Classifications

• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/30—Polarising elements
  • G02B5/3083—Birefringent or phase retarding elements
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/02—Physical, chemical or physicochemical properties
  • B32B7/023—Optical properties
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/06—Non-macromolecular additives organic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
• • 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
  • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
  • C09K19/06—Non-steroidal liquid crystal compounds
  • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
  • C09K19/3491—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having sulfur as hetero atom
• • 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
  • 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
  • C09K19/542—Macromolecular compounds
• • 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
  • G02B5/3016—Polarising elements involving passive liquid crystal 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
  • G02B5/3041—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 comprising multiple thin layers, e.g. multilayer stacks
  • G02B5/305—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 comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
  • G02F1/133528—Polarisers
• • G—PHYSICS
  • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
  • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
  • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
  • H05B33/00—Electroluminescent light sources
  • H05B33/02—Details
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
  • H10K59/80—Constructional details
  • H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
  • H10K59/80—Constructional details
  • H10K59/8793—Arrangements for polarized light emission
• • 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
  • C09K19/06—Non-steroidal liquid crystal compounds
  • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
  • C09K19/3491—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having sulfur as hetero atom
  • C09K19/3497—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having sulfur as hetero atom the heterocyclic ring containing sulfur and nitrogen atoms
• • 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
  • C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
  • C09K2019/0448—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate

Definitions

• the present invention relates to a polarizing plate and an image display device.
• a polymerizable liquid crystal compound exhibiting reverse wavelength dispersibility can accurately convert the light wavelength in a wide wavelength range, and can thin an optical film (phase difference film) because it has a high refractive index. Since it has such characteristics, it is being actively researched.
• Patent Document 1 describes a polarizing film in which a retardation film and a polarizing element are laminated via an adhesive layer ([Claim 1] [Claim 20]).
• the present inventors have examined a known polarizing plate described in Patent Document 1 and the like, that is, a polarizing plate having a polarizing element, an adhesive layer, and an optical film exhibiting anti-wavelength dispersibility adjacent to each other in this order. It was clarified that the adhesiveness between the polarizing element and the optical film was insufficient, and that there was room for improvement in durability.
• the present inventors have found that the maximum absorption wavelength of the polymerization initiator contained in the adhesive composition forming the adhesive layer is in a predetermined range, and the molar absorption coefficient is predetermined. It was found that a polarizing plate having excellent adhesiveness between the polarizing element and the optical film and having good durability can be produced when the value is equal to or higher than the value, and the present invention has been completed. That is, it was found that the above problem can be achieved by the following configuration.
• a polarizing element, an adhesive layer, and an optical film exhibiting anti-wavelength dispersibility are adjacent to each other in this order.
• the adhesive layer is a layer formed by using an adhesive composition containing a polymerizable compound and a polymerization initiator.
• Condition 1 The maximum absorption wavelength of the polymerization initiator is within ⁇ 70 nm of the minimum absorption wavelength of the optical film.
• Condition 2 The molar absorption coefficient of the polymerization initiator is 22,000 mol -1 Lcm -1 or more [2].
• the polymerizable liquid crystal compound is a compound having a linking group represented by any of the formulas (Ar-1) to (Ar-7) described later.
• Polymers having repeating units represented by the formula (B) described later are present on the surface of the optical film on the adhesive layer side or the surface of the adhesive layer on the optical film side, [1] to [3].
• the adhesive composition further contains a sensitizer, Any of [1] to [7], wherein the sensitizer has a maximum absorption wavelength in a wavelength region on the long wavelength side of the maximum absorption wavelength of the polymerization initiator and in which the transmittance of the optical film is 1% or more.
• the polarizing plate according to. [9] The polarizing plate according to any one of [1] to [8], wherein the polymerizable compound is a cationically polymerizable compound.
• the polarizing plate according to any one of [1] to [10] is provided.
• Image display device [12] The image display device according to [11], which is a liquid crystal display device. [13] The image display device according to [11], which is an organic electroluminescence display device.
• a polarizing plate having excellent adhesiveness between a polarizing element and an optical film and having good durability, and an image display device having the same.
• the present invention will be described in detail.
• the description of the constituent elements described below may be based on the representative embodiments of the present invention, but the present invention is not limited to such embodiments.
• the numerical range represented by using "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
• a substance corresponding to each component may be used alone or in combination of two or more.
• the content of the component means the total content of the substances used in combination unless otherwise specified.
• (meth) acrylate is a notation representing "acrylate” or “methacrylate”
• (meth) acrylic is a notation representing "acrylic” or “methacrylic”.
• (Meta) acrylic is a notation representing "acryloyl” or "methacrylic acid”.
• the binding direction of the divalent group (for example, -O-CO-) described in the present specification is not particularly limited, and for example, L 2 is-in the binding of "L 1 -L 2 -L 3 ". In the case of O-CO-, if the position bonded to the L 1 side is * 1 and the position bonded to the L 3 side is * 2, L 2 is * 1-O-CO- * 2. It may be * 1-CO-O- * 2.
• the polarizing plate of the present invention is a polarizing plate having a polarizing element, an adhesive layer, and an optical film exhibiting anti-wavelength dispersibility adjacent to each other in this order.
• the adhesive layer of the polarizing plate of the present invention is a layer formed by using an adhesive composition containing a polymerizable compound and a polymerization initiator.
• the polarizing plate of the present invention is a polarizing plate that satisfies the following conditions 1 and 2.
• Condition 1 The maximum absorption wavelength of the polymerization initiator is within ⁇ 70 nm of the minimum absorption wavelength of the optical film.
• Condition 2 The molar absorption coefficient of the polymerization initiator is 22,000 mol -1 Lcm -1 or more.
• the polymerization initiator contained in the adhesive composition forming the adhesive layer satisfies the above-mentioned conditions 1 and 2, so that the polarizing element and the optical film have excellent adhesiveness and durability. Can produce a good polarizing plate.
• the present inventors speculate as follows. First, when an optical film that does not exhibit reverse wavelength dispersibility is used, as shown in Reference Example 1 described later, there is no problem of adhesion between the splitter and the optical film and no problem of inferior durability. You can see that.
• the polymerization initiator satisfies the above-mentioned conditions 1 and 2, the polymerization initiator is sufficient without being affected by the light absorbed by the liquid crystal compound contained in the optical film exhibiting reverse wavelength dispersibility. It is considered that the adhesiveness between the polymerase and the optical film is improved and the durability is also improved because it is possible to act on the polymer.
• the layer structure of the polarizing plate of the present invention will be described in detail.
• the polarizing plate of the polarizing plate of the present invention is not particularly limited as long as it is a member having a function of converting light into a specific linear polarization, and conventionally known absorption-type and reflection-type splitters can be used. ..
• As the absorption type polarizing element an iodine-based polarizing element, a dye-based polarizing element using a dichroic dye, a polyene-based polarizing element, and the like are used.
• Iodine-based splitters and dye-based splitters include coated and stretched splitters, both of which can be applied, but polarized light produced by adsorbing iodine or a dichroic dye on polyvinyl alcohol and stretching it.
• Japanese Patent No. 5048120 Japanese Patent No. 5143918, Japanese Patent No. 4691205, and Patent No. 5048120
• Patent No. Japanese Patent No. 4751481 and Japanese Patent No. 4751486 can be mentioned, and known techniques relating to these substituents can also be preferably used.
• the reflective classifier a splitter in which thin films having different birefringences are laminated, a wire grid type splitter, a carboxylator in which a cholesteric liquid crystal having a selective reflection region and a 1/4 wave plate are combined, and the like are used.
• At least one selected from the group consisting of a polyvinyl alcohol-based resin (a polymer containing -CH2 -CHOH- as a repeating unit, particularly a polyvinyl alcohol and an ethylene-vinyl alcohol copolymer) in that the adhesion is more excellent. It is preferable that the polymer contains one).
• the thickness of the polarizing element is not particularly limited, but is preferably 3 ⁇ m to 60 ⁇ m, more preferably 3 ⁇ m to 30 ⁇ m, and even more preferably 3 ⁇ m to 10 ⁇ m.
• the optical film included in the polarizing plate of the present invention is an optical film exhibiting reverse wavelength dispersibility.
• the optical film exhibiting reverse wavelength dispersibility includes Re (450), which is an in-plane retardation value measured at a wavelength of 450 nm, and Re (550), which is an in-plane retardation value measured at a wavelength of 550 nm.
• Re (650), which is the value of the in-plane retardation measured at a wavelength of 650 nm refers to an optically anisotropic layer that satisfies the relationship of Re (450) ⁇ Re (550) ⁇ Re (650).
• the optical film preferably has one or more optically anisotropic layers formed by using the polymerizable liquid crystal composition containing the polymerizable liquid crystal compound.
• the polymerizable liquid crystal compound has the following formulas (Ar-1) to (Ar-7) for the reason that the effect of the present invention, that is, the adhesiveness between the polarizing element and the optical film is excellent and the durability is good, becomes apparent. It is preferably a compound having a linking group represented by any one.
• * represents a bond position, that is, a bond position with a portion other than the linking group contained in the polymerizable liquid crystal compound.
• Q 1 represents N or CH
• Q 2 represents -S-, -O-, or -N (R 6 )-
• R 6 is hydrogen.
• Y1 is an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent and 3 to 12 carbon atoms which may have a substituent.
• the alkyl group having 1 to 6 carbon atoms indicated by R 6 is specifically, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and the like. Examples thereof include a tert-butyl group, an n-pentyl group, and an n-hexyl group.
• Examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms indicated by Y 1 include an aryl group such as a phenyl group, a 2,6-diethylphenyl group and a naphthyl group.
• Examples of the aromatic heterocyclic group having 3 to 12 carbon atoms indicated by Y 1 include heteroaryl groups such as a thienyl group, a thiazolyl group, a frill group and a pyridyl group.
• Examples of the alicyclic hydrocarbon group having 6 to 20 carbon atoms indicated by Y 1 include a cyclohexylene group, a cyclopentylene group, a norbornene group, and an adamantylene group.
• Examples of the substituent that Y 1 may have include an alkyl group, an alkoxy group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group, an alkylamino group, a dialkylamino group, an alkylamide group and an alkenyl group.
• Examples thereof include an alkynyl group, a halogen atom, a cyano group, a nitro group, an alkylthiol group, and an N-alkylcarbamate group, among which an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, or a halogen atom is used. preferable.
• the alkyl group is preferably a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, and an alkyl group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, n).
• -Butyl group, isobutyl group, sec-butyl group, t-butyl group, cyclohexyl group, etc. are more preferable, an alkyl group having 1 to 4 carbon atoms is further preferable, and a methyl group or an ethyl group is particularly preferable.
• an alkoxy group having 1 to 18 carbon atoms is preferable, an alkoxy group having 1 to 8 carbon atoms (for example, a methoxy group, an ethoxy group, an n-butoxy group, a methoxyethoxy group, etc.) is more preferable, and an alkoxy group having 1 carbon atom is preferable.
• Alkoxy groups of -4 are more preferred, and methoxy or ethoxy groups are particularly preferred.
• alkoxycarbonyl group examples include a group in which an oxycarbonyl group (—O—CO— group) is bonded to the alkyl group exemplified above, and among them, a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group or an isopropoxy.
• a carbonyl group is preferred, a methoxycarbonyl group is more preferred.
• alkylcarbonyloxy group examples include a group in which a carbonyloxy group (—CO—O— group) is bonded to the alkyl group exemplified above, and among them, a methylcarbonyloxy group, an ethylcarbonyloxy group, and an n-propylcarbonyloxy group.
• a group or an isopropylcarbonyloxy group is preferable, and a methylcarbonyloxy group is more preferable.
• the halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and among them, a fluorine atom or a chlorine atom is preferable.
• Z 1 , Z 2 and Z 3 are independently hydrogen atoms, monovalent aliphatic hydrocarbon groups having 1 to 20 carbon atoms, and carbon.
• Nitro group, -OR 7 , -NR 8 R 9 , -SR 10 , -COOR 11 or -COR 12 where R 7 to R 12 are independently hydrogen atoms or carbon atoms 1 to 6, respectively. Representing an alkyl group, Z 1 and Z 2 may be bonded to each other to form an aromatic ring.
• an alkyl group having 1 to 15 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, and specifically, a methyl group.
• Ethyl group, isopropyl group, tert-pentyl group (1,1-dimethylpropyl group), tert-butyl group, 1,1-dimethyl-3,3-dimethyl-butyl group are more preferable, and methyl group, ethyl group, A tert-butyl group is particularly preferred.
• Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, a methylcyclohexyl group and an ethylcyclohexyl.
• Monocyclic saturated hydrocarbon groups such as groups; cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, cycloheptenyl group, cyclooctenyl group, cyclodecenyl group, cyclopentadienyl group, cyclohexadienyl group, cyclooctadienyl group, cyclodeca Monocyclic unsaturated hydrocarbon groups such as diene; bicyclo [2.2.1] heptyl group, bicyclo [2.2.2] octyl group, tricyclo [5.2.2.10 2,6 ] decyl group, Tricyclo [3.3.1.1 3,7 ] decyl group, tetracyclo [6.2.1.1 3,6 .
• Polycyclic saturated hydrocarbon groups such as dodecyl group and adamantyl group; and the like.
• Specific examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, a 2,6-diethylphenyl group, a naphthyl group, a biphenyl group and the like, and 6 to 12 carbon atoms.
• Aryl groups particularly phenyl groups
• Specific examples of the monovalent aromatic heterocyclic group having 6 to 20 carbon atoms include a 4-pyridyl group, a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, a 2-benzothiazolyl group and the like.
• halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and among them, a fluorine atom, a chlorine atom and a bromine atom are preferable.
• alkyl group having 1 to 6 carbon atoms indicated by R 7 to R 10 specifically, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group and a sec-butyl group.
• Groups, tert-butyl group, n-pentyl group, n-hexyl group and the like can be mentioned.
• Z 1 and Z 2 may be bonded to each other to form an aromatic ring as described above.
• Z 1 and Z 2 in the above formula (Ar-1) may be bonded to each other to form an aromatic ring.
• Examples of the formed structure include a group represented by the following formula (Ar-1a).
• * represents a bonding position
• Q 1 , Q 2 and Y 1 are the same as those described in the above formula (Ar-1).
• A3 and A4 are independently derived from -O-, -N ( R13)-, -S-, and -CO-, respectively.
• X represents a non-metal atom of Group 14 to 16 to which a hydrogen atom or a substituent may be bonded.
• substituents include an alkyl group, an alkoxy group, an alkyl substituted alkoxy group, a cyclic alkyl group, an aryl group (for example, a phenyl group, a naphthyl group, etc.), a cyano group, an amino group, a nitro group, and an alkyl group.
• substituents include a carbonyl group, a sulfo group and a hydroxyl group.
• R 2- , -CR 3 CR 4- , -NR 5- , or a divalent linking group consisting of a combination of two or more of these, and R 1 to R 5 are independent hydrogen atoms, respectively. It represents a fluorine atom or an alkyl group having 1 to 12 carbon atoms.
• R 1 , R 2 and R 5 each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 12 carbon atoms. Of these, any of -CO-, -O-, and -CO-O- is preferable.
• SP 3 and SP 4 are independently single-bonded, a linear or branched alkylene group having 1 to 12 carbon atoms, or a direct group having 1 to 12 carbon atoms.
• One or more of -CH 2- constituting a chain or branched alkylene group is substituted with -O-, -S-, -NH-, -N (Q)-, or -CO-.
• examples of the linear or branched alkylene group having 1 to 12 carbon atoms shown in one aspect of SP 3 and SP 4 include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group and a hexylene group. , Methylhexylene group, heptylene group and the like are preferable.
• one or more of -CH 2- constituting a linear or branched alkylene group having 1 to 12 carbon atoms are -O-, -S-, and -NH. It may be a divalent linking group substituted with ⁇ , ⁇ N (Q) ⁇ or ⁇ CO—, and the substituent represented by Q is Y 1 in the above formula (Ar-1). Examples include the same substituents that may have.
• L 3 and L 4 each independently represent a monovalent organic group.
• Examples of the monovalent organic group indicated by L 3 and L 4 include an alkyl group, an aryl group, and a heteroaryl group.
• the alkyl group may be linear, branched or cyclic, but linear is preferred.
• the number of carbon atoms of the alkyl group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10.
• the aryl group may be monocyclic or polycyclic, but monocyclic is preferable.
• the aryl group preferably has 6 to 25 carbon atoms, more preferably 6 to 10 carbon atoms.
• the heteroaryl group may be monocyclic or polycyclic.
• the number of heteroatoms constituting the heteroaryl group is preferably 1 to 3.
• a nitrogen atom, a sulfur atom and an oxygen atom are preferable.
• the heteroaryl group preferably has 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms.
• the alkyl group, the aryl group and the heteroaryl group may be unsubstituted or may have a substituent. Examples of the substituent include the same substituents that Y 1 in the above formula (Ar-1) may have.
• Ax has at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle, and has 2 to 30 carbon atoms. Represents an organic group.
• Ay is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or an aromatic hydrocarbon ring and an aromatic. It represents an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of group heterocycles.
• the aromatic ring in Ax and Ay may have a substituent, or Ax and Ay may be bonded to form a ring.
• Q3 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.
• Ax and Ay include those described in paragraphs [0039] to [0995] of International Publication No. 2014/010325.
• Specific examples of the alkyl group having 1 to 20 carbon atoms indicated by Q3 include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert.
• -Butyl group, n-pentyl group, n-hexyl group and the like can be mentioned, and examples of the substituent include the same substituents that Y 1 in the above formula (Ar-1) may have. Can be mentioned.
• the polymerizable liquid crystal compound is preferably a compound represented by the following formula (I) for the reason that the retardation of the formed optically anisotropic layer is well expressed.
• Ar represents any aromatic ring selected from the group consisting of the groups represented by the above-mentioned formulas (Ar-1) to (Ar-7).
• q1 in the following formula (I) is 2, the plurality of Ars may be the same or different.
• G 5 independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 12 carbon atoms. However, when q1 is 2 , the plurality of D2s may be the same or different. Further, in the above formula (I), G 1 and G 2 each independently have an aromatic ring having 6 to 20 carbon atoms which may have a substituent, or carbon which may have a substituent. Representing a divalent alicyclic hydrocarbon group of number 5 to 20, one or more of -CH 2- constituting the alicyclic hydrocarbon group is substituted with -O-, -S- or -NH-. May be.
• a 1 and A 2 each independently have an aromatic ring having 6 to 20 carbon atoms which may have a substituent, or carbon which may have a substituent. Representing a divalent alicyclic hydrocarbon group of number 5 to 20, one or more of -CH 2- constituting the alicyclic hydrocarbon group is substituted with -O-, -S- or -NH-. May be.
• SP 1 and SP 2 are independently single-bonded, a linear or branched alkylene group having 1 to 12 carbon atoms, or a linear chain having 1 to 12 carbon atoms.
• Q represents a substituent.
• L 1 and L 2 each independently represent a monovalent organic group, and at least one of L 1 and L 2 represents a polymerizable group.
• Ar is an aromatic ring represented by the following formula (Ar- 3 )
• at least one of L1 and L2 and L3 and L4 in the following formula (Ar- 3 ) is a polymerizable group. Represents.
• a1, a2, g1 and g2 are preferably 1 because the polymerizable liquid crystal composition tends to show the liquid crystal state of the smectic phase. Further, it is preferable that both a1 and a2 are 0 and both g1 and g2 are 1 for the reason that the contrast of the produced image display device becomes better.
• q1 is preferably 1.
• the divalent linking group shown by one aspect of D 1 , D 2 , D 3 , D 4 , D 5 and D 6 is, for example, D 7 in the above formula (Ar-3). And similar to those described in D8. Of these, any of -CO-, -O-, and -CO-O- is preferable.
• examples of the aromatic ring having 6 to 20 carbon atoms represented by one aspect of G 1 and G 2 include aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthroline ring.
• Aromatic heterocycles such as a furan ring, a pyrrole ring, a thiophene ring, a pyridine ring, a thiazole ring, and a benzothiazole ring; Of these, a benzene ring (for example, a 1,4-phenyl group) is preferable.
• the divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms represented by one aspect of G 1 and G 2 is preferably a 5-membered ring or a 6-membered ring.
• the alicyclic hydrocarbon group may be saturated or unsaturated, but a saturated alicyclic hydrocarbon group is preferable.
• the divalent alicyclic hydrocarbon group represented by G 1 and G 2 for example, the description in paragraph [0078] of JP2012-21068A can be referred to, and this content is incorporated in the present specification. ..
• G 1 and G 2 in the above formula (I) are preferably cycloalkane rings for the reason that the contrast of the produced image display device is better.
• the cycloalkane ring include a cyclohexane ring, a cyclopeptane ring, a cyclooctane ring, a cyclododecane ring, a cyclododecane ring, and the like.
• a cyclohexane ring is preferred, a 1,4-cyclohexylene group is more preferred, and a trans-1,4-cyclohexylene group is even more preferred.
• G 1 and G 2 may have a substituent having an aromatic ring having 6 to 20 carbon atoms or a divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms. Can be the same as the substituent that Y 1 in the above formula (Ar-1) may have.
• the aromatic rings having 6 to 20 or more carbon atoms shown in one aspect of A 1 and A 2 are the same as those described in G 1 and G 2 in the above formula (I). Can be mentioned. Further, in the above formula (I), as the divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms represented by one aspect of A 1 and A 2 , in G 1 and G 2 in the above formula (I). Examples are similar to those described. Regarding A 1 and A 2 , the substituent which the aromatic ring having 6 to 20 carbon atoms or the divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms may have is the above-mentioned formula (Ar-). 1) Examples thereof include the same substituents that Y 1 may have.
• Examples of the monovalent organic group represented by L 1 and L 2 in the above formula (I) include those similar to those described in L 3 and L 4 in the above formula (Ar-3).
• the polymerizable group represented by at least one of L 1 and L 2 is not particularly limited, but a polymerizable group capable of radical polymerization or cationic polymerization is preferable.
• a known radically polymerizable group can be used, and suitable examples thereof include an acryloyloxy group and a methacryloyloxy group.
• the acryloyloxy group is generally faster in terms of the polymerization rate, and the acryloyloxy group is preferable from the viewpoint of improving productivity, but the methacryloyloxy group can also be used as the polymerizable group in the same manner.
• a known cationically polymerizable group can be used, and specifically, an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spirorthoester group, and vinyloxy.
• the group can be mentioned.
• an alicyclic ether group or a vinyloxy group is preferable, and an epoxy group, an oxetanyl group, or a vinyloxy group is particularly preferable.
• particularly preferable polymerizable groups include polymerizable groups represented by any of the following formulas (P-1) to (P-20).
• both L 1 and L 2 in the above formula (I) are polymerizable groups because the durability of the polarizing plate is improved, and acryloyloxy group or methacryloyl is preferable. It is more preferably an oxy group.
• Examples of the compound represented by the above formula (I) include the compounds represented by the general formula (1) described in JP-A-2010-084032 (particularly, those described in paragraph numbers [0067] to [0073].
• K side chain structure
• Tables 1 to 3 below, "*" shown in the side chain structure of K represents the bonding position with the aromatic ring.
• the group adjacent to the acryloyloxy group and the methacryloyl group is a propylene group (methyl group becomes an ethylene group, respectively). Represents a substituted group) and represents a mixture of positional isomers with different methyl group positions.
• the above-mentioned polymerizable liquid crystal compound is a compound showing a liquid crystal state of a smectic phase. Is more preferable.
• the polymerizable liquid crystal composition preferably contains a polymerization initiator in addition to the above-mentioned polymerizable liquid crystal compound.
• the polymerization initiator used is preferably a photopolymerization initiator capable of initiating a polymerization reaction by irradiation with ultraviolet rays.
• Examples of the photopolymerization initiator include ⁇ -carbonyl compounds (described in US Pat. Nos. 2,376,661 and 236,670), acidoin ethers (described in US Pat. No. 2,448,828), and ⁇ -hydrogen-substituted fragrances. Group acidloin compounds (described in US Pat. No.
• the polymerization initiator is an oxime-type polymerization initiator, and specific examples thereof are described in paragraphs [0049] to [0052] of International Publication No. 2017/170443. Agents are mentioned.
• the polymerizable liquid crystal composition preferably contains a solvent in addition to the above-mentioned polymerizable liquid crystal compound from the viewpoint of workability for forming an optically anisotropic layer.
• a solvent include ketones (eg, acetone, 2-butanone, methylisobutylketone, cyclohexanone, cyclopentanone, etc.), ethers (eg, dioxane, tetrahydrofuran, etc.), and aliphatic hydrocarbons.
• the polymerizable liquid crystal composition preferably contains a leveling agent from the viewpoint of keeping the surface of the optically anisotropic layer smooth and facilitating orientation control.
• a leveling agent a fluorine-based leveling agent or a silicon-based leveling agent is preferable because it has a high leveling effect on the amount of addition, and a fluorine-based leveling agent is less likely to cause crying (bloom, bleed). Is more preferable.
• Specific examples of the leveling agent include the compounds described in paragraphs [0079] to [0102] of JP-A-2007-069471, and the general formulas described in JP-A-2013-047204.
• the polymerizable liquid crystal composition may contain, if necessary, an orientation control agent in addition to the above-mentioned polymerizable liquid crystal compound.
• the orientation control agent can form various orientation states such as homeotropic orientation (vertical orientation), tilt orientation, hybrid orientation, and cholesteric orientation, in addition to homogenius orientation, and can make a specific orientation state more uniform and more uniform. It can be realized by precise control.
• orientation control agent that promotes homogenius orientation for example, a small molecule orientation control agent or a polymer orientation control agent can be used.
• the small molecule orientation control agent include paragraphs [0009] to [0083] of JP-A-2002-20363, paragraphs [0111]-[0120] of JP-A-2006-106662, and JP-A-2012.
• paragraphs [0021] to [0029] of Japanese Patent Application Laid-Open No. 211306 can be referred to, and this content is incorporated in the present specification.
• orientation control agent for forming or promoting homeotropic orientation examples include a boronic acid compound and an onium salt compound, and specifically, paragraphs [0023] to [0032] of JP-A-2008-225281. , Paragraphs [0052] to [0058] of JP2012-208397A, paragraphs [0024] to [0055] of JP2008-026730, and [0043] to [0055] of JP2016-193869.
• the compounds described in paragraphs and the like can be taken into consideration, the contents of which are incorporated herein by reference.
• the cholesteric orientation can be realized by adding a chiral agent to the polymerizable liquid crystal composition, and the turning direction of the cholesteric orientation can be controlled by the direction of the chirality.
• the pitch of the cholesteric orientation can be controlled according to the orientation regulating force of the chiral agent.
• the content is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, based on the total solid content mass in the composition.
• the content is in this range, it is possible to obtain a uniform and highly transparent cured product without precipitation, phase separation, orientation defects, etc., while achieving the desired orientation state.
• the polymerizable liquid crystal composition may contain a component other than the above-mentioned components, and examples thereof include a surfactant, a tilt angle control agent, an orientation aid, a plasticizer, a cross-linking agent, and an amine compound.
• the amine compound may have a function of not deteriorating the orientation of the polymerizable liquid crystal compound when the polymerizable liquid crystal composition is stored for several days (for example, about one week) after preparation.
• an amine compound an amine compound having a boiling point of 50 to 230 ° C.
• the content is preferably 0.01 to 10% by mass with respect to the mass of the polymerizable liquid crystal compound.
• the method for producing the optically anisotropic layer is not particularly limited, but for example, a polymerizable liquid crystal composition is applied to a predetermined substrate (for example, a support described later or an alignment layer provided on the support) to obtain a coating film. , And the coating film is subjected to an alignment treatment to bring the polymerizable liquid crystal compound into a predetermined orientation state, and then the coating film is subjected to a curing treatment.
• a predetermined substrate for example, a support described later or an alignment layer provided on the support
• the above coating can be carried out by a known method (for example, wire bar coating method, extrusion coating method, direct gravure coating method, reverse gravure coating method, die coating method, etc.).
• the alignment treatment can be performed by drying or heating at room temperature (for example, 20 to 25 ° C.).
• room temperature for example, 20 to 25 ° C.
• the liquid crystal phase formed by the orientation treatment can generally be transferred by a change in temperature or pressure.
• a liquid crystal compound having a lyotropic property it can also be transferred by the composition ratio of the amount of the solvent.
• the heating time is preferably 10 seconds to 5 minutes, more preferably 10 seconds to 3 minutes, still more preferably 10 seconds to 2 minutes.
• the curing treatment (irradiation of active energy rays (light irradiation treatment) and / or heat treatment) on the coating film can also be said to be an immobilization treatment for fixing the orientation of the specific liquid crystal compound.
• the light irradiation treatment In the polymerization by light irradiation, it is preferable to use ultraviolet rays.
• the irradiation amount is preferably 10 mJ / cm 2 to 50 J / cm 2 , more preferably 20 mJ / cm 2 to 5 J / cm 2 , further preferably 30 mJ / cm 2 to 3 J / cm 2 , and particularly preferably 50 to 1000 mJ / cm 2 . preferable.
• light irradiation treatment may be carried out under heating conditions.
• the optically anisotropic layer formed by using the polymerizable liquid crystal composition has an optical difference in which the liquid crystal state of the smectic phase is fixed. It is preferably an anisotropic layer.
• the optical film of the present invention has at least one optically anisotropic layer in which the liquid crystal state of the smectic phase is immobilized.
• an optically anisotropic layer is preferably a positive A plate or a positive C plate, and more preferably a positive A plate.
• the positive A plate (positive A plate) and the positive C plate (positive C plate) are defined as follows.
• the refractive index in the slow phase axial direction (the direction in which the refractive index in the plane is maximized) in the film plane is nx
• the refractive index in the direction orthogonal to the slow phase axis in the plane in the plane is ny
• the refraction in the thickness direction is nz
• the positive A plate satisfies the relation of the formula (A1)
• the positive C plate satisfies the relation of the formula (C1).
• the positive A plate shows a positive value for Rth
• the positive C plate shows a negative value for Rth.
• ⁇ includes not only the case where both are completely the same but also the case where both are substantially the same. “Substantially the same” means that in the positive A plate, for example, (ny-nz) ⁇ d (where d is the thickness of the film) is -10 to 10 nm, preferably -5 to 5 nm. It is included in “ny ⁇ nz”, and when (nx-nz) xd is -10 to 10 nm, preferably -5 to 5 nm, it is also included in "nx ⁇ nz”.
• (nx-ny) ⁇ d (where d is the thickness of the film) is 0 to 10 nm, preferably 0 to 5 nm, it is also included in “nx ⁇ ny”.
• Re (550) is preferably 100 to 180 nm, more preferably 120 to 160 nm, and 130 to 150 nm from the viewpoint of functioning as a ⁇ / 4 plate. It is more preferably 130 to 140 nm, and particularly preferably 130 to 140 nm.
• the " ⁇ / 4 plate” is a plate having a ⁇ / 4 function, and specifically, a function of converting linear polarization of a specific wavelength into circular polarization (or circular polarization into linear polarization). It is a plate having.
• the thickness of the optically anisotropic layer is not particularly limited, but is preferably 0.1 to 10 ⁇ m, and more preferably 0.5 to 5 ⁇ m.
• the optical film of the present invention may have a support as a base material for forming the optically anisotropic layer.
• a support is preferably transparent, and specifically, the light transmittance is preferably 80% or more.
• Examples of such a support include a glass substrate and a polymer film, and examples of the polymer film material include a cellulose-based polymer; an acrylic-based polymer having an acrylic acid ester polymer such as polymethylmethacrylate and a lactone ring-containing polymer.
• thermoplastic norbornene polymers polycarbonate polymers; polyester polymers such as polyethylene terephthalate and polyethylene naphthalate; styrene polymers such as polystyrene and acrylonitrile / styrene copolymers (AS resin); polyethylene, polypropylene, ethylene / propylene Polyolefin-based polymers such as polymers; Vinyl chloride-based polymers; Amido-based polymers such as nylon and aromatic polyamides; Imid-based polymers; Examples thereof include vinylidene chloride-based polymers; vinyl alcohol-based polymers; vinyl butyral-based polymers; allylate-based polymers; polyoxymethylene-based polymers; epoxy-based polymers; or polymers in which these polymers are mixed. Further, the stator described later may also serve as such a support.
• the thickness of the support is not particularly limited, but is preferably 5 to 60 ⁇ m, more preferably 5 to 40 ⁇ m.
• the optical film of the present invention has any of the above-mentioned supports, it is preferable that the optical film has an alignment film between the support and the cured product.
• the support described above may also serve as an alignment film.
• the alignment film is generally composed of a polymer as a main component.
• the polymer material for an alignment film has been described in a large number of documents, and a large number of commercially available products are available.
• the polymer material used in the present invention is preferably polyvinyl alcohol or polyimide, and its derivatives. Particularly modified or unmodified polyvinyl alcohol is preferable.
• the alignment film that can be used in the present invention for example, the alignment film described in International Publication No. 01/88574, page 43, lines 24 to 49, line 8; paragraphs [0071] to [00905] of Japanese Patent No. 3907735. ].
• a photoalignment film as the alignment film because it is possible to prevent surface deterioration by not contacting the surface of the alignment film when the alignment film is formed.
• the photoalignment film is not particularly limited, but is a polymer material such as a polyamide compound or a polyimide compound described in paragraphs [0024] to [0043] of International Publication No. 2005/096041; A liquid crystal alignment film formed by a liquid crystal alignment agent having a photo-oriented group; a trade name LPP-JP265CP manufactured by Polyimide, etc. can be used.
• the thickness of the alignment film is not particularly limited, but from the viewpoint of alleviating the surface irregularities that may exist on the support and forming an optically anisotropic layer having a uniform film thickness, 0. It is preferably 01 to 10 ⁇ m, more preferably 0.01 to 1 ⁇ m, and even more preferably 0.01 to 0.5 ⁇ m.
• the optical film of the present invention preferably contains an ultraviolet (UV) absorber in consideration of the influence of external light (particularly ultraviolet light).
• the ultraviolet absorber may be contained in the optically anisotropic layer, or may be contained in a member other than the optically anisotropic layer.
• a support is preferably mentioned.
• the ultraviolet absorber any conventionally known agent capable of exhibiting ultraviolet absorption can be used.
• a benzotriazole-based or hydroxyphenyltriazine-based ultraviolet absorber may be used from the viewpoint of obtaining the ultraviolet absorbing ability (ultraviolet blocking ability) used in an image display device because of its high ultraviolet absorbing ability. preferable.
• two or more kinds of ultraviolet absorbers having different maximum absorption wavelengths can be used in combination.
• the ultraviolet absorber include the compounds described in paragraphs [0258] to [0259] of JP2012-18395, paragraphs [0055] to [0105] of JP2007-72163. Examples thereof include the compounds described in.
• Tinuvin 400, Tinuvin 405, Tinuvin 460, Tinuvin 477, Tinuvin 479, Tinuvin 1577 can be used as commercially available products.
• the adhesive layer of the polarizing plate of the present invention is a layer formed by using an adhesive composition containing a polymerizable compound and a polymerization initiator. Further, in the polarizing plate of the present invention, the polymerization initiator contained in the adhesive composition satisfies the conditions 1 and 2 shown below. When the adhesive composition contains a plurality of types of polymerization initiators, any one of the polymerization initiators may satisfy the following conditions 1 and 2.
• Condition 1 The maximum absorption wavelength of the polymerization initiator is within ⁇ 70 nm of the minimum absorption wavelength of the optical film.
• Condition 2 The molar absorption coefficient of the polymerization initiator is 22,000 mol -1 Lcm -1 or more.
• the method for measuring the maximum absorption wavelength of the polymerization initiator is an absorption spectrum (measurement range) using a spectrophotometer (UV-3150, manufactured by Shimadzu Corporation) using a solution in which 5 mg of the polymerization initiator is dissolved in 1000 mL of chloroform. : 200 to 800 nm) to determine the maximum absorption wavelength.
• the method for measuring the minimum absorption wavelength of the optical film is to measure the absorption spectrum (measurement range: 200 to 800 nm) with a spectrophotometer (UV-3150, manufactured by Shimadzu Corporation) using a 40 mm square optical film. , The minimum absorption wavelength shall be obtained.
• the method for measuring the molar extinction coefficient of the polymerization initiator is to use a solution of 5 mg of the polymerization initiator dissolved in 1000 mL of chloroform and measure the absorbance of this solution using a spectrophotometer (UV-3150, manufactured by Shimadzu Corporation). It shall be measured and the molar extinction coefficient ⁇ shall be calculated from the following formula.
• the optical path length of the cell used in this measurement is 1 cm.
• A ⁇ ⁇ C ⁇ l (A: Absorbance, C: Concentration (mol / L), l: Optical path length (cm))
• the maximum absorption wavelength of the polymerization initiator and the minimum absorption wavelength of the optical film are both in the range of 250 to 400 nm.
• the adhesive composition is not particularly limited as long as it is a composition containing a polymerizable compound and a polymerization initiator, but is an active energy ray-curable adhesive composition such as an electron beam curable type, an ultraviolet curable type, and a visible light curable type. It is preferably a product, and more preferably an ultraviolet curable adhesive composition.
• Examples of the polymerizable compound contained in the adhesive composition include conventionally known cationically polymerizable compounds and radically polymerizable compounds.
• cationically polymerizable compound examples include a monofunctional cationically polymerizable compound having one cationically polymerizable functional group in the molecule and a polyfunctional cationically polymerizable compound having two or more cationically polymerizable functional groups in the molecule. ..
• the cationically polymerizable functional group examples include an epoxy group, an oxetanyl group, a vinyl ether group and the like.
• Examples of the compound having an epoxy group include phenylglycidyl ether, p-tert-butylphenylglycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide, and 1,3-butadiene mono.
• Oxide, 1,2-epoxydodecane, epichlorohydrin, 1,2-epoxydecane, styrene oxide, cyclohexene oxide, 3-methacryloyloxymethylcyclohexene oxide, 3-acryloyloxymethylcyclohexene oxide, 3-vinylcyclohexene oxide, 4 -Vinylcyclohexene oxide and the like can be mentioned.
• Examples of the compound having an oxetanyl group include 3-ethyl-3-hydroxymethyloxetane, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, and 3-ethyl-3- (phenoxymethyl).
• Examples thereof include oxetane, di [(3-ethyl-3-oxetanyl) methyl] ether, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, and phenol novolac oxetane.
• Examples of the compound having a vinyl ether group include 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, vinyl ether such as diethylene glycol, triethylene glycol divinyl ether, cyclohexanedimethanol divinyl ether, cyclohexanedimethanol monovinyl ether, and tricyclo.
• Examples thereof include decane vinyl ether, cyclohexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, and pentaerythritol type tetravinyl ether.
• radically polymerizable compound examples include compounds having a radically polymerizable functional group of a carbon-carbon double bond such as a (meth) acryloyl group and a vinyl group. Further, as the radically polymerizable compound, either a monofunctional radically polymerizable compound or a bifunctional or higher polyfunctional radically polymerizable compound can be used.
• Examples of the monofunctional radically polymerizable compound include (meth) acrylamide derivatives having a (meth) acrylamide group and various (meth) acrylic acid derivatives having a (meth) acryloyloxy group.
• (meth) acrylamide derivative examples include N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, and N-isopropyl (meth) acrylamide.
• N-Alkyl group-containing (meth) acrylamide derivatives such as N-butyl (meth) acrylamide, N-hexyl (meth) acrylamide; N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-methylol- N-hydroxyalkyl group-containing (meth) acrylamide derivatives such as N-propane (meth) acrylamide; N-aminoalkyl group-containing (meth) acrylamide derivatives such as aminomethyl (meth) acrylamide and aminoethyl (meth) acrylamide; N- N-alkyl group-containing (meth) acrylamide derivatives such as methoxymethylacrylamide and N-ethoxymethylacrylamide; N-mercaptoalkyl group-containing (meth) acrylamide derivatives such as mercaptomethyl (meth) acrylamide and mercaptoethyl (meth) acrylamide; etc. Can be mentioned.
• the (meth) acrylic acid derivative include, for example. Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 2-methyl-2-nitropropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) ) Acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, t-pentyl (meth) acrylate, 3-pentyl (meth) acrylate, 2,2-dimethylbutyl ( Meta) acrylate, n-hexyl (meth) acrylate, cetyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate
• Hydroxyl-containing (meth) acrylates such as acrylates, cyclohexanedimethanol mono (meth) acrylates, 2-hydroxy-3-phenoxypropyl (meth) acrylates; Epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether; 2,2,2-Trifluoroethyl (meth) acrylate, 2,2,2-trifluoroethyl ethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoropropyl (meth) acrylate, octafluoropentyl (meth) ) Halogen-containing (meth) acrylates such as acrylates, heptadecafluorodecyl (meth) acrylates, 3-chloro-2-hydroxypropyl (meth) acrylates
• Examples of the monofunctional radically polymerizable compound include carboxyl group-containing monomers such as (meth) acrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid.
• carboxyl group-containing monomers such as (meth) acrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid.
• Examples of the monofunctional radically polymerizable compound include lactam-based vinyl monomers such as N-vinylpyrrolidone, N-vinyl- ⁇ -caprolactam, and methylvinylpyrrolidone; vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazine, and vinylpyrazine.
• lactam-based vinyl monomers such as N-vinylpyrrolidone, N-vinyl- ⁇ -caprolactam, and methylvinylpyrrolidone
• vinylpyridine vinylpiperidone, vinylpyrimidine, vinylpiperazine, and vinylpyrazine
• Examples thereof include vinyl-based monomers having a nitrogen-containing heterocycle such as vinylpyrrole, vinylimidazole, vinyloxazole, and vinylmorpholin.
• a radically polymerizable compound having an active methylene group can be used as the monofunctional radically polymerizable compound.
• a radically polymerizable compound having an active methylene group is a compound having an active double bond group such as a (meth) acrylic group at the terminal or in a molecule and having an active methylene group.
• the active methylene group include an acetoacetyl group, an alkoxymalonyl group, a cyanoacetyl group and the like, and an acetoacetyl group is preferable.
• radically polymerizable compound having an active methylene group examples include 2-acetoacetoxyethyl (meth) acrylate, 2-acetacetoxypropyl (meth) acrylate, and 2-acetacetoxy-1-methylethyl (meth).
• Acetacetoxyalkyl (meth) acrylates such as acrylates; 2-ethoxymalonyloxyethyl (meth) acrylates, 2-cyanoacetoxyethyl (meth) acrylates, N- (2-cyanoacetoxyethyl) acrylamides, N- (2-propionyl).
• the radically polymerizable compound having an active methylene group is preferably acetoacetoxyalkyl (meth) acrylate.
• bifunctional or higher polyfunctional radically polymerizable compound examples include N, N'-methylenebis (meth) acrylamide, which is a polyfunctional (meth) acrylamide derivative, tripropylene glycol di (meth) acrylate, and tetraethylene glycol di (meth).
• ⁇ Polymer initiator> As the polymerization initiator contained in the adhesive composition, conventionally known photocationic polymerization initiators or photoradical polymerization initiators that satisfy the above-mentioned conditions 1 and 2 can be appropriately used.
• the photocationic polymerization initiator generates a cationic species or Lewis acid by irradiation with active energy rays such as visible light, ultraviolet rays, X-rays, and electron beams, and initiates a polymerization reaction of an epoxy group or an oxetanyl group.
• active energy rays such as visible light, ultraviolet rays, X-rays, and electron beams
• the photocationic polymerization initiator for example, known sulfonium salts, ammonium salts, iodonium salts (for example, diaryliodonium salts), triarylsulfonium salts, diazonium salts, iminium salts and the like can be used as the component (e).
• Examples thereof include those exemplified as the cationic polymerization catalyst in paragraph 0020 of the publication.
• Photoradical polymerization initiator examples include benzophenone compounds such as benzyl, benzophenone, benzoylbenzoic acid, and 3,3'-dimethyl-4-methoxybenzophenone; 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2).
• -Aromatic ketone compounds such as (propyl) ketone, ⁇ -hydroxy- ⁇ , ⁇ '-dimethylacetophenone, 2-methyl-2-hydroxypropiophenone, ⁇ -hydroxycyclohexylphenylketone; methoxyacetophenone, 2,2-dimethoxy- Acetphenone compounds such as 2-phenylacetophenone, 2,2-diethoxyacetophenone, 2-methyl-1- [4- (methylthio) -phenyl] -2-morpholinopropane-1; venzoine methyl ether, Benzoin ether compounds such as venzoin ethyl ether, benzoin isopropyl ether, venzoin butyl ether and anisoin methyl ether; aromatic ketal compounds such as benzyl dimethyl ketal; aromatic sulfonyl chlorides such as 2-naphthalene sulfonyl chloride.
• Photoactive oxime compounds such as 1-phenone-1,1-propanedione-2- (o-ethoxycarbonyl) oxime; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, Thioxantone compounds such as isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diisopropylthioxanthone, 2,4-diisopropylthioxanthone, dodecylthioxanthone; camphorquinone; halogenated ketone; acylphosphinoxide; acylphosphonate, etc. Can be mentioned.
• the adhesive composition preferably contains a sensitizer because the durability of the polarizing plate is further improved, and is on the long wavelength side of the maximum absorption wavelength of the polymerization initiator contained in the adhesive composition. Moreover, it is more preferable that the sensitizer having a maximum absorption wavelength is contained in the wavelength region where the transmittance of the optical film is 1% or more.
• the method for measuring the maximum absorption wavelength of the sensitizer is an absorption spectrum (measurement range) using a spectrophotometer (UV-3150, manufactured by Shimadzu Corporation) using a solution in which 5 mg of the sensitizer is dissolved in 1000 mL of chloroform. : 200 to 800 nm) to determine the maximum absorption wavelength.
• the transmittance of the optical film is measured by measuring the transmittance (measurement range: 200 to 800 nm) with a spectrophotometer (UV-3150, manufactured by Shimadzu Corporation) using a 40 mm square optical film.
• the transmittance shall be calculated.
• the maximum absorption wavelength of the sensitizer is preferably in the range of 250 to 400 nm.
• a photosensitizer is preferable, and specific examples thereof include xanthone compounds such as xanthone and thioxanthone (for example, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, etc.); anthracene and an alkoxy group.
• Anthracene compounds containing anthracene eg, dibutoxyanthracene, etc.
• phenothiazine, rubrene, etc. may be mentioned.
• the content of the sensitizer is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the polymerizable compound. , 0.5-8 parts by mass is more preferable.
• the polarizing plate of the present invention has a surface on the adhesive layer side of the optical film (hereinafter, abbreviated as "surface A1” in this paragraph) or adhesion for the reason that the adhesiveness between the polarizing element and the optical film is improved. It is preferable that a polymer having a repeating unit represented by the following formula (B) is present on the surface of the layer on the optical film side (hereinafter, abbreviated as “surface A2” in this paragraph), and it is preferable that the polymer is present. It is more preferable that a polymer having a repeating unit represented by the following formula (B) is present on the surface A1 for the reason that the adhesiveness to the optical film is further improved.
• the presence of the polymer on the surface A1 and the surface A2 can be confirmed by, for example, time-of-flight secondary ion mass spectrometry (TOF-SIMS).
• TOF-SIMS time-of-flight secondary ion mass spectrometry
• the method described in "Surface Analysis Technology Selection Book Secondary Ion Mass Spectrometry” edited by Japan Surface Science Society, Maruzen Co., Ltd. (published in 1999) can be adopted.
• the fragment derived from the repeating unit represented by the following formula (B) is detected together.
• R b1 represents a hydrogen atom, a fluorine atom, a chlorine atom, or an alkyl group having 1 to 20 carbon atoms.
• L b1 represents a single bond or a divalent linking group.
• U b1 and U b2 independently represent -O-, -S-, -COO-, -OCO-, -CONH-, -NHCOO-, or -NH-.
• R b2 and R b3 independently represent a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, respectively.
• R b2 and R b3 may be bonded to each other via a linking group.
• an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 8 carbon atoms (for example, a methyl group, etc.) Ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, and cyclohexyl group) are more preferable, and alkyl groups having 1 to 4 carbon atoms are more preferable, and methyl groups are more preferable.
• an ethyl group is particularly preferable.
• R b1 preferably represents a hydrogen atom or a methyl group.
• examples of the divalent linking group represented by one aspect of L b1 include -O-, -S-, -COO-, -OCO-, -CONR b4-, and -NR b4 COO- . , -CR b4 N-, a substituted or unsubstituted divalent aliphatic group, a substituted or unsubstituted divalent aromatic group, and a divalent linking group selected from the group consisting of a combination thereof.
• R b4 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
• substituents that the divalent aliphatic group may have include the same specific examples as those described in the substituent group Y described later, and specific examples of R b4 include. , The same as the specific example of R b1 can be mentioned.
• divalent linking groups -O-, -COO-, -OCO-, -CONR 9- , -NR 9 COO-, substituted or unsubstituted divalent aliphatic groups, substituted or unsubstituted.
• a divalent aromatic group and a divalent linking group selected from the group consisting of combinations thereof are preferable.
• L b1 contains a substituted or unsubstituted divalent aromatic group, the number of aromatic rings is preferably 1 to 3, more preferably 1 to 2, and even more preferably 1.
• U b1 and U b2 are independently of -O-, -S-, -COO-, -OCO-, -CONH-, -NHCOO-, or -NH, respectively, as described above.
• an alkyl group an alkenyl group or an alkynyl group which may have a substituent may be used.
• the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group and a tridecyl group.
• alkenyl group examples include a linear group such as a vinyl group, a 1-propenyl group, a 1-butenyl group, a 1-methyl-1-propenyl group, a 1-cyclopentenyl group and a 1-cyclohexenyl group. , Branched or cyclic alkenyl groups.
• alkynyl group include an ethynyl group, a 1-propynyl group, a 1-butynyl group, a 1-octynyl group and the like.
• substituted or unsubstituted aryl group represented by one aspect of R b2 and R b3 for example, one in which one to four benzene rings form a fused ring, a benzene ring and an unsaturated five-membered ring are used.
• examples thereof include those in which a fused ring is formed, and specific examples thereof include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenabutenyl group, a fluorenyl group, a pyrenyl group and the like.
• a heteroaromatic ring containing one or more heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom for example, a heteroaromatic ring containing one or more heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom.
• a heteroaryl group obtained by removing one of the above hydrogen atoms can be mentioned.
• Specific examples of the heteroaromatic ring containing one or more heteroatoms selected from the group consisting of nitrogen atom, oxygen atom and sulfur atom include, for example, pyrrole, furan, thiophene, pyrazole, imidazole, triazole, oxazole and isooxazole.
• R b2 and R b3 may have include monovalent non-metal atomic groups excluding hydrogen, and are selected from the following substituent group Y, for example.
• substituent group Y Halogen atom (-F, -Br, -Cl, -I), hydroxyl group, alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group , N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-ally Lucarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diary
• Diarylphosphonooxy groups (-OPO 3 (aryl) 2 ), alkylarylphosphonooxy groups (-OPO 3 (alkyl) (aryl)), monoalkylphosphonooxy groups (-OPO 3 H (alkyl)) and Its conjugated base group, monoarylphosphonooxy group (-OPO 3H (aryl)) and its conjugated base group, cyano group, nitro group, aryl group, alkenyl group and alkynyl group, and substituents thereof. May form a ring by bonding substituents to each other or to a hydrocarbon group substituted, if possible.
• a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group is preferable, a hydrogen atom, a substituted or unsubstituted alkyl group is more preferable, and hydrogen. It is more preferable that they are linked to each other by an atom or an alkylene linking group.
• monomers forming the repeating unit represented by the above formula (B) include the monomers represented by the following formulas 3-1 to 3-26.
• the polymer is a copolymer having a repeating unit represented by the following formula (F), for the reason that the adhesiveness between the polarizing element and the optical film is further improved. ..
• R f1 represents a hydrogen atom, a fluorine atom, a chlorine atom, or an alkyl group having 1 to 20 carbon atoms.
• L f1 represents a single bond or a divalent linking group.
• R f2 represents a group containing at least one group of the following (a) to (c).
• A A group represented by any of the following formulas (1) to (3)
• the alkyl group having 1 to 20 carbon atoms represented by one aspect of R f1 is the same as the alkyl group having 1 to 20 carbon atoms represented by one aspect of R b1 in the above formula (B). Things can be mentioned. Of these, an alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group or an ethyl group is particularly preferable.
• R f1 preferably represents a hydrogen atom or a methyl group.
• examples of the divalent linking group represented by one aspect of L f1 include the same as the divalent linking group represented by one aspect of L b1 in the above formula (B). Of these, -O-, -CO-O-, -CO-NH-, and -O-CO- are preferable.
• R f2 represents a group containing at least one group of the above (a) to (c).
• RF1 of the repeating unit formula (F-1) having a group represented by the formula (a) (1), (2) or (3) is a group represented by the above formula (1), (2) or (3).
• the formula (F-1) is a repeating unit represented by the following formula (4).
• Rfa is a group represented by the above formula (1), (2) or (3).
• R 1B is a divalent group having 2 to 50 carbon atoms.
• the divalent group having 2 to 50 carbon atoms represented by R 1B may contain a hetero atom, and may contain an aromatic group, a hetero aromatic group, a hetero ring group, an aliphatic group, and an alicyclic group. It may be a group. Specific examples of R 1B include the following groups.
• X is an alkyl group having 1 to 3 carbon atoms (methyl group, ethyl group, propyl group), an alkoxy group having 1 to 4 carbon atoms (methoxy group, ethoxy group, propoxy group, butoxy group, etc.) and a halogen atom.
• Y represents -O-CO-, -CO-O-, -CONH- or -NHCO-.
• X is preferably 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, and more preferably 1,4-phenylene.
• Specific examples of the particularly preferable divalent group having 2 to 50 carbon atoms represented by R 1B include a divalent group having the following structure.
• R 2 is a hydrogen atom or a methyl group.
• RF1 has a perfluoropolyether group.
• the perfluoropolyether group is a divalent group in which a plurality of fluorocarbon groups are bonded by an ether bond.
• the perfluoropolyether group is preferably a divalent group in which a plurality of perfluoroalkylene groups are bonded by an ether bond.
• the perfluoropolyether group may have a linear structure, a branched structure, or a cyclic structure, and is preferably a linear structure or a branched structure, and more preferably a linear structure.
• the formula (F-1) is preferably a structural unit represented by the following formula (Ib).
• LF1 represents the same group as in formula (F-1).
• R 11 represents a hydrogen atom, a fluorine atom, a chlorine atom, or an alkyl group having 1 to 20 carbon atoms.
• Rf 1 and Rf 2 independently represent a fluorine atom or a perfluoroalkyl group. When a plurality of Rf 1s exist, they may be the same or different from each other. When there are a plurality of Rf 2 , they may be the same or different.
• u represents an integer of 1 or more.
• p represents an integer of 1 or more.
• R 12 represents a hydrogen atom or a substituent, and the substituent is not particularly limited, but for example, a fluorine atom, a perfluoroalkyl group (preferably 1 to 10 carbon atoms), and an alkyl group (preferably 1 to 1 carbon atoms). 10), hydroxyalkyl groups (preferably 1 to 10 carbon atoms) and the like can be mentioned.
• u represents an integer of 1 or more, preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3.
• p represents an integer of 1 or more, preferably represents 1 to 100, more preferably represents 1 to 80, and further preferably represents 1 to 60.
• the p [CRf 1 Rf 2 ] uOs may be the same or different.
• the compound having a proton donor functional group and the compound having a proton acceptor functional group are preferably compounds represented by any of the following formulas (1-1) to (1 to 3).
• n 1 to 1.
• the sum of m and n represents an integer of 2 to 6.
• HB represents the above-mentioned hydrogen-bondable functional group (that is, a proton donor functional group and a proton acceptor functional group), and m is 2.
• the plurality of HBs may be the same or different from each other.
• the proton donor functional group include a carboxy group and a sulfonic acid group.
• proton acceptor functional group include a group containing a nitrogen atom.
• X1 and X2 independently represent a single bond or a divalent linking group, and when m is an integer of 2 to 5, a plurality of them are present. X1 may be the same or different, and when n is an integer of 2 to 5, the plurality of X2s may be the same or different.
• HB and X2 may form a ring with a part of HB and X2, and in the above formula (1-3), RL and X1 are RL and X1.
• a ring may be formed with a part of.
• a linear chain having 1 to 10 carbon atoms which may have a substituent may be used.
• a state, a branched or cyclic alkylene group, an arylene group having 6 to 12 carbon atoms which may have a substituent, an ether group (—O—), a carbonyl group (—C ( O) ⁇ ), and Included are at least one or more groups selected from the group consisting of imino groups (-NH-) which may have substituents.
• examples of the substituent that the alkylene group, arylene group and imino group may have include an alkyl group, an alkoxy group, a halogen atom, a hydroxyl group and the like.
• the alkyl group for example, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, etc.) is preferable.
• n-butyl group, isobutyl group, sec-butyl group, t-butyl group, cyclohexyl group, etc.) are more preferable, alkyl groups having 1 to 4 carbon atoms are more preferable, and methyl groups or ethyl groups are preferable. Especially preferable.
• alkoxy group for example, an alkoxy group having 1 to 18 carbon atoms is preferable, an alkoxy group having 1 to 8 carbon atoms (for example, a methoxy group, an ethoxy group, an n-butoxy group, a methoxyethoxy group, etc.) is more preferable, and carbon.
• halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and among them, a fluorine atom and a chlorine atom are preferable.
• the linear alkylene group specifically includes, for example, a methylene group, an ethylene group, a propylene group, a butylene group and a pentylene group. Examples include a hexylene group and a decylene group. Specific examples of the branched alkylene group include a dimethylmethylene group, a methylethylene group, a 2,2-dimethylpropylene group and a 2-ethyl-2-methylpropylene group.
• cyclic alkylene group examples include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cyclooctylene group, a cyclodecylene group, an adamantane-diyl group, and a norbornane-diyl group.
• arylene group having 6 to 12 carbon atoms include a phenylene group, a xylylene group, a biphenylene group, a naphthylene group, a 2,2'-methylenebisphenyl group, and the like, among which the phenylene group is used. preferable.
• X3 represents a single bond or a 2- to hexavalent linking group.
• divalent linking group represented by one aspect of X3 those described as the divalent linking group represented by one aspect of X1 and X2 in the above formulas (1-1) to (1-3) are described.
• examples of the 3- to hexavalent linking group shown in one aspect of X3 include cycloalkylene rings such as cyclohexane ring and cyclohexene ring; aromatic hydrocarbons such as benzene ring, naphthalene ring, anthracene ring and phenanthroline ring.
• a hydrogen atom bonded to a carbon atom forming a ring in a ring structure such as a hydrogen ring; an aromatic heterocycle such as a furan ring, a pyrrole ring, a thiophene ring, a pyridine ring, a thiazole ring, or a benzothiazole ring;
• Examples include structures excluding 3 to 6 pieces.
• a benzene ring for example, a benzene-1,2,4-yl group is preferable.
• RL represents a substituent containing a fluorine atom or an alkyl group having 6 or more carbon atoms, and when n is an integer of 2 to 5, a plurality of RLs are used.
• the RLs may be the same or different.
• examples of the monovalent substituent containing a fluorine atom include an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms in which at least one carbon atom has a fluorine atom as a substituent. Be done.
• the compound having a proton donor functional group is specifically, for example, a compound represented by the following formula. Can be mentioned.
• the compound having a proton acceptor functional group is specifically represented by, for example, the following formula.
• Compounds include.
• the image display device of the present invention is an image display device having the optical film of the present invention or the polarizing plate of the present invention.
• the display element used in the image display device of the present invention is not particularly limited, and examples thereof include a liquid crystal cell, an organic electroluminescence (hereinafter abbreviated as “EL”) display panel, and a plasma display panel.
• EL organic electroluminescence
• a liquid crystal cell and an organic EL display panel are preferable, and a liquid crystal cell is more preferable.
• the image display device of the present invention is preferably a liquid crystal display device using a liquid crystal cell as a display element and an organic EL display device using an organic EL display panel as a display element, and the liquid crystal display device is preferable. More preferred.
• the liquid crystal display device which is an example of the image display device of the present invention, is a liquid crystal display device having the above-mentioned polarizing plate of the present invention and a liquid crystal cell.
• the polarizing plate of the present invention among the polarizing plates provided on both sides of the liquid crystal cell, it is preferable to use the polarizing plate of the present invention as the polarizing plate on the front side, and the polarizing plate of the present invention as the polarizing plate on the front side and the rear side. Is more preferable to use.
• the liquid crystal cells constituting the liquid crystal display device will be described in detail below.
• the liquid crystal cell used in the liquid crystal display device is a VA (Vertical Element) mode, an OCB (Optically Compensated Bend) mode, an IPS (In-Plane-Switching) mode, an FFS (Fringe-Field-Switching) mode, or a TN (Tw) mode.
• VA Vertical Element
• OCB Optically Compensated Bend
• IPS In-Plane-Switching
• FFS Feringe-Field-Switching
• TN Tw
• the Nematic) mode is preferred, but is not limited to these.
• the rod-shaped liquid crystal molecules are substantially horizontally oriented when no voltage is applied, and are further twisted to 60 to 120 °.
• the TN mode liquid crystal cell is most often used as a color TFT liquid crystal display device, and has been described in many documents.
• the rod-shaped liquid crystal molecules are substantially vertically oriented when no voltage is applied.
• a VA mode liquid crystal cell in a narrow sense (1) in which rod-shaped liquid crystal molecules are oriented substantially vertically when no voltage is applied and substantially horizontally when a voltage is applied
• 176625 Japanese Patent Publication No. 176625
• SID97 Voltage of technique. Papers (Proceedings) 28 (1997) 845 in which the VA mode is multi-domainized for expanding the viewing angle.
• Liquid crystal cells in a mode in which rod-shaped liquid crystal molecules are substantially vertically oriented when no voltage is applied and twisted and multi-domain oriented when a voltage is applied. (1998)) and (4) SURVIVAL mode liquid crystal cell (announced at LCD International 98). Further, it may be any of PVA (Patternized Vertical Alignment) type, optical alignment type (Optical Alignment), and PSA (Polymer-Stained Alignment). Details of these modes are described in Japanese Patent Application Laid-Open No. 2006-215326 and Japanese Patent Application Laid-Open No. 2008-538819.
• the rod-shaped liquid crystal molecules are oriented substantially parallel to the substrate, and the liquid crystal molecules respond in a planar manner when an electric field parallel to the substrate surface is applied.
• the display is black when no electric field is applied, and the absorption axes of the pair of upper and lower polarizing plates are orthogonal to each other.
• Methods for reducing leakage light when displaying black in an oblique direction and improving the viewing angle by using an optical compensation sheet are described in JP-A-10-54982, JP-A-11-202323, and JP-A-9-292522. It is disclosed in JP-A-11-133408, JP-A-11-305217, JP-A-10-307291, and the like.
• the organic EL display device which is an example of the image display device of the present invention, includes, for example, a ⁇ / 4 plate (positive A plate) composed of a polarizing element, an optically anisotropic layer of the present invention, and an organic EL from the viewing side.
• a mode having a display panel in this order is preferably mentioned.
• the organic EL display panel is a display panel configured by using an organic EL element formed by sandwiching an organic light emitting layer (organic electroluminescence layer) between electrodes (between a cathode and an anode).
• the configuration of the organic EL display panel is not particularly limited, and a known configuration is adopted.
• ⁇ Matte solution ⁇ ⁇ Silica particles with an average particle size of 20 nm (AEROSIL R972, manufactured by Nippon Aerosil Co., Ltd.) 2 parts by mass ⁇ Methylene chloride (first solvent) 76 parts by mass ⁇ Methanol (second solvent) 11 parts by mass ⁇ Core layer cellulose acylate dope 1 1 part by mass ⁇
• ⁇ Making protective film 1> Three layers of the core layer cellulose acylate dope 1 and the outer layer cellulose acylate dope 1 on both sides thereof were simultaneously poured from the discharge port onto a drum at 20 ° C. With the solvent content of the film on the drum being approximately 20% by mass, the film was peeled off from the drum, and both ends of the obtained film in the width direction were fixed with tenter clips, and the residual solvent in the film was 3 to 15% by mass. The film was dried while being stretched 1.2 times in the lateral direction in the state of%. Then, the obtained film was transferred between the rolls of the heat treatment apparatus to prepare a cellulose acylate film 1 having a thickness of 25 ⁇ m, which was used as a protective film 1.
• a hard coat curable composition shown in Table 4 below was prepared.
• the hard coat curable composition 1 is applied onto the surface of the protective film 1 prepared above, then dried at 100 ° C. for 60 seconds, and UV is 1.5 kW under the condition of nitrogen 0.1% or less. , 300 mJ was irradiated and cured to prepare a protective film 1 with a hard coat layer having a hard coat layer having a film thickness of 5 ⁇ m. The film thickness of the hard coat layer was adjusted by using a slot die and adjusting the coating amount in the die coat method.
• a polarizing plate 1 with a single-sided protective film (hereinafter, also simply referred to as “polarizing plate 1”) was produced by laminating them by roll-to-roll so that the polarization axis and the longitudinal direction of the film were orthogonal to each other. At this time, the protective film was bonded so that the cellulose acylate film side was on the polarizing element side.
• polarizing plate 2 with single-sided protective film [Preparation of polarizing plate 2 with single-sided protective film]
• the polarizing plate 2 with a single-sided protective film (hereinafter, also simply referred to as “polarizing plate 2”) was produced in the same manner except that the hard coat layer was not provided on the surface of the protective film 1.
• each liquid crystal display device was manufactured by using the polarizing plate 1 on the visual recognition side and the polarizing plate 2 on the backlight side.
• Polyester (number average molecular weight 800)
• Matte solution ⁇ ⁇ Silica particles with an average particle size of 20 nm (AEROSIL R972, manufactured by Nippon Aerosil Co., Ltd.) 2 parts by mass ⁇ Methylene chloride (first solvent) 76 parts by mass ⁇ Methanol (second solvent) 11 parts by mass ⁇ Core layer cellulose acylate dope 1 part by mass ⁇
• ⁇ Making protective film 2> After filtering the core layer cellulose acylate dope 2 and the outer layer cellulose acylate dope 2 with a filter paper having an average pore diameter of 34 ⁇ m and a sintered metal filter having an average pore diameter of 10 ⁇ m, the core layer cellulose acylate dope 2 and outer layer cellulose on both sides thereof are filtered. Three layers of acylate dope 2 were simultaneously cast on a drum at 20 ° C. from the casting port (band spreading machine). Next, with the solvent content of the film on the drum being approximately 20% by mass, the film was peeled off from the drum, both ends of the film in the width direction were fixed with tenter clips, and the film was stretched laterally at a stretching ratio of 1.1 times.
• the obtained film was further dried by transporting it between the rolls of the heat treatment apparatus to prepare a cellulose acylate film 2 having a film thickness of 40 ⁇ m, which was used as a protective film 2.
• composition 1 for forming an optically anisotropic layer having the following composition was prepared.
• Composition for forming an optically anisotropic layer 1 ⁇ -The following liquid crystal compound R1 42.00 parts by mass-The following liquid crystal compound R2 42.00 parts by mass-The following polymerizable compound A1 12.00 parts by mass-The following polymerizable compound A2 4.00 parts by mass-The following polymerization initiator S1 0.
• the group adjacent to the acryloyloxy group of the following liquid crystal compounds R1 and R2 represents a propylene group (a group in which a methyl group is replaced with an ethylene group), and the following liquid crystal compounds R1 and R2 have different positional isomers of the methyl group. Represents a mixture of bodies.
• ⁇ Preparation of the first optically anisotropic layer> A die coating method using a slot die described in Example 1 of JP-A-2006-122889 was applied to one side of the prepared protective film 2 to form a photo-alignment film forming material, and a transfer speed of 30 m / min was used. And dried at 120 ° C. for 1 minute to remove the solvent. Then, by irradiating with polarized ultraviolet rays (10 mJ / cm 2 , using an ultrahigh pressure mercury lamp), a photoalignment film 1 having a thickness of 0.3 ⁇ m was formed.
• composition 1 for forming an optically anisotropic layer prepared above was applied onto the photoalignment film 1 with a spin coater so that the film thickness after drying was 2.5 ⁇ m.
• the mixture is heated in a temperature range indicating the liquid crystal state of the nematic phase for 30 seconds, cooled to a temperature 10 ° C. lower than the phase transition temperature from the nematic phase to the smectic phase, and then UV-irradiated at that temperature (300 mJ / cm 2 ). ) was carried out to prepare a first optically anisotropic layer immobilized in a liquid crystal state of the smectic (Sm) phase.
• a layer was prepared to obtain an optical film 1.
• the layer structure of the optical film 1 is a layer structure having a protective film 2, a photoalignment film 1, a first optically anisotropic layer, and a second optically anisotropic layer in this order.
• the retardation Rth2 (550) in the thickness direction of the obtained second optically anisotropic layer was ⁇ 100 nm, and Rth2 (450) / Rth2 (550) was 0.95.
• the wavelength dispersibility of the obtained optical film 1, that is, Re (450) / Re (550) was 0.86.
• Compound K1 (A-600, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) 8.0 parts by mass ⁇ 3.0 parts by mass of the polymerization initiator S1 ⁇ 0.4 parts by mass of the following leveling agent P2 ⁇
• the following leveling agent P3 0. 5 parts by mass, methyl ethyl ketone 175.0 parts by mass, cyclopentanone 75.0 parts by mass, methanol 12.5 parts by mass, isopropanol 12.5 parts by mass ⁇ ⁇
• the adhesive composition 1-1 After corona-treating the surface of the produced optical film 1 on the side of the second optically anisotropic layer with a discharge amount of 150 W ⁇ min / m 2 , the adhesive composition 1-1 is applied so as to have a film thickness of 3.0 ⁇ m. And formed an adhesive layer. After that, the adhesive-coated surface was bonded to the polarizing element surface of the polarizing plate 1 with a single-sided protective film, and ultraviolet rays were irradiated at 300 mJ / cm 2 from the substrate side of the laminate at room temperature in an atmospheric atmosphere. A polarizing plate was prepared.
• ⁇ Preparation of protective film 3> The PMMA dope described above was uniformly cast on a stainless steel band (casting support) from the casting die (band casting machine). The film was peeled off with a solvent content of about 20% by mass in the cast film, both ends in the width direction of the film were fixed with tenter clips, and the film was dried while being stretched laterally at a stretching ratio of 1.1 times. Then, the obtained film was further dried by transporting it between the rolls of the heat treatment apparatus to prepare a PMMA film having a film thickness of 20 ⁇ m, which was used as a protective film 3.
• Adhesive Composition 2 The following compounds were mixed at the ratios described to prepare an adhesive composition 2.
• Polymerizable compound (Aronix M-220, manufactured by Toa Synthetic Co., Ltd.): 20 parts by mass Polymerizable compound (4-hydroxybutyl acrylate, manufactured by Nippon Kasei Co., Ltd.): 40 parts by mass Polymerizable compound (-2-ethylhexyl acrylate, Mitsubishi Chemical Co., Ltd.): 40 parts by mass Polymerizable initiator (Irgacure907, manufactured by BASF): 1.5 parts by mass Sensitizer (KAYACURE DETX-S, manufactured by Nippon Kayaku Co., Ltd.): 0.5 parts by mass
• the first optically anisotropic layer and the second The first polarizing plate containing the two optically anisotropic layers is on the visual recognition side
• the second polarizing plate is on the backlight side
• the absorption axes of the polarizing elements in the respective polarizing plates are orthogonal to each other, and the inside of the liquid crystal cell.
• the liquid crystal display device of Example 1 was manufactured by laminating with a 20 ⁇ m acrylic pressure-sensitive adhesive so that the orientation direction of the liquid crystal of No. 1 was orthogonal to the absorption axis of the polarizing element in the first polarizing plate.
• the liquid crystal cell in the liquid crystal display device includes a color filter layer on the substrate on the first polarizing plate side and a TFT layer on the substrate on the second polarizing plate side, and each Rth (550) is 10 nm. It was 2 nm. Further, ⁇ n ⁇ d of the liquid crystal compound in the liquid crystal cell was 340, and the tilt angle of the liquid crystal compound with respect to the substrate surface was 0.1 °.
• Example 2 Adhesive in the same manner as the adhesive composition 1-1, except that a polymerization initiator (CPI-300, manufactured by San-Apro Co., Ltd.) was used instead of the polymerization initiator (Irgcure 290, BASF Japan Ltd.). Composition 1-2 was prepared. Next, the first polarizing plate and the liquid crystal display device were produced in the same manner as in Example 1 except that the adhesive composition 1-2 was used instead of the adhesive composition 1-1.
• a polymerization initiator CPI-300, manufactured by San-Apro Co., Ltd.
• Example 3 The first polarizing plate was prepared by the method shown below. Further, a liquid crystal display device was produced in the same manner as in Example 1 except that the first polarizing plate produced by the method shown below was used.
• Example 4 to 10 The first polarizing plate and the first polarizing plate and the liquid crystal compound used for forming the second optical anisotropy were changed to the liquid crystal compounds shown in Table 5 below in the same manner as in Example 1. , A liquid crystal display device was manufactured.
• Example 11 The composition 3 for forming an optically anisotropic layer was prepared by the same method as in Example 1 except that the leveling agent P3 was not blended.
• the first polarizing plate and the liquid crystal display device were used in the same manner as in Example 1 except that the composition 3 for forming an optically anisotropic layer was used instead of the composition 2 for forming an optically anisotropic layer. Made.
• Example 12 The first polarizing plate and the liquid crystal display device were produced in the same manner as in Example 1 except that the first optically anisotropic layer was immobilized in the liquid crystal state of the nematic (Nm) phase.
• Example 13 The adhesive composition 1-4 was prepared in the same manner as the adhesive composition 1-1 except that the sensitizer (isopropylthioxanthone, manufactured by Tokyo Chemical Industry Co., Ltd.) was not blended. Next, the first polarizing plate and the liquid crystal display device were produced in the same manner as in Example 1 except that the adhesive composition 1-4 was used instead of the adhesive composition 1-1.
• the sensitizer isopropylthioxanthone, manufactured by Tokyo Chemical Industry Co., Ltd.
• Example 1 As the adhesive composition used for producing the first polarizing plate, the same as in Example 1 except that the adhesive composition 2 used for producing the second polarizing plate was used instead of the adhesive composition 1-1.
• the first polarizing plate and the liquid crystal display device were manufactured by the same method.
• the black brightness was measured using a measuring device (EZ-Contrast XL88, manufactured by ELDIM) when the liquid crystal display device displayed black in a dark room.
• the average value of the brightness at the azimuth angles of 45 °, 135 °, 225 ° and 315 ° at the polar angle of 60 ° was defined as the light leakage Y, and the evaluation was performed according to the following criteria. The results are shown in Tables 5 and 6 below.
• the absorption axis direction of the polarizing element on the viewing side is 0 ° (and 180 °)
• the absorption axis direction of the polarizing element on the backlight side (second polarizing element) is 90 °.
• the azimuth was defined to be (and 270 °).
• the prepared first polarizing plate was cut into a polarizing element of 400 mm ⁇ 400 mm, bonded to a glass substrate via an adhesive (SK-2057, manufactured by Soken Chemical Co., Ltd.), and held at 65 ° C. at 90% for 500 hours.
• the degree of polarization P was measured with VAP-7070 (manufactured by JASCO Corporation) and evaluated according to the following criteria. The results are shown in Tables 5 and 6 below. (Evaluation criteria) A: P ⁇ 99% B: 90% ⁇ P ⁇ 99% C: P ⁇ 90%
• Liquid crystal compound R3 A mixture of the following liquid crystal compounds (RA) (RB) (RC) at 83: 15: 2 (mass ratio).
• the polarizing plate using the optical film exhibiting forward wavelength dispersibility does not have the problem of adhesion between the splitter and the optical film and the problem of inferior durability.
• the polymerization initiator does not satisfy the above-mentioned condition 1 or condition 2
• the polarizing plate using the optical film exhibiting the reverse wavelength dispersibility is inferior in the adhesiveness between the polarizing element and the optical film and has durability.
• Example 14 The first polarizing plate was produced by the same method as in Example 1 except that the second optically anisotropic layer was not formed. Further, when the adhesiveness and durability of the produced first polarizing plate were evaluated by the same method as in Example 1, the adhesiveness evaluation result was "B" as shown in Table 7 below, and the durability was evaluated. The result was "A”.
• Example 15 The composition 1 for forming an optically anisotropic layer was changed to the composition 3 for forming an optically anisotropic layer below, and the same method as in Example 1 was used except that the second optically anisotropic layer was not formed.
• the first polarizing plate was prepared. In Example 15, it was confirmed by the above-mentioned method that the leveling agent P3 was present on the surface of the first optically anisotropic layer on the adhesive layer side. Moreover, when the adhesiveness and durability of the produced first polarizing plate were evaluated by the same method as in Example 1, all the evaluation results were "A" as shown in Table 7 below.
• composition for forming an optically anisotropic layer 3 ⁇ -The liquid crystal compound R1 42.00 parts by mass-The liquid crystal compound R2 42.00 parts by mass-The polymerizable compound A1 12.00 parts by mass-The polymerizable compound A2 4.00 parts by mass-The polymerization initiator S1 0. 50 parts by mass, 0.23 parts by mass of the above leveling agent, High Solve Polymer (manufactured by Toho Chemical Industry Co., Ltd.) 2,000 parts by mass, NK ester A-200 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) 1.00 parts by mass, methyl ethyl ketone 424 .8 parts by mass ⁇
• Example 16 The composition 1 for forming an optically anisotropic layer is changed to the composition 4 for forming an optically anisotropic layer below, and the composition 2 for forming an optically anisotropic layer is changed to the composition 5 for forming an optically anisotropic layer below.
• the first polarizing plate was produced in the same manner as in Example 1 except for the above. Moreover, when the adhesiveness and durability of the produced first polarizing plate were evaluated by the same method as in Example 1, all the evaluation results were "A" as shown in Table 8 below.
• composition for forming an optically anisotropic layer 4 ⁇ -The following liquid crystal compound R21 20.00 parts by mass-The following liquid crystal compound R22 27.00 parts by mass-The following liquid crystal compound R23 16.50 parts by mass-The following liquid crystal compound R24 16.50 parts by mass-The above liquid crystal compound R2 20.00 parts by mass -The following polymerizable compound A3 15.00 parts by mass-NK ester DCP (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) 3.00 parts by mass-The above-mentioned polymerization initiator S1 1.50 parts by mass-DIPEA (manufactured by Koei Chemical Industry Co., Ltd.) 0. 04 parts by mass ⁇

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