liquid crystal compound is heated to 130 ° C.
• T2 is a phase transition temperature to a phase
• T2 is a mixture of 100 parts by mass of the polymerizable liquid crystal compound and 1 part by mass of the antioxidant. It is the phase transition temperature to the liquid crystal phase that appears at the lowest temperature when the phase transition temperature is measured while cooling to 23 ° C.)
• a polymerizable liquid crystal composition satisfying the requirements.
• the antioxidant is represented by formulas (2), (3) and (4):
• R 1 to R 5 each independently represents —H, —OH, —NH 2 , a branched or unbranched alkyl group having 1 to 12 carbon atoms, or A branched or unbranched alkoxy group having 1 to 12 carbon atoms, and in formulas (2) and (3), at least one of R 1 to R 5 is —OH or —NH 2 , respectively]
• the polymerizable liquid crystal composition according to any one of [1] to [6], wherein the polymerizable liquid crystal composition has any one of structures represented by: [8]
• the antioxidant is represented by the formula (5): A 1 -L 1- (A 2 -L 2 ) n -A 3 (5) [Where: L 1 and L 2 are each independently a single bond or a divalent linking group, A 1 represents formula (2), (3) or (4):
• R 6 to R 9 are each independently —H, —OH, —NH 2 , a branched or unbranched alkyl group having 1 to 12 carbon atoms, or A branched or unbranched alkoxy group having 1 to 12 carbon atoms]
• a group represented by A 3 represents the formula (8) or (9):
• R 10 to R 14 each independently represent —H, —OH, —NH 2 , a branched or unbranched alkyl group having 1 to 12 carbon atoms, or A branched or unbranched alkoxy group having 1 to 12 carbon atoms] Wherein n is an integer of 0 to 2, and when n is 2, two A 2 may be the same or different from each other]
• T1 is a liquid crystal that appears on the lowest temperature
• T2 is a phase transition temperature to a phase
• T2 is a mixture of 100 parts by mass of the polymerizable liquid crystal compound and 1 part by mass of the antioxidant. It is the phase transition temperature to the liquid crystal phase that appears at the lowest temperature when the phase transition temperature is measured while cooling to 23 ° C.) Satisfying the polarizing film.
• the retardation film has the formula (X): 100 ⁇ Re (550) ⁇ 180 (X) [Where Re (550) represents an in-plane retardation value at a wavelength of 550 nm] And the angle formed by the slow axis of the retardation film and the absorption axis of the polarizing film is substantially 45 °.
• the retardation film has the formula (Y): Re (450) / Re (550) ⁇ 1 (Y) [Where Re (450) and Re (550) represent in-plane retardation values at wavelengths of 450 nm and 550 nm, respectively]
• the polarizing plate according to [10] or [11], which satisfies the above.
• the polymerizability suitable for forming a polarizing film having a high inhibitory effect on the modification of the dichroic dye when exposed to sunlight and capable of suppressing a decrease in polarization performance over time can be provided.
• the polymerizable liquid crystal composition of the present invention includes a polymerizable liquid crystal compound having at least one polymerizable group and exhibiting smectic liquid crystallinity (hereinafter also referred to as “polymerizable liquid crystal compound (A)”).
• polymerizable liquid crystal compound (A) By using a polymerizable liquid crystal compound exhibiting smectic liquid crystallinity, a polarizing film having a high degree of alignment order can be formed.
• the liquid crystal state represented by the polymerizable liquid crystal compound (A) is a smectic phase (smectic liquid crystal state), and is more preferably a higher order smectic phase (higher order smectic liquid crystal state) from the viewpoint of realizing a higher degree of alignment order. preferable.
• the higher-order smectic phase means a smectic B phase, a smectic D phase, a smectic E phase, a smectic F phase, a smectic G phase, a smectic H phase, a smectic I phase, a smectic J phase, a smectic K phase, and a smectic L phase.
• the smectic B phase, the smectic F phase, and the smectic I phase are more preferable.
• the thermic liquid crystal may be either a thermotropic liquid crystal or a lyotropic liquid crystal, but the thermotropic liquid crystal is preferred in terms of enabling precise film thickness control.
• the polymerizable liquid crystal compound may be a monomer, but may be an oligomer or a polymer in which a polymerizable group is polymerized.
• the polymerizable liquid crystal compound (A) is a liquid crystal compound having at least one polymerizable group.
• the polymerizable group refers to a group that can participate in a polymerization reaction by an active radical or an acid generated from a polymerization initiator.
• the polymerizable group possessed by the polymerizable liquid crystal compound (A) includes vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, acryloyloxy group, methacryloyloxy group, oxiranyl group, oxetanyl group. Etc.
• a radical polymerizable group is preferable, an acryloyloxy group, a methacryloyloxy group, a vinyl group, and a vinyloxy group are more preferable, an acryloyloxy group and a methacryloyloxy group are further preferable, and an acryloyloxy group is still more preferable.
• the polymerizable liquid crystal compound (A) is not particularly limited as long as it has at least one polymerizable group and exhibits smectic liquid crystal properties, and a known polymerizable liquid crystal compound can be used.
• Examples of the polymerizable liquid crystal compound (A) include a compound represented by the formula (A1) and a polymer of the compound (hereinafter, the compound and the polymer are collectively referred to as “polymerizable liquid crystal compound (A1)”). There are some cases).
• X 1 , X 2 and X 3 each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group, wherein the divalent aromatic group or divalent alicyclic ring
• the hydrogen atom contained in the formula hydrocarbon group is substituted with a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group.
• the carbon atom constituting the divalent aromatic group or divalent alicyclic hydrocarbon group may be substituted with an oxygen atom, a sulfur atom or a nitrogen atom.
• X 1 , X 2 and X 3 is a 1,4-phenylene group which may have a substituent or a cyclohexane-1,4-diyl group which may have a substituent It is.
• Y 1 and Y 2 are each independently a single bond or a divalent linking group.
• U 1 represents a hydrogen atom or a polymerizable group.
• U 2 represents a polymerizable group.
• W 1 and W 2 are each independently a single bond or a divalent linking group.
• V 1 and V 2 each independently represent an optionally substituted alkanediyl group having 1 to 20 carbon atoms, and —CH 2 — constituting the alkanediyl group is —O—, It may be replaced by —CO—, —S— or NH—.
• X 1 , X 2 and X 3 are preferably independent of each other and preferably have a 1,4-phenylene group which may have a substituent or a substituent.
• An optionally cyclohexane-1,4-diyl group, and at least one of X 1 , X 2 and X 3 is a 1,4-phenylene group which may have a substituent, or a substituent
• X 1 and X 3 are preferably a cyclohexane-1,4-diyl group which may have a substituent, and the cyclohexane-1,4-diyl group is trans-cyclohexane- More preferably, it is a 1,4-diyl group.
• Examples of the substituent that the optionally substituted 1,4-phenylene group or the optionally substituted cyclohexane-1,4-diyl group include a methyl group, an ethyl group, And alkyl groups having 1 to 4 carbon atoms such as a butyl group and a cyano group, and halogen atoms such as a chlorine atom and a fluorine atom. Preferably it is unsubstituted.
• Y 1 and Y 2 have the same structure, it is preferable that at least one of X 1 , X 2 and X 3 is a different structure. When at least one of X 1 , X 2 and X 3 has a different structure, smectic liquid crystallinity tends to be easily exhibited.
• R a and R b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
• Y 1 is more preferably —CH 2 CH 2 —, —COO— or a single bond
• Y 2 is more preferably —CH 2 CH 2 — or CH 2 O—.
• Y 1 and Y 2 have different structures.
• smectic liquid crystallinity tends to be easily exhibited.
• U 2 is a polymerizable group.
• U 1 is a hydrogen atom or a polymerizable group, preferably a polymerizable group.
• U 1 and U 2 are preferably both polymerizable groups, and both are preferably radically polymerizable groups.
• Examples of the polymerizable group include the same groups as those exemplified above as the polymerizable group of the polymerizable liquid crystal compound (A).
• the polymerizable group represented by U 1 and the polymerizable group represented by U 2 may be different from each other, but are preferably the same type of group.
• Examples of the alkanediyl group represented by V 1 and V 2 include methylene group, ethylene group, propane-1,3-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, pentane- 1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, decane-1,10-diyl group, tetradecane-1,14-diyl Group and icosane-1,20-diyl group and the like.
• V 1 and V 2 are preferably alkanediyl groups having 2 to 12 carbon atoms, and more preferably alkanediyl groups having 6 to 12 carbon atoms.
• alkanediyl group optionally has include a cyano group and a halogen atom.
• the alkanediyl group is preferably unsubstituted, and is an unsubstituted linear alkanediyl group. Is more preferable.
• W 1 and W 2 independently of each other, a single bond, —O—, —S—, —COO— or —OCOO— is preferable, and a single bond or —O— is more preferable.
• Examples of the polymerizable liquid crystal compound (A1) include compounds represented by formulas (A-1) to (A-25).
• the cyclohexane-1,4-diyl group is preferably a trans isomer.
• formula (A-2), formula (A-3), formula (A-4), formula (A-5), formula (A-6), formula (A-7), formula (A- 8) at least one selected from the group consisting of compounds represented by formula (A-13), formula (A-14), formula (A-15), formula (A-16) and formula (A-17) Species are preferred.
• the polymerizable liquid crystal compound (A1) one type may be used alone, or two or more types may be used in combination.
• Polymerizable liquid crystal compound (A1) is disclosed in Lub et al., Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996), or a known method described in Japanese Patent No. 4719156.
• the polymerizable liquid crystal composition of the present invention may contain a polymerizable liquid crystal compound other than the polymerizable liquid crystal compound (A) as long as the effects of the present invention are not impaired.
• the ratio of the polymerizable liquid crystal compound (A) to the total mass of all polymerizable liquid crystal compounds in the polymerizable liquid crystal composition is preferably 51% by mass or more, more preferably. It is 70 mass% or more, More preferably, it is 90 mass% or more.
• the polymerizable liquid crystal composition of the present invention contains two or more polymerizable liquid crystal compounds (A), at least one of them may be the polymerizable liquid crystal compound (A1), and all of them are polymerizable liquid crystal compounds. (A1) may be sufficient. By combining a plurality of polymerizable liquid crystal compounds, it may be possible to temporarily maintain liquid crystallinity even at a temperature lower than the liquid crystal-crystal phase transition temperature.
• the content of the polymerizable liquid crystal compound in the polymerizable liquid crystal composition of the present invention is preferably 40 to 99.9% by mass, more preferably 60 to 99% by mass, based on the solid content of the polymerizable liquid crystal composition. More preferably, it is 70 to 99% by mass.
• solid content means the total amount of the component remove
• the polymerizable liquid crystal composition of the present invention contains a dichroic dye.
• the dichroic dye means a dye having a property that the absorbance in the major axis direction of the molecule is different from the absorbance in the minor axis direction.
• the dichroic dye that can be used in the present invention is not particularly limited as long as it has the above properties, and may be a dye or a pigment. Two or more dyes or pigments may be used in combination, or a dye and pigment may be used in combination.
• dichroic dye those having a maximum absorption wavelength ( ⁇ MAX ) in the range of 300 to 700 nm are preferable.
• dichroic dyes include acridine dyes, oxazine dyes, cyanine dyes, naphthalene dyes, azo dyes and anthraquinone dyes.
• K 2 is an optionally substituted p-phenylene group, an optionally substituted naphthalene-1,4-diyl group, or an optionally substituted divalent heterocyclic ring. Represents a group.
• p represents an integer of 1 to 4. When p is an integer greater than or equal to 2 , several K2 may mutually be same or different.
• the —N ⁇ N— bond may be replaced with a —C ⁇ C—, —COO—, —NHCO—, or —N ⁇ CH— bond within the visible absorption range.
• Examples of the monovalent heterocyclic group include groups in which one hydrogen atom has been removed from a heterocyclic compound such as quinoline, thiazole, benzothiazole, thienothiazole, imidazole, benzimidazole, oxazole, and benzoxazole.
• Examples of the divalent heterocyclic group include groups in which two hydrogen atoms have been removed from the heterocyclic compound.
• naphthalene-1,4-diyl group and divalent heterocyclic group in K 2 optionally have Is an alkyl group having 1 to 4 carbon atoms; an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, or a butoxy group; a fluorinated alkyl group having 1 to 4 carbon atoms such as a trifluoromethyl group; a cyano group; Nitro group; halogen atom; substituted or unsubstituted amino group such as amino group, diethylamino group, pyrrolidino group (substituted amino group is an amino group having one or two alkyl groups having 1 to 6 carbon atoms, or two An amino group in which substituted alkyl groups are bonded to each other to form an alkanediy
• B 1 to B 30 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, a nitro group, a substituted or unsubstituted amino group (substituted amino group). And the definition of the unsubstituted amino group is as described above), and represents a chlorine atom or a trifluoromethyl group.
• n1 to n4 each independently represents an integer of 0 to 3.
• the plurality of B 2 when n1 is 2 or more, the plurality of B 2 may be the same as or different from each other; when n2 is 2 or more, the plurality of B 6 may be the same as or different from each other; when n3 is 2 or more, the plurality of B 9 may be the same as or different from each other; When n4 is 2 or more, the plurality of B 14 may be the same as or different from each other. ]
• the anthraquinone dye is preferably a compound represented by the formula (I-9).
• R 1 to R 8 each independently represent a hydrogen atom, —R x , —NH 2 , —NHR x , —NR x 2 , —SR x or a halogen atom.
• R x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms.
• the oxazone dye is preferably a compound represented by the formula (I-10).
• R 9 to R 15 each independently represent a hydrogen atom, —R x , —NH 2 , —NHR x , —NR x 2 , —SR x or a halogen atom.
• R x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms.
• the acridine dye is preferably a compound represented by the formula (I-11).
• R 16 to R 23 each independently represent a hydrogen atom, —R x , —NH 2 , —NHR x , —NR x 2 , —SR x or a halogen atom.
• R x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms.
• the alkyl group having 1 to 6 carbon atoms of R x is a methyl group, an ethyl group, a propyl group, a butyl group or a pentyl group. And a hexyl group.
• the aryl group having 6 to 12 carbon atoms include a phenyl group, a toluyl group, a xylyl group, and a naphthyl group.
• cyanine dye a compound represented by the formula (I-12) and a compound represented by the formula (I-13) are preferable.
• D 1 and D 2 each independently represent a group represented by any one of formulas (I-12a) to (I-12d).
• n5 represents an integer of 1 to 3.
• D 3 and D 4 each independently represent a group represented by any one of formulas (I-13a) to (1-13h).
• n6 represents an integer of 1 to 3.
• the polymerizable liquid crystal composition of the present invention is excellent in the effect of suppressing the light deterioration of the dichroic dye in the polarizing film when the polarizing film is formed, it is weak to light such as ultraviolet rays in sunlight, and the light deterioration In the case of using a dichroic dye that is likely to cause the effects of the present invention, the effects of the present invention can be exhibited particularly remarkably. Therefore, the polymerizable liquid crystal composition of the present invention is particularly advantageous when a dichroic dye that easily causes photodegradation is used.
• the dichroic dye contained in the polymerizable liquid crystal composition of the present invention is preferably an azo dye.
• the content of the dichroic dye in the polymerizable liquid crystal composition of the present invention can be appropriately determined according to the type of the dichroic dye to be used, etc., but preferably 0.1% with respect to 100 parts by mass of the polymerizable liquid crystal compound.
• the amount is 1 to 50 parts by mass, more preferably 0.1 to 20 parts by mass, and still more preferably 0.1 to 12 parts by mass.
• the content of the dichroic dye is within the above range, it is difficult to disturb the alignment of the polymerizable liquid crystal compound, and a polarizing film having a high degree of alignment order can be obtained.
• the polymerizable liquid crystal composition of the present invention contains an antioxidant.
• the antioxidant is represented by the formula (1) in relation to the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition: 0.8 °C ⁇ T1-T2 (1) Meet.
• T1 indicates the phase transition temperature while the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition is heated to 130 ° C. in the air and then cooled to 23 ° C. at 5 ° C./min. This is the phase transition temperature to the liquid crystal phase that appears on the lowest temperature side when measured.
• T2 is a phase transition in which a mixture of 100 parts by mass of the polymerizable liquid crystal compound and 1 part by mass of the antioxidant is heated to 130 ° C. in the air and then cooled to 23 ° C. at 5 ° C./min. This is the phase transition temperature to the liquid crystal phase that appears on the lowest temperature side when the temperature is measured.
• T1 and T2 are polymerizable liquid crystal compounds having the same composition as the polymerizable liquid crystal compound constituting the polymerizable liquid crystal composition ( Mixture).
• the detailed measurement method of T1 and T2 is as described in Examples described later.
• T1-T2 is an index representing the influence of the antioxidant on the phase transition temperature in the liquid crystal state. The larger the value of T1-T2, the more similar the polymerizable liquid crystal compound and the antioxidant are in the molecular structure, and they exist in a more mixed state in the liquid crystal state, and the antioxidant is aligned with the polymerizable liquid crystal compound.
• T1-T2 the closer the intermolecular distance between the dichroic dye and the antioxidant that are contained in the polymerizable liquid crystal compound, and the higher the suppression of photodegradation of the dichroic dye. It is presumed that a polarizing film having a high degree of orientational order can be obtained while exhibiting the effect and hardly disturbing the orientation of the polymerizable liquid crystal compound.
• the value of T1-T2 is 0.8 ° C. or higher, preferably 0.9 ° C. or higher, more preferably 1.0 ° C. or higher. Yes, more preferably 1.2 ° C or higher, particularly preferably 1.5 ° C or higher. If the value of T1-T2 is less than 0.8 ° C., the molecular structure of the polymerizable liquid crystal compound and the molecular structure of the antioxidant are greatly different, and the antioxidant is aligned with the polymerizable liquid crystal compound in a high degree of order. It is difficult. As a result, it is difficult to sufficiently exhibit the effect of suppressing light deterioration with respect to the dichroic dye.
• the value of T1-T2 is within the above range, an antioxidant can be disposed in the vicinity of the dichroic dye included in the polymerizable liquid crystal compound, and a high suppression effect on the decrease in polarization performance can be obtained. I can expect.
• the upper limit value of T1-T2 is not particularly limited, but is usually 35 ° C. or lower, preferably 30 ° C. or lower, more preferably 25 ° C. or lower.
• the antioxidant is not particularly limited as long as it satisfies the above formula (1) with the polymerizable liquid crystal compound and can exhibit the effects of the present invention. Can be used. From the viewpoint of having a high inhibitory effect on photodegradation of the dichroic dye, a so-called primary antioxidant having a function of capturing radicals and preventing auto-oxidation is preferable. Therefore, the antioxidant contained in the polymerizable liquid crystal composition of the present invention is more preferably at least one selected from the group consisting of phenolic compounds, alicyclic alcohol compounds, and amine compounds. An antioxidant may be used individually by 1 type, or may be used in combination of 2 or more type.
• antioxidants selected from the group consisting of phenolic compounds, alicyclic alcohol compounds and amine compounds include, for example, formulas (2), (3) and (4):
• R 1 to R 5 each independently represent —H, —OH, —NH 2 , a branched or unbranched alkyl group having 1 to 12 carbon atoms, or carbon A branched or unbranched alkoxy group of formula 1 to 12, and in formulas (2) and (3), at least one of R 1 to R 5 is —OH or —NH 2 , respectively.
• Examples of the branched or unbranched alkyl group having 1 to 12 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, tert-butyl group, pentyl group, hexyl group, 2-ethylhexyl group, heptyl group Octyl group, nonyl group, decyl group, undecyl group, dodecyl group and the like.
• Examples of the branched or unbranched alkoxy group having 1 to 12 carbon atoms include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, A decyloxy group, an undecyloxy group, a dodecyloxy group, etc. are mentioned.
• R 1 to R 5 is preferably present in R 1, in which case R 2 to R 5 are H is more preferably a branched or unbranched alkyl group having 1 to 12 carbon atoms, or a branched or unbranched alkoxy group having 1 to 12 carbon atoms, and more preferably —H.
• antioxidants having the structure represented by the above formula (2), (3) or (4) include, for example, the formula (5): A 1 -L 1- (A 2 -L 2 ) n -A 3 (5) The compound shown by these is mentioned.
• L 1 and L 2 are each independently a single bond or a divalent linking group.
• a 1 is a group represented by the above formula (2), (3) or (4).
• a 2 represents formula (6) or (7):
• R 6 to R 9 are each independently —H, —OH, —NH 2 , a branched or unbranched alkyl group having 1 to 12 carbon atoms, or A branched or unbranched alkoxy group having 1 to 12 carbon atoms] It is group represented by these.
• a 3 represents the formula (8) or (9):
• R 10 to R 14 each independently represent —H, —OH, —NH 2 , a branched or unbranched alkyl group having 1 to 12 carbon atoms, or A branched or unbranched alkoxy group having 1 to 12 carbon atoms] It is group represented by these.
• n is an integer of 0 to 2, and when n is 2, two A 2 may be the same or different from each other.
• L 1 and L 2 examples include a single bond, an ether group, a carbonyl group, an ester group, an amide group, and an azo group.
• L 1 and L 2 are preferably a bond type that does not absorb visible light as an antioxidant, more preferably a single bond, an ether group, and an ester group, and particularly preferably a single bond and an ether group.
• a 1 includes the same groups as those exemplified above as the structures represented by the above formulas (2), (3) and (4), and the groups represented by the formula (2) or (4) And more preferably a group represented by the formula (2), R 1 is —OH, and R 2 to R 5 are each independently —H or —CH 3. Is more preferable, and it is particularly preferable that all of R 2 to R 5 are —H.
• R 6 to R 9 are each independently preferably —H or —CH 3 , more preferably —H, and still more preferably all of R 6 to R 9 are —H or —CH 3 , particularly preferably all of R 6 to R 9 are —H.
• R 12 is a branched or unbranched alkyl group having 1 to 12 carbon atoms, or a branched or unbranched alkoxy group having 1 to 12 carbon atoms
• R 10 , R 11 , R 13 and R 14 is preferably independently —H or —CH 3 , and it is particularly preferred that all of R 10 , R 11 , R 13 and R 14 are —H.
• the weight average molecular weight of antioxidant is 600 or less, More preferably, it is 500 or less, More preferably, it is 450 or less.
• the weight average molecular weight of the antioxidant is 600 or less, the antioxidant can be disposed in the vicinity of the dichroic dye without greatly disturbing the orientation of the polymerizable liquid crystal compound. The deterioration suppressing effect can be further improved.
• the weight average molecular weight of the antioxidant is 400 or less, since it becomes difficult to absorb in the visible light wavelength region, and a decrease in polarization performance can be more effectively reduced.
• examples of the antioxidant include the following compounds.
• an antioxidant having a small steric hindrance and a high linearity as a molecular structure is preferable because it tends to be aligned with the polymerizable liquid crystal compound and is excellent in the effect of suppressing photodegradation of the dichroic dye.
• the antioxidant in the polymerizable liquid crystal composition of the present invention is not limited to this, but 4-n-octyloxyphenol, 4-n-decyloxyphenol, 4-n-dodecyloxyphenol, 4, 4′-biphenol, 4-ethoxy-4′-hydroxybiphenyl, 4-butoxy-4′-hydroxybiphenyl, 4-octyloxy-4′-hydroxybiphenyl, 4-decyloxy-4′-hydroxybiphenyl, 4-dodecyloxy-4 '-Hydroxybiphenyl is preferred.
• the content of the antioxidant in the polymerizable liquid crystal composition of the present invention is preferably 0.1 to 15 parts by mass, more preferably 0.3 parts by mass or more, with respect to 100 parts by mass of the polymerizable liquid crystal compound. More preferably, it is 0.5 mass part or more, More preferably, it is 12 mass parts or less, More preferably, it is 8 mass parts or less, Most preferably, it is 4 mass parts or less.
• the content of the antioxidant is not less than the above lower limit value, it is possible to effectively suppress the photodegradation of the dichroic dye.
• the content of the antioxidant is not more than the above upper limit value, it is difficult to disturb the orientation of the polymerizable liquid crystal compound, and a high inhibitory effect on photodegradation of the dichroic dye can be expected.
• the polymerizable liquid crystal composition of the present invention may contain a polymerization initiator.
• the polymerization initiator is a compound capable of initiating a polymerization reaction of the polymerizable liquid crystal compound, and a photopolymerization initiator is preferable in that the polymerization reaction can be initiated under a lower temperature condition.
• Specific examples include photopolymerization initiators that can generate active radicals or acids by the action of light. Among these, photopolymerization initiators that generate radicals by the action of light are preferred.
• a polymerization initiator can be used individually or in combination of 2 or more types.
• polymerization initiator examples include benzoin compounds, benzophenone compounds, alkylphenone compounds, acylphosphine oxide compounds, triazine compounds, iodonium salts, and sulfonium salts.
• benzoin compound examples include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.
• benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone And 2,4,6-trimethylbenzophenone.
• alkylphenone compound examples include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) butane.
• -1-one 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1,2-diphenyl-2,2-dimethoxyethane-1-one, 2-hydroxy-2-methyl-1- [ 4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one
• An oligomer etc. are mentioned.
• acylphosphine oxide compound examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide.
• triazine compounds examples include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1 , 3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine and 2,4-bis (
• a commercially available polymerization initiator can be used.
• examples of commercially available polymerization initiators include “Irgacure (registered trademark) 907”, “Irgacure (registered trademark) 184”, “Irgacure (registered trademark) 651”, “Irgacure (registered trademark) 819”, “ “Irgacure (registered trademark) 250", “Irgacure (registered trademark) 369” (Ciba Japan Co., Ltd.); “Sequor (registered trademark) BZ", “Sequor (registered trademark) Z", “Sequor (registered trademark) BEE” "Kayacure (registered trademark) BP100" (Nippon Kayaku Co., Ltd.); “Kayacure (registered trademark) UVI-6992" (manufactured by Dow); “Adekaoptomer SP” -152 ”,“ Adekaoptomer SP
• the content may be appropriately determined according to the type and amount of the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition.
• the amount is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 10 parts by mass, and still more preferably 0.5 to 8 parts by mass with respect to 100 parts by mass of the compound.
• the content of the polymerizable initiator is within the above range, the polymerization can be performed without disturbing the alignment of the polymerizable liquid crystal compound.
• the polymerizable liquid crystal composition may further contain a photosensitizer.
• a photosensitizer By using a photosensitizer, the polymerization reaction of the polymerizable liquid crystal compound can be further promoted.
• Photosensitizers include xanthone compounds such as xanthone and thioxanthone (2,4-diethylthioxanthone, 2-isopropylthioxanthone, etc.); anthracene compounds such as anthracene and alkoxy group-containing anthracene (such as dibutoxyanthracene); phenothiazine and rubrene, etc. Is mentioned.
• a photosensitizer can be used individually or in combination of 2 or more types.
• the content of the photosensitizer in the polymerizable liquid crystal composition of the present invention may be appropriately determined according to the type and amount of the photopolymerization initiator and the polymerizable liquid crystal compound. On the other hand, 0.1 to 30 parts by mass is preferable, 0.5 to 10 parts by mass is more preferable, and 0.5 to 8 parts by mass is further preferable.
• the polymerizable liquid crystal composition of the present invention may contain a leveling agent.
• the leveling agent has the function of adjusting the fluidity of the polymerizable liquid crystal composition and flattening the coating film obtained by applying the polymerizable liquid crystal composition.
• a leveling agent at least 1 sort (s) chosen from the group which consists of a leveling agent which has a polyacrylate compound as a main component, and a leveling agent which has a fluorine atom containing compound as a main component is preferable.
• Leveling agents can be used alone or in combination of two or more.
• Leveling agents mainly composed of polyacrylate compounds include “BYK-350”, “BYK-352”, “BYK-353”, “BYK-354”, “BYK-355”, “BYK-358N”, “ BYK-361N ”,“ BYK-380 ”,“ BYK-381 ”,“ BYK-392 ”(BYK Chemie) and the like.
• Leveling agents mainly composed of fluorine atom-containing compounds include “Megafac (registered trademark) R-08”, “R-30”, “R-90”, “F-410”, and “F”. -411 ",” F-443 “,” F-445 “,” F-470 “,” F-471 “,” F-477 “,” F-479 “,” F- “ 482 “and” F-483 “(DIC Corporation);” Surflon (registered trademark) S-381 “,” S-382 “,” S-383 “,” S-393 “,” “SC-101", “SC-105", “KH-40” and “SA-100” (AGC Seimi Chemical Co., Ltd.); “E1830", “E5844” (Daikin Fine Chemical Laboratory Co., Ltd.); F-top EF301 “,” F-top EF303 “,” F-top E 351 “and” EFTOP EF352 "(Mitsubishi Materials Electronic Chemicals Co.) and the like.
• the content of the leveling agent in the polymerizable liquid crystal composition of the present invention is preferably 0.05 to 5 parts by mass, more preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound.
• the content of the leveling agent is within the above range, the polymerizable liquid crystal compound is easily horizontally aligned, and unevenness hardly occurs, and a smoother polarizing film tends to be obtained.
• the polymerizable liquid crystal composition of the present invention may contain additives other than the polymerization initiator, the photosensitizer, and the leveling agent.
• additives include colorants such as mold release agents, stabilizers, and bluing agents, flame retardants, and lubricants.
• the content of the other additive is preferably more than 0% and 20% by mass or less with respect to the solid content of the polymerizable liquid crystal composition. More preferably, it is more than 0% and 10% by mass or less.
• the polymerizable liquid crystal composition of the present invention may contain a solvent.
• a solvent since a compound exhibiting smectic liquid crystallinity has a high viscosity, it can be easily applied by adding a solvent to the polymerizable liquid crystal composition, and as a result, a polarizing film can be easily formed.
• the solvent can be appropriately selected according to the solubility of the polymerizable liquid crystal compound and the dichroic dye.
• water, methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl Alcohol solvents such as ether; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, ⁇ -butyrolactone, propylene glycol methyl ether acetate, ethyl lactate; acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone, methyl Ketone solvents such as isobutyl ketone; Aliphatic hydrocarbon solvents such as pentane, hexane and heptane; Aromatic hydrocarbon solvents such as toluene and xylene; Acetonite Nitrile solvents such as Le; tetrahydrofuran, ethers solvents such as dime
• the content of the solvent is preferably 100 to 1900 parts by weight, more preferably 150 to 900 parts by weight, and still more preferably 180 to 600 parts with respect to 100 parts by weight of the solid component constituting the polymerizable liquid crystal composition. Part by mass.
• the polymerizable liquid crystal composition of the present invention can be usually prepared by mixing and stirring a polymerizable liquid crystal compound, a dichroic dye and an antioxidant, and, if necessary, the above-described additives and solvents. .
• the polymerizable liquid crystal composition of the present invention is excellent in the effect of suppressing photodegradation of a dichroic dye, and can obtain a polarizing film in which the polarization performance hardly deteriorates with time. Can be used.
• a polarizing film having a high degree of alignment order can be produced from the polymerizable liquid crystal composition of the present invention.
• a polarizing film having a high degree of orientational order can obtain a Bragg peak derived from a higher order structure such as a hexatic phase or a crystal phase in X-ray diffraction measurement.
• the Bragg peak means a peak derived from a surface periodic structure of molecular orientation. Therefore, in the polarizing film formed from the polymerizable liquid crystal composition of the present invention, it is preferable that the polymerizable liquid crystal compound or the polymer thereof is oriented so that the polarizing film exhibits a Bragg peak in X-ray diffraction measurement.
• the “horizontal alignment” in which the molecules of the polymerizable liquid crystal compound are aligned in the direction of absorbing light is more preferable.
• a polarizing film having a plane interval of molecular orientation of 3.0 to 6.0 mm is preferable.
• a high degree of alignment order exhibiting a Bragg peak can be realized by controlling the type of polymerizable liquid crystal compound used, the type and amount of antioxidant, the type and amount of dichroic dye, and the like.
• the present invention provides a polarizing film that is a cured product of a polymerizable liquid crystal composition containing a dichroic dye, a polymerizable liquid crystal compound, and an antioxidant, and the polarizing film exhibits a Bragg peak in X-ray diffraction measurement.
• the antioxidant is represented by the formula (1) in relation to the polymerizable liquid crystal compound: 0.8 °C ⁇ T1-T2 (1)
• T1 is a liquid crystal that appears on the lowest temperature side when the phase transition temperature is measured while the polymerizable liquid crystal compound is heated to 130 ° C. in the air and then cooled to 23 ° C. at 5 ° C./min.
• T2 is a phase transition temperature to a phase
• T2 is a mixture of 100 parts by mass of the polymerizable liquid crystal compound and 1 part by mass of the antioxidant. It is the phase transition temperature to the liquid crystal phase that appears at the lowest temperature when the phase transition temperature is measured while cooling to 23 ° C.)
• a polarizing film satisfying the above is also targeted.
• the polymerizable liquid crystal composition used for forming the polarizing film of the present invention as the polymerizable liquid crystal compound, the dichroic dye and the antioxidant, the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition of the present invention, examples of the dichroic dye and the antioxidant are the same as those exemplified above.
• the polymerizable liquid crystal composition used for forming the polarizing film of the present invention may contain a polymerization initiator, a leveling agent, other additives, a solvent, and the like. Examples of these components include the same components as those exemplified above as components contained in the polymerizable liquid crystal composition of the present invention.
• the polarizing film of the present invention forms a coating film of the polymerizable liquid crystal composition of the present invention, Removing the solvent from the coating film,
• the temperature of the polymerizable liquid crystal compound is raised to a temperature higher than or equal to the temperature at which the liquid crystal compound phase transitions to the liquid phase, and the temperature of the polymerizable liquid crystal compound is lowered to the smectic phase (smectic liquid crystal state);
• It can be produced by a method comprising polymerizing a polymerizable liquid crystal compound while maintaining the smectic phase (smectic liquid crystal state).
• Formation of the coating film of the polymerizable liquid crystal composition is carried out by forming a polymerizable liquid crystal composition, particularly a polymerizable liquid crystal composition (hereinafter referred to as “polarizing film”) having a viscosity adjusted by adding a solvent on a substrate or an alignment film described later.
• the composition can also be applied by applying a “forming composition”.
• the polymerizable liquid crystal composition may be directly applied on the retardation film and other layers constituting the polarizing plate of the present invention.
• the base material is usually a transparent base material.
• the base material When the base material is not installed on the display surface of the display element, for example, when a laminate obtained by removing the base material from the polarizing film is installed on the display surface of the display element, the base material may not be transparent.
• the transparent substrate means a substrate having transparency capable of transmitting light, particularly visible light, and the transparency means a property that the transmittance for light having a wavelength of 380 to 780 nm is 80% or more. Say. Specific examples of the transparent substrate include a translucent resin substrate.
• the resin constituting the translucent resin base material examples include polyolefins such as polyethylene and polypropylene; cyclic olefin resins such as norbornene polymers; polyvinyl alcohol; polyethylene terephthalate; polymethacrylate esters; polyacrylate esters; Cellulose esters such as diacetylcellulose and cellulose acetate propionate; polyethylene naphthalate; polycarbonate; polysulfone; polyethersulfone; polyetherketone; polyphenylene sulfide and polyphenylene oxide. From the viewpoint of easy availability and transparency, polyethylene terephthalate, polymethacrylic acid ester, cellulose ester, cyclic olefin resin or polycarbonate is preferred.
• Cellulose ester is obtained by esterifying a part or all of hydroxyl groups contained in cellulose, and can be easily obtained from the market.
• Cellulose ester base materials can also be easily obtained from the market.
• Commercially available cellulose ester base materials include “Fujitack Film” (Fuji Photo Film Co., Ltd.); “KC8UX2M”, “KC8UY” and “KC4UY” (Konica Minolta Opto Co., Ltd.).
• the properties required for the substrate vary depending on the configuration of the polarizing film, but usually a substrate having as little retardation as possible is preferable.
• the substrate having as little retardation as possible include cellulose ester films having no phase difference such as zero tack (Konica Minolta Opto Co., Ltd.) and Z tack (Fuji Film Co., Ltd.).
• An unstretched cyclic olefin resin substrate is also preferred.
• the surface of the base material on which the polarizing film is not laminated may be subjected to a hard coat treatment, an antireflection treatment, an antistatic treatment or the like.
• the thickness of the substrate is usually 5 to 300 ⁇ m, preferably 20 to 200 ⁇ m, more preferably 20 to 100 ⁇ m, because if the substrate is too thin, the strength tends to decrease and the workability tends to be poor.
• a spin coating method As a method for applying the polarizing film forming composition to a substrate or the like, a spin coating method, an extrusion method, a gravure coating method, a die coating method, a bar coating method, an application method such as an applicator method, a printing such as a flexo method, etc.
• Known methods such as the method may be mentioned.
• a dry coating film is formed by removing the solvent by drying or the like under a condition that the polymerizable liquid crystal compound contained in the coating film obtained from the polarizing film forming composition does not polymerize.
• drying methods include natural drying, ventilation drying, heat drying, and reduced pressure drying.
• phase transition in order to cause the polymerizable liquid crystal compound to undergo a phase transition to the liquid phase, the temperature of the polymerizable liquid crystal compound is lowered to a temperature higher than the temperature at which the polymerizable liquid crystal compound transitions to the liquid phase, and then the polymerizable liquid crystal compound is changed to a smectic phase (smectic liquid crystal state).
• phase transition may be performed after removing the solvent in the coating film, or may be performed simultaneously with the removal of the solvent.
• a cured film of the polymerizable liquid crystal composition is formed as a polarizing film by polymerizing the polymerizable liquid crystal compound while maintaining the smectic liquid crystal state of the polymerizable liquid crystal compound.
• a photopolymerization method is preferred as the polymerization method.
• the light applied to the dried coating film includes the type of photopolymerization initiator contained in the dried coating film, the type of polymerizable liquid crystal compound (particularly, the type of polymerizable group possessed by the polymerizable liquid crystal compound). It is appropriately selected according to the amount.
• ultraviolet light is preferable in that it is easy to control the progress of the polymerization reaction and that a wide variety of photopolymerization apparatuses can be used in this field, and the polymerization is performed so that photopolymerization can be performed by ultraviolet light. It is preferable to select the type of polymerizable liquid crystal compound and photopolymerization initiator contained in the liquid crystal composition.
• polymerization temperature can also be controlled by irradiating light, cooling a dry coating film with a suitable cooling means.
• a cooling means By adopting such a cooling means, if a polymerizable liquid crystal compound is polymerized at a lower temperature, a polarizing film can be appropriately formed even if a substrate having a relatively low heat resistance is used.
• a patterned polarizing film can be obtained by masking or developing.
• the light source of the active energy ray includes a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a halogen lamp, a carbon arc lamp, a tungsten lamp, a gallium lamp, an excimer laser, a wavelength range of 380 to Examples include LED light sources that emit light of 440 nm, chemical lamps, black light lamps, microwave-excited mercury lamps, and metal halide lamps.
• the ultraviolet irradiation intensity is usually 10 to 3,000 mW / cm 2 .
• the ultraviolet irradiation intensity is preferably an intensity in a wavelength region effective for activating the photopolymerization initiator.
• the irradiation time is usually 0.1 second to 10 minutes, preferably 1 second to 5 minutes, more preferably 5 seconds to 3 minutes, and further preferably 10 seconds to 1 minute.
• the integrated light quantity is 10 to 3,000 mJ / cm 2 , preferably 50 to 2,000 mJ / cm 2 , more preferably 100 to 1,000 mJ / cm 2. 2 .
• the polymerizable liquid crystal compound is polymerized while maintaining the liquid crystal state of a smectic phase, preferably a higher order smectic phase, and a polarizing film is formed.
• a polarizing film obtained by polymerizing a polymerizable liquid crystal compound while maintaining the liquid crystal state of the smectic phase is accompanied by the action of the dichroic dye, and from the conventional host guest type polarizing film, that is, from the liquid crystal state of the nematic phase.
• the polarization performance is high.
• it is excellent in strength as compared with a case where only a dichroic dye or a lyotropic liquid crystal is applied.
• the thickness of the polarizing film can be appropriately selected depending on the display device to be applied, and is preferably 0.1 to 10 ⁇ m, more preferably 0.3 to 4 ⁇ m, and further preferably 0.5 to 3 ⁇ m.
• the polarizing film is preferably formed on the alignment film.
• the alignment film has an alignment regulating force that aligns the liquid crystal of the polymerizable liquid crystal compound in a desired direction.
• the alignment film has a solvent resistance that does not dissolve due to application of a composition containing a polymerizable liquid crystal compound, etc., and has heat resistance in heat treatment for solvent removal or alignment of the polymerizable liquid crystal compound.
• Examples of such an alignment film include an alignment film containing an alignment polymer, a photo-alignment film, a groove alignment film having a concavo-convex pattern and a plurality of grooves on the surface, and a stretched film extending in the alignment direction. From the viewpoint of quality, a photo-alignment film is preferable.
• orientation polymer examples include polyamides and gelatins having an amide bond in the molecule, polyimides having an imide bond in the molecule and hydrolyzates thereof, polyamic acid, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, polyoxazole, Examples include polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid and polyacrylic acid ester. Among these, polyvinyl alcohol is preferable.
• the orientation polymers can be used alone or in combination of two or more.
• the alignment film containing the alignment polymer is usually applied to a substrate with a composition in which the alignment polymer is dissolved in a solvent (hereinafter sometimes referred to as an “alignment polymer composition”), and the solvent is removed, or It is obtained by applying the orientation polymer composition to a substrate, removing the solvent, and rubbing (rubbing method).
• a solvent the thing similar to the solvent illustrated previously as a solvent which can be used when forming a polarizing film is mentioned.
• the concentration of the orienting polymer in the orienting polymer composition may be within the range in which the orienting polymer material can be completely dissolved in the solvent, but is preferably 0.1 to 20% in terms of solid content with respect to the solution, and 0 About 1 to 10% is more preferable.
• a commercially available alignment film material may be used as it is as the alignment polymer composition.
• Examples of commercially available alignment film materials include Sunever (registered trademark, manufactured by Nissan Chemical Industries, Ltd.), Optmer (registered trademark, manufactured by JSR).
• Examples of the method for applying the orientation polymer composition to the substrate include the same methods as those exemplified as the method for applying the polarizing film forming composition to the substrate.
• Examples of the method for removing the solvent contained in the orientation polymer composition include a natural drying method, a ventilation drying method, a heat drying method and a vacuum drying method.
• rubbing treatment can be performed as necessary (rubbing method).
• a rubbing cloth was wound, and the orientation polymer composition was applied to the rotating rubbing roll and annealed, and formed on the substrate surface.
• membrane of an orientation polymer contact is mentioned.
• the photo-alignment film is usually obtained by applying a composition containing a polymer or monomer having a photoreactive group and a solvent (hereinafter also referred to as “photo-alignment film-forming composition”) to a substrate, and polarizing (preferably, It is obtained by irradiating polarized UV).
• the photo-alignment film is more preferable in that the direction of the alignment regulating force can be arbitrarily controlled by selecting the polarization direction of the polarized light to be irradiated.
• the photoreactive group refers to a group that produces liquid crystal alignment ability when irradiated with light.
• groups involved in photoreactions that are the origin of liquid crystal alignment ability such as molecular orientation induction or isomerization reaction, dimerization reaction, photocrosslinking reaction or photodecomposition reaction caused by light irradiation.
• a group involved in the dimerization reaction or the photocrosslinking reaction is preferable in terms of excellent orientation.
• an unsaturated bond particularly a group having a double bond is preferable, and a carbon-carbon double bond (C ⁇ C bond), a carbon-nitrogen double bond (C ⁇ N bond), or a nitrogen-nitrogen two-bond.
• a group having at least one selected from the group consisting of a heavy bond (N ⁇ N bond) and a carbon-oxygen double bond (C ⁇ O bond) is particularly preferred.
• Examples of the photoreactive group having a C ⁇ C bond include a vinyl group, a polyene group, a stilbene group, a stilbazole group, a stilbazolium group, a chalcone group, and a cinnamoyl group.
• Examples of the photoreactive group having a C ⁇ N bond include groups having a structure such as an aromatic Schiff base and an aromatic hydrazone.
• Examples of the photoreactive group having a C ⁇ O bond include a benzophenone group, a coumarin group, an anthraquinone group, and a maleimide group. These groups may have a substituent such as an alkyl group, an alkoxy group, an aryl group, an allyloxy group, a cyano group, an alkoxycarbonyl group, a hydroxyl group, a sulfonic acid group, and a halogenated alkyl group.
• a photoreactive group involved in the photodimerization reaction is preferable, the amount of polarized light irradiation necessary for photoalignment is relatively small, and a photoalignment film excellent in thermal stability and temporal stability can be easily obtained.
• a cinnamoyl group and a chalcone group are preferred.
• the polymer having a photoreactive group a polymer having a cinnamoyl group in which the terminal portion of the polymer side chain has a cinnamic acid structure is particularly preferable.
• a photo-alignment inducing layer can be formed on a substrate by applying the composition for forming a photo-alignment film on the substrate.
• the solvent contained in the composition include the same solvents as those exemplified above as the solvent that can be used for forming the polarizing film, depending on the solubility of the polymer or monomer having a photoreactive group. You can choose.
• the content of the polymer or monomer having a photoreactive group in the composition for forming a photoalignment film can be appropriately adjusted depending on the type of the polymer or monomer and the thickness of the desired photoalignment film.
• the mass is preferably at least 0.2 mass%, more preferably in the range of 0.3 to 10 mass%.
• the composition for forming a photo-alignment film may contain a polymer material such as polyvinyl alcohol or polyimide, or a photosensitizer.
• Examples of the method for applying the composition for forming a photo-alignment film to a substrate include the same methods as those for applying the alignment composition to a substrate.
• Examples of the method for removing the solvent from the applied composition for forming a photo-alignment film include a natural drying method, a ventilation drying method, a heat drying method and a reduced pressure drying method.
• the polarized light is irradiated from the substrate side to transmit the polarized light. It may be in the form of irradiation. It is particularly preferable that the polarized light is substantially parallel light.
• the wavelength of the polarized light to be irradiated is preferably in a wavelength region in which the photoreactive group of the polymer or monomer having a photoreactive group can absorb light energy. Specifically, UV (ultraviolet light) having a wavelength in the range of 250 to 400 nm is particularly preferable.
• Examples of the light source used for the polarized light irradiation include xenon lamps, high pressure mercury lamps, ultra high pressure mercury lamps, metal halide lamps, ultraviolet lasers such as KrF and ArF, and high pressure mercury lamps, ultra high pressure mercury lamps and metal halide lamps. preferable.
• a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, and a metal halide lamp are preferable because of high emission intensity of ultraviolet rays having a wavelength of 313 nm.
• polarized UV light can be irradiated.
• a polarizing prism such as a polarizing filter, Glan Thompson, or Grand Taylor, or a wire grid type polarizer can be used.
• a plurality of regions (patterns) having different directions of liquid crystal alignment can be formed by performing masking during rubbing or polarized light irradiation.
• the groove alignment film is a film having a concavo-convex pattern or a plurality of grooves (grooves) on the film surface.
• a polymerizable liquid crystal compound is applied to a film having a plurality of linear grooves arranged at equal intervals, liquid crystal molecules are aligned in a direction along the groove.
• a method for obtaining a groove alignment film a method of forming a concavo-convex pattern by performing development and rinsing after exposure through an exposure mask having a pattern-shaped slit on the photosensitive polyimide film surface, a plate having grooves on the surface A layer of a pre-curing UV curable resin is formed on the original master, a method of curing the resin layer after transferring the formed resin layer to the base material, and a pre-curing UV curable resin film formed on the base material, Examples include a method in which a roll-shaped master having a plurality of grooves is pressed to form irregularities and then cured.
• the thickness of the alignment film is usually in the range of 10 to 10000 nm, preferably in the range of 10 to 1000 nm, more preferably 500 nm or less, and still more preferably The range is from 10 to 200 nm, particularly preferably from 50 to 150 nm.
• the present invention includes a polarizing plate (elliptical polarizing plate) comprising the polarizing film of the present invention and a retardation film.
• the retardation film has the formula (X): 100 ⁇ Re (550) ⁇ 180 (X) [Where Re (550) represents an in-plane retardation value at a wavelength of 550 nm] It is preferable to satisfy.
• the retardation film has an in-plane retardation value represented by (X), it functions as a so-called ⁇ / 4 plate.
• the formula (X) is preferably 100 nm ⁇ Re (550) ⁇ 180 nm, more preferably 120 nm ⁇ Re (550) ⁇ 160 nm.
• Re (550) can be measured by the method described in the examples.
• the angle formed between the slow axis of the retardation film and the absorption axis of the polarizing film is preferably substantially 45 °.
• substantially 45 ° means 45 ° ⁇ 5 °.
• the retardation film has the formula (Y): Re (450) / Re (550) ⁇ 1 (Y) [Wherein, Re (450) and Re (550) represent in-plane retardation values at wavelengths of 450 nm and 550 nm, respectively] It is preferable to satisfy.
• the retardation film satisfying the above formula (Y) has so-called reverse wavelength dispersion and exhibits excellent polarization performance.
• the value of Re (450) / Re (550) is preferably 0.93 or less, more preferably 0.88 or less, still more preferably 0.86 or less, preferably 0.80 or more, more preferably 0.8. 82 or more.
• the retardation film may be a stretched film that gives a retardation by stretching a polymer.
• a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound hereinafter, “ It is preferably a cured product of the polymerizable liquid crystal composition (B) ”, and is composed of a polymer in the alignment state of the polymerizable liquid crystal compound.
• the polymerizable liquid crystal compound forming the retardation film hereinafter also referred to as “polymerizable liquid crystal compound (B)” means a liquid crystal compound having a polymerizable functional group, particularly a photopolymerizable functional group.
• the photopolymerizable functional group refers to a group that can participate in a polymerization reaction by an active radical or an acid generated from a photopolymerization initiator.
• the photopolymerizable functional group include a vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, acryloyloxy group, methacryloyloxy group, oxiranyl group, and oxetanyl group.
• acryloyloxy group, methacryloyloxy group, vinyloxy group, oxiranyl group and oxetanyl group are preferable, and acryloyloxy group is more preferable.
• the polymerizable liquid crystal compound (B) may be either a thermotropic liquid crystal or a lyotropic liquid crystal, and the phase ordered structure may be a nematic liquid crystal or a smectic liquid crystal.
• the polymerizable liquid crystal compound (B) only one type may be used, or two or more types may be used in combination.
• Examples of the polymerizable liquid crystal compound (B) include compounds satisfying all of the following (A) to (E) from the viewpoint of easy film formation and providing the retardation represented by the formula (Y). .
• (A) a compound having a thermotropic liquid crystallinity
• (A) The polymerizable liquid crystal compound has ⁇ electrons on the major axis direction (a).
• C) It has ⁇ electrons on the direction [cross direction (b)] intersecting with the major axis direction (a).
• (D) The polymerizable liquid crystal compound defined by formula (i) where N ( ⁇ a) is the total of ⁇ electrons present in the major axis direction (a) and N (Aa) is the total molecular weight present in the major axis direction.
• ⁇ electron density in the major axis direction (a): D ( ⁇ a) N ( ⁇ a) / N (Aa) (i) And the total of ⁇ electrons present in the cross direction (b) is N ( ⁇ b), and the total molecular weight present in the cross direction (b) is N (Ab).
• ⁇ electron density in cross direction (b): D ( ⁇ b) N ( ⁇ b) / N (Ab) (ii) And 0 ⁇ [D ( ⁇ a) / D ( ⁇ b)] ⁇ 1 [In other words, the ⁇ electron density in the cross direction (b) is larger than the ⁇ electron density in the major axis direction (a)).
• the polymerizable liquid crystal compound (B) satisfying all of the above (a) to (d) can be applied on an alignment film formed by rubbing treatment and heated to a temperature higher than the phase transition temperature to form a nematic phase. It is.
• the polymerizable liquid crystal compound is usually aligned so that the major axis directions thereof are parallel to each other, and the major axis direction is the alignment direction of the nematic phase. It becomes.
• the polymerizable liquid crystal compound (B) having the above characteristics generally exhibits reverse wavelength dispersion.
• formula (II) for example, formula (II):
• the compound represented by these is mentioned.
• the compounds represented by the formula (II) can be used alone or in combination of two or more.
• Ar represents a divalent aromatic group which may have a substituent.
• the aromatic group here is a group having a planar structure having a planarity, and the number of ⁇ electrons of the cyclic structure is [4n + 2] according to the Hückel rule.
• n represents an integer.
• a ring structure is formed including a heteroatom such as —N ⁇ or —S—, the case where the Huckel's rule is satisfied including the non-covalent electron pair on the heteroatom and the aromatic structure is included.
• the divalent aromatic group preferably contains at least one of a nitrogen atom, an oxygen atom and a sulfur atom.
• G 1 and G 2 each independently represents a divalent aromatic group or a divalent alicyclic hydrocarbon group.
• the hydrogen atom contained in the divalent aromatic group or divalent alicyclic hydrocarbon group is a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, or a carbon atom.
• the carbon atom constituting the divalent aromatic group or divalent alicyclic hydrocarbon group which may be substituted with an alkoxy group, cyano group or nitro group of formulas 1 to 4 is an oxygen atom, a sulfur atom Alternatively, it may be substituted with a nitrogen atom.
• L 1 , L 2 , B 1 and B 2 are each independently a single bond or a divalent linking group.
• k and l each independently represent an integer of 0 to 3, and satisfy the relationship of 1 ⁇ k + 1.
• B 1 and B 2 may be the same or different from each other.
• E 1 and E 2 each independently represents an alkanediyl group having 1 to 17 carbon atoms, wherein a hydrogen atom contained in the alkanediyl group may be substituted with a halogen atom, The —CH 2 — contained may be substituted with —O—, —S—, or —Si—.
• P 1 and P 2 each independently represent a polymerizable group or a hydrogen atom, and at least one is a polymerizable group.
• G 1 and G 2 are each independently preferably a 1,4-phenylenediyl group optionally substituted with at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms 1,4-cyclohexanediyl group optionally substituted with at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, more preferably 1 substituted with a methyl group , 4-phenylenediyl group, unsubstituted 1,4-phenylenediyl group, or unsubstituted 1,4-trans-cyclohexanediyl group, particularly preferably unsubstituted 1,4-phenylenediyl group or Substituted 1,4-trans-cyclohexanediyl group.
• At least one of a plurality of G 1 and G 2 is preferably a divalent alicyclic hydrocarbon group, and at least one of G 1 and G 2 bonded to L 1 or L 2 is two. It is more preferably a valent alicyclic hydrocarbon group.
• L 1 and L 2 are each independently preferably a single bond, an alkylene group having 1 to 4 carbon atoms, —O—, —S—, —R a1 OR a2 —, —R a3 COOR a4 —, —R a5 OCOR a6 —, R a7 OC ⁇ OOR a8 —, —N ⁇ N—, —CR c ⁇ CR d —, or —C ⁇ C—.
• R a1 to R a8 each independently represents a single bond or an alkylene group having 1 to 4 carbon atoms
• R c and R d each represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom.
• L 1 and L 2 are each independently more preferably a single bond, —OR a2-1 —, —CH 2 —, —CH 2 CH 2 —, —COOR a4-1 —, or —OCOR a6-1 —. is there.
• R a2-1 , R a4-1 , and R a6-1 each independently represent a single bond, —CH 2 —, or —CH 2 CH 2 —.
• L 1 and L 2 are each independently a single bond, —O—, —CH 2 CH 2 —, —COO—, —COOCH 2 CH 2 —, or —OCO—.
• At least one of G 1 and G 2 in formula (II) is a divalent alicyclic hydrocarbon group, and the divalent alicyclic hydrocarbon group is
• a polymerizable liquid crystal compound in which a divalent aromatic group Ar which may have a substituent and L 1 and / or L 2 which are —COO— is used.
• B 1 and B 2 are each independently preferably a single bond, an alkylene group having 1 to 4 carbon atoms, —O—, —S—, —R a9 OR a10 —, —R a11 COOR a12 —, —R a13 OCOR a14 —, or R a15 OC ⁇ OOR a16 —.
• R a9 to R a16 each independently represents a single bond or an alkylene group having 1 to 4 carbon atoms.
• B 1 and B 2 are each independently more preferably a single bond, —OR a10-1 —, —CH 2 —, —CH 2 CH 2 —, —COOR a12-1 —, or —OCOR a14-1 —. is there.
• R a10-1 , R a12-1 and R a14-1 each independently represents a single bond, —CH 2 — or —CH 2 CH 2 —.
• B 1 and B 2 are each independently more preferably a single bond, -O -, - CH 2 CH 2 -, - COO -, - COOCH 2 CH 2 -, - OCO-, or -OCOCH 2 CH 2 - in is there.
• E 1 and E 2 are each independently preferably an alkanediyl group having 1 to 17 carbon atoms, and more preferably an alkanediyl group having 4 to 12 carbon atoms.
• Examples of the polymerizable group represented by P 1 or P 2 include epoxy group, vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, acryloyloxy group, methacryloyloxy group, and oxiranyl group. And an oxetanyl group.
• acryloyloxy group, methacryloyloxy group, vinyloxy group, oxiranyl group and oxetanyl group are preferable, and acryloyloxy group is more preferable.
• Ar preferably has at least one selected from an aromatic hydrocarbon ring which may have a substituent, an aromatic heterocycle which may have a substituent, and an electron-withdrawing group.
• aromatic hydrocarbon ring examples include a benzene ring, a naphthalene ring, and an anthracene ring, and a benzene ring and a naphthalene ring are preferable.
• aromatic heterocycle examples include furan ring, benzofuran ring, pyrrole ring, indole ring, thiophene ring, benzothiophene ring, pyridine ring, pyrazine ring, pyrimidine ring, triazole ring, triazine ring, pyrroline ring, imidazole ring, pyrazole ring. , Thiazole ring, benzothiazole ring, thienothiazole ring, oxazole ring, benzoxazole ring, phenanthrolin ring, and the like.
• a thiazole ring a benzothiazole ring, or a benzofuran ring
• Ar contains a nitrogen atom
• the nitrogen atom preferably has ⁇ electrons.
• the total number N of ⁇ electrons contained in the divalent aromatic group represented by Ar is preferably 8 or more, more preferably 10 or more, still more preferably 14 or more, Preferably it is 16 or more. Preferably it is 30 or less, More preferably, it is 26 or less, More preferably, it is 24 or less.
• Examples of the aromatic group represented by Ar include groups of formula (Ar-1) to formula (Ar-23).
• Z 0 , Z 1 and Z 2 are each independently a hydrogen atom, a halogen atom or an alkyl having 1 to 12 carbon atoms.
• Q 1 and Q 2 each independently represent —CR 2 ′ R 3 ′ —, —S—, —NH—, —NR 2 ′ —, —CO— or —O—, wherein R 2 ′ and R 3 'each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
• J 1 and J 2 each independently represent a carbon atom or a nitrogen atom.
• Y 1 , Y 2 and Y 3 each independently represents an optionally substituted aromatic hydrocarbon group or aromatic heterocyclic group.
• W 1 and W 2 each independently represents a hydrogen atom, a cyano group, a methyl group or a halogen atom, and m represents an integer of 0 to 6.
• Examples of the aromatic hydrocarbon group for Y 1 , Y 2 and Y 3 include aromatic hydrocarbon groups having 6 to 20 carbon atoms such as a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and a biphenyl group.
• Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and a biphenyl group.
• a phenyl group and a naphthyl group are preferable, and a phenyl group is more preferable.
• the aromatic heterocyclic group examples include an aromatic heterocyclic group having 4 to 20 carbon atoms and containing at least one hetero atom such as a nitrogen atom, an oxygen atom, or a sulfur atom.
• the aromatic heterocyclic group examples include a furyl group, a pyrrolyl group, a thienyl group, a pyridinyl group, a thiazolyl group, and a benzothiazolyl group, and a furyl group, a thienyl group, a pyridinyl group, a thiazolyl group, and a benzothiazolyl group are preferable.
• Y 1 and Y 2 may each independently be an optionally substituted polycyclic aromatic hydrocarbon group or polycyclic aromatic heterocyclic group.
• the polycyclic aromatic hydrocarbon group refers to a condensed polycyclic aromatic hydrocarbon group or a group derived from an aggregate of aromatic rings.
• the polycyclic aromatic heterocyclic group refers to a condensed polycyclic aromatic heterocyclic group or a group derived from an aromatic ring assembly.
• Z 0 , Z 1 and Z 2 are each independently preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyano group, a nitro group, or an alkoxy group having 1 to 12 carbon atoms.
• 0 is more preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a cyano group.
• Z 1 and Z 2 are more preferably a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group or a cyano group.
• Q 1 and Q 2 are preferably —NH—, —S—, —NR 2 ′ —, and —O—, and R 2 ′ is preferably a hydrogen atom.
• Q 1 and Q 2 are particularly preferably —S—, —O—, and —NH—.
• the formulas (Ar-1) to (Ar-23) are preferable from the viewpoint of molecular stability.
• Y 1 may form an aromatic heterocyclic group together with the nitrogen atom to which it is bonded and Z 0 .
• the aromatic heterocyclic group include those described above as the aromatic heterocyclic ring that Ar may have. Examples include a pyrrole ring, an imidazole ring, a pyrroline ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, an indole ring, a quinoline ring, an isoquinoline ring, a purine ring, and a pyrrolidine ring.
• This aromatic heterocyclic group may have a substituent.
• Y 1 may be the above-mentioned optionally substituted polycyclic aromatic hydrocarbon group or polycyclic aromatic heterocyclic group together with the nitrogen atom to which it is bonded and Z 0 .
• the polycyclic aromatic heterocyclic group include a benzofuran ring, a benzothiazole ring, and a benzoxazole ring.
• the compound represented by the formula (II) can be produced, for example, according to the method described in JP 2010-31223 A.
• the content of the polymerizable liquid crystal compound (B) in the polymerizable liquid crystal composition (B) is, for example, 70 to 99.5 parts by mass with respect to 100 parts by mass of the solid content of the polymerizable liquid crystal composition (B).
• the amount is preferably 80 to 99 parts by mass, and more preferably 90 to 98 parts by mass.
• solid content means the total amount of the component remove
• the polymerizable liquid crystal composition (B) may contain a polymerization initiator for initiating a polymerization reaction of the polymerizable liquid crystal compound (B).
• a polymerization initiator the thing similar to what was illustrated previously as a polymerization initiator which can be used in a polymerizable liquid crystal composition (A) is mentioned.
• the polymerizable liquid crystal composition (B) may contain a photosensitizer, a leveling agent, an additive exemplified as an additive contained in the polymerizable liquid crystal composition (A), and the like as necessary. .
• a photosensitizer and a leveling agent the thing similar to what was illustrated previously as what is contained in a polymeric liquid crystal composition (A) is mentioned.
• the retardation film is a composition prepared by adding a solvent to a polymerizable liquid crystal composition (B) containing a polymerizable liquid crystal compound (B) and, if necessary, a polymerization initiator and additives, and mixing and stirring.
• the product (hereinafter also referred to as “a retardation film forming composition”) is applied onto a substrate or an alignment film, the solvent is removed by drying, and the polymerizable liquid crystal compound (B) in the obtained coating film is removed. It can be obtained by curing by heating and / or active energy rays.
• the substrate and / or alignment film used for the production of the retardation film include the same materials as those exemplified above as those that can be used for producing the polarizing film of the present invention.
• the solvent used for the retardation film-forming composition, the coating method of the retardation film-forming composition, the curing conditions using active energy rays, and the like are all the same as those that can be employed in the method for producing a polarizing film of the present invention. Things.
• the thickness of the retardation film can be appropriately selected depending on the display device to be applied, but is preferably 0.1 to 10 ⁇ m and more preferably 1 to 5 ⁇ m from the viewpoint of thinning and flexibility. More preferably, it is 1 to 3 ⁇ m.
• the polarizing plate of the present invention comprises the polarizing film and retardation film of the present invention, and preferably comprises a substrate, an alignment film (particularly a photoalignment film), and the polarizing film and retardation film of the present invention.
• the polarizing plate of the present invention may further contain other layers (protective layer, adhesive layer, etc.) other than these.
• the polarizing film and the retardation film of the present invention may be bonded via an adhesive layer or an adhesive layer.
• the retardation film may be directly formed on the polarizing film of the present invention by directly coating the retardation film-forming composition on the polarizing film of the present invention.
• the thickness of the polarizing plate of the present invention is preferably 10 to 300 ⁇ m, more preferably 20 to 200 ⁇ m, still more preferably 25 to 100 ⁇ m, from the viewpoint of the flexibility and visibility of the display device.
• the present invention includes a display device comprising the polarizing film of the present invention or the polarizing plate of the present invention.
• the display device of the present invention can be obtained, for example, by bonding the polarizing film or polarizing plate of the present invention to the surface of the display device via an adhesive layer.
• a display device is a device having a display mechanism and includes a light-emitting element or a light-emitting device as a light-emitting source.
• Display devices include liquid crystal display devices, organic electroluminescence (EL) display devices, inorganic electroluminescence (EL) display devices, touch panel display devices, electron emission display devices (field emission display devices (FED, etc.), surface field emission display devices.
• the liquid crystal display device includes any of a transmissive liquid crystal display device, a transflective liquid crystal display device, a reflective liquid crystal display device, a direct view liquid crystal display device, a projection liquid crystal display device, and the like. These display devices may be a display device that displays a two-dimensional image, or may be a stereoscopic display device that displays a three-dimensional image.
• an organic EL display device and a touch panel display device are preferable, and an organic EL display device is particularly preferable.
• polarizing film forming composition ⁇ Preparation of polymerizable liquid crystal composition (hereinafter also referred to as “polarizing film forming composition”)> The following components were mixed and stirred at 80 ° C. for 1 hour to obtain a polarizing film forming composition (1).
• dichroic dye an azo dye described in Examples of JP2013-101328A was used.
• % and part in the examples mean mass% and part by mass, respectively, unless otherwise specified.
• the polarizing film was formed in the same manner as the polarizing film forming composition (1) except that the following compounds as antioxidants were mixed in the polarizing film forming composition (1) in the amounts shown in Table 1. Forming compositions (2) to (18) were obtained.
• the addition amount of the antioxidant in Table 1 indicates an amount with respect to 100 parts by mass of the polymerizable liquid crystal compound in the polarizing film forming composition.
• Antioxidant A 4-n-octyloxyphenol
• Antioxidant B 4,4'-biphenol
• Antioxidant C 4-ethoxy-4′-hydroxybiphenyl
• Antioxidant D 4-butoxy-4′-hydroxybiphenyl
• Antioxidant E 4-octyloxy-4′-hydroxybiphenyl
• Antioxidant F Dibutylhydroxytoluene
• Antioxidant G Tinuvin 770; manufactured by BASF
• Antioxidant H Sumilizer GP; manufactured by Sumitomo Chemical Co., Ltd.
• Antioxidant I p-methoxyphenol
• ⁇ Measurement of liquid crystal phase transition temperature change T1-T2> Formation of alignment film On a glass substrate, a 2% by weight aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified type, manufactured by Wako Pure Chemical Industries, Ltd.) was applied by spin coating, dried, and then 100 nm in thickness. A film was formed. Subsequently, an alignment film was formed by subjecting the surface of the obtained film to a rubbing treatment.
• polyvinyl alcohol polyvinyl alcohol 1000 completely saponified type, manufactured by Wako Pure Chemical Industries, Ltd.
• the rubbing process uses a semi-automatic rubbing apparatus (trade name: LQ-008 type, manufactured by Joyo Engineering Co., Ltd.) and a push-in amount of 0.15 mm using a cloth (trade name: YA-20-RW, manufactured by Yoshikawa Chemical Co., Ltd.). , Under the conditions of 500 rpm and 16.7 mm / s.
• T1 As a polymerizable liquid crystal compound, 90 parts of a compound represented by the formula (A-6), 10 parts of a compound represented by the formula (A-7), and 400 parts of o-xylene were heated at 80 ° C. for 1 hour. By stirring, a uniformly mixed composition was obtained. The obtained mixed composition was applied onto the glass with an alignment film by a spin coating method, and dried on a hot plate at 130 ° C. for 3 minutes to remove o-xylene as a solvent. Thereafter, the obtained coating film was quickly cooled to room temperature to obtain a dry film of a polymerizable liquid crystal compound. The dried film was heated again to 130 ° C.
• phase transition temperature was measured by observing with a polarizing microscope when the temperature was lowered to 23 ° C. at a rate of 5 ° C./min.
• a phase transition to a nematic liquid crystal phase at 113.7 ° C. a phase transition to a smectic A phase at 109.6 ° C.
• a phase transition to a smectic B phase at 92.0 ° C. a phase transition to a smectic B phase until 23 ° C. Confirmed to maintain.
• T1 since the liquid crystal phase that appears on the lowest temperature side was the smectic B phase, T1 was defined as 92.0 ° C., which is the phase transition temperature to the smectic B phase.
• T2 The same as the measurement of T1 in (2) above, except that 1 part by mass of antioxidants A to I was added to 100 parts by mass of the polymerizable liquid crystal compound. By the method, a dry film comprising a mixture of an antioxidant and a polymerizable liquid crystal compound was obtained.
• the phase transition temperature As a result of measuring the phase transition temperature by the same method as the measurement of T1 in (2) above, the liquid crystal phase that appeared on the lowest temperature side in all the mixtures was the smectic B phase.
• Table 2 shows the phase transition temperature (T2) to the liquid crystal phase that appears on the lowest temperature side when each antioxidant is contained.
• Example 1 (1) Preparation of photo-alignment film on substrate (i) Preparation of composition for forming photo-alignment film The following components described in JP2013-033249A were mixed, and the resulting mixture was stirred at 80 ° C for 1 hour. By stirring, a composition for forming a photo-alignment film was obtained.
• Photo-alignment polymer
• the polarizing film-forming composition (2) was applied on the film with a photo-alignment film obtained as described above by the bar coating method (# 9 30 mm / s) and dried at 120 ° C.
• the polymerizable liquid crystal compound was transformed into a liquid phase by heating and drying in an oven for 1 minute, and then cooled to room temperature to cause the polymerizable liquid crystal compound to undergo a phase transition into a smectic liquid crystal state.
• SPOT CURE SP-7 manufactured by USHIO INC.
• the layer formed from the composition for forming a polarizing film is irradiated with an ultraviolet ray having an exposure amount of 1000 mJ / cm 2 (365 nm standard).
• the polymerizable liquid crystal compound contained in the dry film was polymerized while maintaining the smectic liquid crystal state of the polymerizable liquid crystal compound, and a polarizing film was formed from the dry film.
• a polarizing film was formed from the dry film.
• Example 1 the polarizing film of Example 1 is bonded on the protective layer through a pressure-sensitive adhesive (made by Lintec Co., Ltd., film thickness: 25 ⁇ m) through a pressure-sensitive adhesive layer (Corning, EagleXG). A laminate was obtained.
• a pressure-sensitive adhesive made by Lintec Co., Ltd., film thickness: 25 ⁇ m
• a pressure-sensitive adhesive layer Cornning, EagleXG
• Example 2 was carried out in the same manner except that each of the polarizing film forming compositions (1) and (3) to (18) shown in Table 3 was used instead of the polarizing film forming composition (2).
• the polarizing film laminated body of -15, the comparative example 1, the comparative example 2, and the reference example 1 was obtained.
• the polarizing film laminate is placed on a triacetyl cellulose film surface as a base and placed in a light resistance tester (Suntest XLS +; manufactured by ATLAS). After light irradiation under the condition of 23070 KJ / m 2 , The degree of change before and after the light resistance test was calculated by measuring the polarization degree Py and single transmittance Ty of the laminate again.
• the polarizing film forming compositions 2 to 16 that is, the polarizing films prepared from the polymerizable liquid crystal composition of the present invention (Examples 1 to 15) have good light resistance.
• Example 16 Provide of circularly polarizing plate> On the protective layer of the polarizer with a protective layer obtained in the production process of the polarizing film laminate of Example 5, through an adhesive layer formed from a pressure-sensitive adhesive (made by Lintec Corporation, film thickness 25 ⁇ m), A retardation film produced according to Example 1 of JP-A-2015-143786 was transferred. Subsequently, an aluminum metal plate was bonded through an adhesive layer formed from a pressure-sensitive adhesive (manufactured by Lintec Corporation, film thickness 25 ⁇ m) to obtain an elliptically polarizing plate.
• a pressure-sensitive adhesive made by Lintec Corporation, film thickness 25 ⁇ m
• the elliptically polarizing plate provided with the polarizing film of the present invention was confirmed to have a small amount of change in chromaticity and good light resistance.

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