WO2022224494A1 - 位相差層付偏光板 - Google Patents

位相差層付偏光板 Download PDF

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Publication number
WO2022224494A1
WO2022224494A1 PCT/JP2021/046980 JP2021046980W WO2022224494A1 WO 2022224494 A1 WO2022224494 A1 WO 2022224494A1 JP 2021046980 W JP2021046980 W JP 2021046980W WO 2022224494 A1 WO2022224494 A1 WO 2022224494A1
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Prior art keywords
layer
retardation layer
polarizing plate
liquid crystal
retardation
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PCT/JP2021/046980
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English (en)
French (fr)
Japanese (ja)
Inventor
一晃 米澤
拓也 永田
寛 友久
Original Assignee
日東電工株式会社
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Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to KR1020237035714A priority Critical patent/KR20230169171A/ko
Priority to CN202180097208.8A priority patent/CN117178211A/zh
Publication of WO2022224494A1 publication Critical patent/WO2022224494A1/ja

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3083—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
    • 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
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • 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
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • 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
    • 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
    • B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
    • B32B2309/08—Dimensions, e.g. volume
    • B32B2309/10—Dimensions, e.g. volume linear, e.g. length, distance, width
    • B32B2309/105—Thickness

Definitions

  • the present invention relates to a polarizing plate with a retardation layer.
  • the present invention has been made to solve the conventional problems described above, and its main purpose is to provide a polarizing plate with a retardation layer in which the occurrence of cracks is suppressed in a low-temperature environment.
  • the polarizing plate with a retardation layer of the present invention comprises a protective layer, a polarizer, a retardation layer and an adhesive layer in this order, the total thickness from the protective layer to the retardation layer is 80 ⁇ m or less, and the adhesive
  • the storage modulus G'-30 of the agent layer at -30 °C is 250 kPa or less.
  • the storage elastic modulus G'-30 at -30 °C of the pressure-sensitive adhesive layer and the storage elastic modulus G'25 at 25 °C of the pressure-sensitive adhesive layer satisfy the following formula (1): . 1 ⁇ G'- 30 / G'25 ⁇ 10 (1)
  • the pressure-sensitive adhesive layer has a storage modulus G'-30 at -30 °C of 200 kPa or less.
  • the pressure-sensitive adhesive layer is composed of an acrylic pressure-sensitive adhesive containing an acrylic base polymer.
  • the acrylic base polymer contains 1 to 40 parts by weight of C 10-20 linear alkyl (meth)acrylic acid relative to 100 parts by weight of total monomer components.
  • the acrylic base polymer contains lauryl acrylate as the C 10-20 linear alkyl (meth)acrylate.
  • the acrylic base polymer contains one or more monomers selected from nitrogen atom-containing ring-containing monomers, hydroxyl group-containing monomers and carboxy group-containing monomers with respect to a total of 100 parts by weight of the monomer components. It contains 5 to 30 parts by weight of a polar group-containing monomer.
  • the acrylic base polymer contains 10 parts by weight or less of a hydroxyl group-containing monomer with respect to a total of 100 parts by weight of the monomer components.
  • the total thickness from the protective layer to the retardation layer is 60 ⁇ m or less.
  • the thickness of the polarizer is 10 ⁇ m or less.
  • the protective layer has a thickness of 45 ⁇ m or less.
  • the retardation layer has a laminated structure of a first liquid crystal alignment fixed layer and a second liquid crystal alignment fixed layer, and Re (550) of the first liquid crystal alignment fixed layer is 200 nm to 300 nm, the angle formed by the slow axis and the absorption axis of the polarizer is 10 ° to 20 °, the Re (550) of the second liquid crystal alignment fixed layer is 100 nm to 190 nm, The angle between the slow axis and the absorption axis of the polarizer is 70° to 80°.
  • the retardation layer is a single layer of a liquid crystal alignment fixed layer, Re (550) of the retardation layer is 100 nm to 180 nm, and Re (450) ⁇ Re (550) ⁇ The relation Re(650) is satisfied, and the angle between the slow axis and the absorption axis of the polarizer is 35° to 55°.
  • a polarizing plate with a retardation layer comprises a protective layer, a polarizer, a retardation layer and an adhesive layer in this order, and the total thickness from the protective layer to the retardation layer is 80 ⁇ m. and the storage elastic modulus G'-30 at ⁇ 30 ° C. of the pressure-sensitive adhesive layer is 250 kPa or less, thereby realizing a retardation layer-attached polarizing plate in which the occurrence of cracks during bending in a low-temperature environment is suppressed. can do.
  • FIG. 1 is a schematic cross-sectional view of a polarizing plate with a retardation layer according to one embodiment of the present invention
  • FIG. 4 is a schematic cross-sectional view of a polarizing plate with a retardation layer according to another embodiment of the invention
  • refractive index (nx, ny, nz) is the refractive index in the direction in which the in-plane refractive index is maximum (i.e., slow axis direction), and "ny” is the in-plane direction orthogonal to the slow axis (i.e., fast axis direction) and "nz” is the refractive index in the thickness direction.
  • In-plane retardation (Re) “Re( ⁇ )” is an in-plane retardation measured at 23° C. with light having a wavelength of ⁇ nm.
  • Re(550) is the in-plane retardation measured with light having a wavelength of 550 nm at 23°C.
  • Thickness direction retardation (Rth) is the retardation in the thickness direction measured at 23° C. with light having a wavelength of ⁇ nm.
  • Rth(550) is the retardation in the thickness direction measured at 23° C. with light having a wavelength of 550 nm.
  • FIG. 1 is a schematic cross-sectional view of a polarizing plate with a retardation layer according to one embodiment of the invention.
  • a polarizing plate 100 with a retardation layer in the illustrated example has a protective layer 10, a polarizer 20, a retardation layer 30, and an adhesive layer 40 in this order.
  • the retardation layer 30 may be composed of a first liquid crystal alignment fixed layer 31 and a second liquid crystal alignment fixed layer 32 as shown in FIG. Alternatively, as shown in FIG.
  • the retardation layer 30 is a single layer of the liquid crystal alignment fixed layer, and another retardation layer 33 is provided between the retardation layer 30 and the adhesive layer 40. good too.
  • the retardation layer 30 is typically provided directly on the polarizer 20 (that is, without any other layer other than the adhesive layer).
  • the retardation layer-attached polarizing plate has a total thickness of 80 ⁇ m or less from the protective layer to the retardation layer, and the pressure-sensitive adhesive layer has a storage elastic modulus G′-30 at ⁇ 30 ° C. of 250 kPa. It is below.
  • the total thickness from the protective layer to the retardation layer is configured to be within the above range, and the storage elastic modulus of the adhesive layer at -30 ° C. is defined as above, so that cracks during bending in a low temperature environment are prevented.
  • a polarizing plate with a retardation layer in which the generation is suppressed can be realized.
  • the storage elastic modulus in a low temperature environment eg, -30 ° C.
  • a normal temperature environment eg, 25 ° C.
  • the conventional polarizing plate with a retardation layer has a problem that desired bending resistance cannot be obtained in a severe environment (especially in a low temperature environment).
  • the ratio of the storage modulus of the pressure-sensitive adhesive at ⁇ 30° C. and the storage modulus at 25° C. within a specific range, the desired is satisfied, and the flex resistance of the retardation layer-attached polarizing plate can be maintained.
  • the polarizing plate with a retardation layer has a total thickness of 80 ⁇ m or less, preferably 70 ⁇ m or less, and more preferably 60 ⁇ m or less, from the protective layer to the retardation layer.
  • the lower limit of the total thickness from the protective layer to the retardation layer can be 20 ⁇ m, for example.
  • the retardation layer-attached polarizing plate may further include other optical functional layers.
  • the type, properties, number, combination, arrangement position, etc. of the optical functional layers that can be provided in the polarizing plate with a retardation layer can be appropriately set according to the purpose.
  • the polarizing plate with a retardation layer may further have a conductive layer or an isotropic substrate with a conductive layer (neither is shown).
  • a conductive layer or an isotropic substrate with a conductive layer is typically provided on the side of the retardation layer 30 opposite to the polarizer 20 .
  • the polarizing plate with a retardation layer is incorporated with a touch sensor between the organic EL cell and the polarizing plate, so-called inner touch panel type input display device can be applied. .
  • the polarizing plate with a retardation layer may be sheet-shaped or elongated.
  • the term "long shape” means an elongated shape whose length is sufficiently long relative to its width, for example, an elongated shape whose length is 10 times or more, preferably 20 times or more, its width. include.
  • the elongated retardation layer-attached polarizing plate can be wound into a roll.
  • a release film is preferably temporarily attached to the surface of the pressure-sensitive adhesive layer 40 until the polarizing plate with a retardation layer is used. By temporarily attaching the release film, it is possible to protect the pressure-sensitive adhesive layer and to form a roll of the retardation layer-attached polarizing plate.
  • the resin film forming the polarizer may be a single-layer resin film or a laminate of two or more layers.
  • the polarizer composed of a single-layer resin film include hydrophilic polymer films such as polyvinyl alcohol (PVA) films, partially formalized PVA films, and partially saponified ethylene/vinyl acetate copolymer films.
  • hydrophilic polymer films such as polyvinyl alcohol (PVA) films, partially formalized PVA films, and partially saponified ethylene/vinyl acetate copolymer films.
  • oriented polyene films such as those dyed with dichroic substances such as iodine and dichroic dyes and stretched, and dehydrated PVA and dehydrochlorinated polyvinyl chloride films.
  • a polarizer obtained by dyeing a PVA-based film with iodine and uniaxially stretching the film is preferably used because of its excellent optical properties.
  • the dyeing with iodine is performed, for example, by immersing the PVA-based film in an aqueous iodine solution.
  • the draw ratio of the uniaxial drawing is preferably 3 to 7 times. Stretching may be performed after the dyeing treatment, or may be performed while dyeing. Moreover, you may dye after extending
  • the PVA-based film is subjected to swelling treatment, cross-linking treatment, washing treatment, drying treatment, and the like. For example, by immersing the PVA-based film in water and washing it with water before dyeing, not only can dirt and anti-blocking agents on the surface of the PVA-based film be washed away, but also the PVA-based film can be swollen to remove uneven dyeing. can be prevented.
  • the polarizer obtained using a laminate include a laminate of a resin substrate and a PVA-based resin layer (PVA-based resin film) laminated on the resin substrate, or a resin substrate and the resin
  • a polarizer obtained by using a laminate with a PVA-based resin layer formed by coating on a substrate can be mentioned.
  • a polarizer obtained by using a laminate of a resin base material and a PVA-based resin layer formed by coating on the resin base material is obtained, for example, by applying a PVA-based resin solution to the resin base material and drying the resin base material.
  • stretching typically includes immersing the laminate in an aqueous boric acid solution and stretching. Furthermore, stretching may further include stretching the laminate in air at a high temperature (eg, 95° C. or higher) before stretching in an aqueous boric acid solution, if necessary.
  • the obtained resin substrate/polarizer laminate may be used as it is (that is, the resin substrate may be used as a protective layer for the polarizer), or the resin substrate may be peeled off from the resin substrate/polarizer laminate.
  • any appropriate protective layer may be laminated on the release surface according to the purpose. Details of such a polarizer manufacturing method are described in, for example, Japanese Patent Application Laid-Open No. 2012-73580 (Patent No. 5414738) and Japanese Patent No. 6470455. These publications are incorporated herein by reference in their entireties.
  • the thickness of the polarizer is preferably 10 ⁇ m or less, more preferably 8 ⁇ m or less, and even more preferably 6 ⁇ m or less.
  • a lower limit for the thickness of the polarizer can be, for example, 1 ⁇ m. If the thickness of the polarizer is within such a range, it is possible to satisfactorily suppress curling during heating, and obtain excellent durability in appearance during heating. Furthermore, if the thickness of the polarizer is within such a range, the desired total thickness can be achieved.
  • the polarizer preferably exhibits absorption dichroism at any wavelength of 380 nm to 780 nm.
  • the single transmittance of the polarizer is, for example, 41.5% to 46.0%, preferably 43.0% to 46.0%, and preferably 44.5% to 46.0%.
  • the degree of polarization of the polarizer is preferably 97.0% or higher, more preferably 99.0% or higher, still more preferably 99.9% or higher.
  • the protective layer is formed of any appropriate film.
  • the material that is the main component of the film include cellulose resins such as triacetyl cellulose (TAC), polyesters, polyvinyl alcohols, polycarbonates, polyamides, polyimides, polyethersulfones, polysulfones, Examples include transparent resins such as polystyrene, polynorbornene, polyolefin, (meth)acrylic, and acetate.
  • Thermosetting resins such as (meth)acrylic, urethane, (meth)acrylic urethane, epoxy, and silicone, or ultraviolet curable resins may also be used.
  • a glassy polymer such as a siloxane-based polymer can also be used.
  • polymer films described in JP-A-2001-343529 (WO01/37007) can also be used.
  • Materials for this film include, for example, a resin composition containing a thermoplastic resin having a substituted or unsubstituted imide group in a side chain and a thermoplastic resin having a substituted or unsubstituted phenyl group and nitrile group in a side chain.
  • a resin composition comprising an alternating copolymer of isobutene and N-methylmaleimide and an acrylonitrile/styrene copolymer.
  • the polymer film can be, for example, an extrudate of the resin composition.
  • the polarizing plate with a retardation layer according to the embodiment of the present invention is typically arranged on the viewing side of the organic EL display device, and the protective layer 10 is arranged on the viewing side. Therefore, the protective layer 10 may be subjected to surface treatment such as hard coat treatment, anti-reflection treatment, anti-sticking treatment, and anti-glare treatment, if necessary.
  • the thickness of the protective layer is preferably 45 ⁇ m or less, more preferably 40 ⁇ m or less, and still more preferably 35 ⁇ m or less.
  • a lower limit for the thickness of the protective layer can be, for example, 10 ⁇ m.
  • the thickness of the protective layer 10 is the thickness including the thickness of the surface treatment layer.
  • the retardation layer 30 is, in one embodiment, C-1. , it has a laminated structure of a first liquid crystal alignment fixed layer 31 and a second liquid crystal alignment fixed layer 32 . In another embodiment, C-2. , the retardation layer 30 is a single layer of the liquid crystal alignment solidified layer, and another retardation layer 33 is provided between the retardation layer 30 and the adhesive layer 40 .
  • the first liquid crystal alignment fixed layer 31 can function as a so-called ⁇ /2 plate.
  • the first liquid crystal alignment fixed layer is a so-called ⁇ / 2 plate
  • the second liquid crystal alignment fixed layer described later is a so-called ⁇ / 4 plate
  • these slow axes are in a predetermined direction with respect to the absorption axis of the polarizer
  • the in-plane retardation Re(550) of the first liquid crystal alignment fixed layer is preferably 200 nm to 300 nm, more preferably 220 nm to 290 nm, still more preferably 250 nm to 280 nm.
  • the angle formed by the slow axis of the first liquid crystal alignment fixed layer 31 and the absorption axis of the polarizer 20 is preferably 10° to 20°, more preferably 13° to 17° as described above, and further Preferably it is about 15°.
  • the angle formed by the slow axis of the first liquid crystal alignment fixed layer and the absorption axis of the polarizer is in such a range, the in-plane retardation of the first liquid crystal alignment fixed layer and the second liquid crystal alignment fixed layer are each set within a predetermined range, and the slow axis of the second liquid crystal alignment fixed layer is arranged at a predetermined angle as described later with respect to the absorption axis of the polarizer, so that circularly polarized light that is very excellent in a wide band Optical stacks with properties (resulting in very good antireflection properties) can be obtained.
  • the thickness of the first liquid crystal alignment fixed layer is preferably 1 ⁇ m to 7 ⁇ m, more preferably 1.5 ⁇ m to 2.5 ⁇ m.
  • the thickness can be significantly reduced. Therefore, it is possible to realize an in-plane retardation equivalent to that of a resin film with a thickness much thinner than that of a resin film.
  • liquid crystal compounds typically include liquid crystal compounds whose liquid crystal phase is a nematic phase (nematic liquid crystal).
  • a liquid crystal compound for example, a liquid crystal polymer or a liquid crystal monomer can be used. Either lyotropic or thermotropic mechanism may be used to develop the liquid crystallinity of the liquid crystal compound.
  • the liquid crystal polymer and liquid crystal monomer may be used alone or in combination.
  • the liquid crystal monomer is preferably a polymerizable monomer and a crosslinkable monomer.
  • the alignment state of the liquid crystal monomer can be fixed by polymerizing or cross-linking (that is, curing) the liquid crystal monomer. After aligning the liquid crystal monomers, for example, the alignment state can be fixed by polymerizing or cross-linking the liquid crystal monomers.
  • a polymer is formed by polymerization and a three-dimensional network structure is formed by cross-linking, but these are non-liquid crystalline.
  • the formed first liquid crystal orientation fixed layer does not undergo a transition to a liquid crystal phase, a glass phase, or a crystal phase due to, for example, temperature changes peculiar to liquid crystalline compounds.
  • the first liquid crystal alignment fixed layer becomes a layer with excellent stability that is not affected by temperature changes.
  • the temperature range in which the liquid crystal monomer exhibits liquid crystallinity differs depending on the type. Specifically, the temperature range is preferably 40°C to 120°C, more preferably 50°C to 100°C, and most preferably 60°C to 90°C.
  • liquid crystal monomer Any appropriate liquid crystal monomer can be adopted as the liquid crystal monomer.
  • polymerizable mesogenic compounds described in JP-T-2002-533742 WO00/37585
  • EP358208 US5211877
  • EP66137 US4388453
  • WO93/22397 EP0261712, DE19504224, DE4408171, and GB2280445
  • Specific examples of such polymerizable mesogenic compounds include LC242 (trade name) available from BASF, E7 (trade name) available from Merck, and LC-Sillicon-CC3767 (trade name) available from Wacker-Chem.
  • LC242 trade name
  • E7 trade name
  • LC-Sillicon-CC3767 trade name
  • the first liquid crystal alignment fixed layer is formed by subjecting the surface of a predetermined base material to alignment treatment, coating the surface with a coating liquid containing a liquid crystal compound, and orienting the liquid crystal compound in the direction corresponding to the alignment treatment. , can be formed by fixing the orientation state.
  • alignment treatment it is possible to align the liquid crystal compound in a predetermined direction with respect to the longitudinal direction of the elongated substrate, and as a result, the liquid crystal alignment fixed layer to be formed is aligned in a predetermined direction.
  • a slow axis can be expressed. For example, it is possible to form a liquid crystal alignment fixed layer having a slow axis in a direction at 15° to the longitudinal direction on a long substrate.
  • Such a liquid crystal alignment fixed layer can be laminated using roll-to-roll even when it is desired to have a slow axis in an oblique direction, so the productivity of the optical laminate is significantly improved. can improve.
  • the base material is any suitable resin film, and the alignment fixed layer formed on the base material can be transferred to the surface of the polarizer.
  • the substrate can be an inner protective layer (inner protective film). In this case, the transfer step can be omitted, and lamination can be performed by roll-to-roll continuously from the formation of the alignment fixed layer.
  • orientation treatment can be adopted as the orientation treatment.
  • Specific examples include mechanical orientation treatment, physical orientation treatment, and chemical orientation treatment.
  • Specific examples of mechanical orientation treatment include rubbing treatment and stretching treatment.
  • Specific examples of physical orientation treatment include magnetic orientation treatment and electric field orientation treatment.
  • Specific examples of chemical alignment treatment include oblique vapor deposition and photo-alignment treatment.
  • Arbitrary appropriate conditions can be adopted as the processing conditions for various alignment treatments depending on the purpose.
  • the alignment of the liquid crystal compound is performed by processing at a temperature that exhibits a liquid crystal phase depending on the type of liquid crystal compound. By performing such a temperature treatment, the liquid crystal compound assumes a liquid crystal state, and the liquid crystal compound is aligned in accordance with the orientation treatment direction of the surface of the base material.
  • the alignment state is fixed by cooling the liquid crystal compound aligned as described above.
  • the orientation state is fixed by subjecting the liquid crystal compound oriented as described above to a polymerization treatment or a crosslinking treatment.
  • liquid crystal compound and details of the method for forming the alignment fixed layer are described in JP-A-2006-163343. The description of the publication is incorporated herein by reference.
  • the second liquid crystal alignment fixed layer 32 can function as a so-called ⁇ /4 plate.
  • the second liquid crystal alignment fixed layer is a so-called ⁇ /4 plate
  • the first liquid crystal alignment fixed layer is a so-called ⁇ /2 plate as described above
  • the slow axis of these is a predetermined with respect to the absorption axis of the polarizer.
  • the in-plane retardation Re(550) of the second liquid crystal alignment fixed layer is preferably 100 nm to 190 nm, more preferably 110 nm to 170 nm, still more preferably 130 nm to 150 nm, as described above.
  • the angle formed by the slow axis of the second liquid crystal alignment fixed layer 32 and the absorption axis of the polarizer 20 is preferably 65° to 85°, more preferably 72° to 78° as described above, and further Preferably it is about 75°.
  • the angle formed by the slow axis of the second liquid crystal alignment fixed layer and the absorption axis of the polarizer is in such a range, the in-plane retardation of the first liquid crystal alignment fixed layer and the second liquid crystal alignment fixed layer are each set within a predetermined range, and the slow axis of the first liquid crystal alignment fixed layer is arranged at the predetermined angle as described above with respect to the absorption axis of the polarizer, so that circularly polarized light that is very excellent in a wide band Optical stacks with properties (resulting in very good antireflection properties) can be obtained.
  • the thickness of the second liquid crystal alignment fixed layer is preferably 0.5 ⁇ m to 2 ⁇ m, more preferably 1 ⁇ m to 1.5 ⁇ m.
  • the constituent materials, characteristics, manufacturing method, etc. of the second liquid crystal alignment fixed layer are as described in the above section C-1-1 regarding the first liquid crystal alignment fixed layer.
  • the angle between the slow axis of the first liquid crystal alignment fixed layer 31 and the absorption axis of the polarizer 20 is about 15°, and the slow axis of the second liquid crystal alignment fixed layer 32 and the absorption axis of the polarizer 20 Although an embodiment has been described in which the angle between the two is approximately 75°, this axial angle relationship may be reversed.
  • the angle formed by the slow axis of the first liquid crystal alignment fixed layer 31 and the absorption axis of the polarizer 20 is preferably 65° to 85°, more preferably 72° to 78°, further preferably It may be about 75°; in this case, the angle formed by the slow axis of the second liquid crystal alignment fixed layer 32 and the absorption axis of the polarizer 20 is preferably 10° to 20°, more preferably 13°. ⁇ 17°, more preferably about 15°.
  • the first liquid crystal alignment fixed layer 31 may be a ⁇ /4 plate and the second liquid crystal alignment fixed layer 32 may be a ⁇ /2 plate.
  • the retardation layer 30 is a single layer of an alignment fixed layer of a liquid crystal compound.
  • the retardation layer can typically function as a ⁇ /4 plate.
  • the in-plane retardation Re(550) of the retardation layer is preferably 100 nm to 180 nm, more preferably 110 nm to 160 nm, still more preferably 120 nm to 140 nm.
  • the Nz coefficient of the retardation layer is preferably 0.9 to 1.5, more preferably 0.9 to 1.3.
  • the retardation layer preferably exhibits reverse dispersion wavelength characteristics in which the retardation value increases according to the wavelength of the measurement light.
  • the retardation layer satisfies the relationship Re(450) ⁇ Re(550) ⁇ Re(650), and Re(450)/Re(550) of the retardation layer is preferably 0.8 or more and less than 1. and more preferably 0.8 or more and 0.95 or less. With such a configuration, very excellent antireflection properties can be achieved.
  • the angle formed by the slow axis of the retardation layer and the absorption axis of the polarizer is preferably 35° to 55°, more preferably 40° to 50°, still more preferably 42° to 48°. , particularly preferably about 45°. If the angle is within such a range, an organic EL display device having extremely excellent antireflection properties can be obtained by using a ⁇ /4 plate as the retardation layer as described above.
  • the retardation layer can be made of any suitable material as long as it can satisfy the properties described above.
  • the retardation layer may be a stretched resin film.
  • a representative example of the resin that constitutes the resin film is a polycarbonate-based resin or a polyester carbonate-based resin (hereinafter sometimes simply referred to as a polycarbonate-based resin). Any appropriate polycarbonate-based resin can be used as the polycarbonate-based resin as long as the desired moisture permeability can be obtained.
  • a polycarbonate-based resin includes a structural unit derived from a fluorene-based dihydroxy compound, a structural unit derived from an isosorbide-based dihydroxy compound, an alicyclic diol, an alicyclic dimethanol, di-, tri- or polyethylene glycol, and an alkylene and a structural unit derived from at least one dihydroxy compound selected from the group consisting of glycols or spiroglycols.
  • the polycarbonate-based resin contains a structural unit derived from a fluorene-based dihydroxy compound, a structural unit derived from an isosorbide-based dihydroxy compound, a structural unit derived from an alicyclic dimethanol, and/or di-, tri- or polyethylene glycol.
  • a structural unit derived from a fluorene-based dihydroxy compound More preferably, a structural unit derived from a fluorene-based dihydroxy compound, a structural unit derived from an isosorbide-based dihydroxy compound, and a structural unit derived from di-, tri- or polyethylene glycol.
  • the polycarbonate-based resin may contain structural units derived from other dihydroxy compounds as necessary.
  • the retardation layer can be formed by stretching a film composed of a polycarbonate-based resin as described above under any appropriate stretching conditions.
  • the details of the method for forming the polycarbonate resin and the retardation layer for example, JP-A-2014-10291, JP-A-2014-26266 (Patent No. 5528606), JP-A-2015-212816 (Patent No.
  • the thickness of the retardation layer can typically be set to a thickness that allows it to function properly as a ⁇ /4 plate.
  • Another Retardation Layer A polarizing plate with a retardation layer in another embodiment of the present invention may further include another retardation layer 33 between the retardation layer 30 and the adhesive layer 40 .
  • the thickness direction retardation Rth (550) of the other retardation layer is preferably ⁇ 50 nm to ⁇ 300 nm, more preferably ⁇ 70 nm to ⁇ 250 nm, still more preferably ⁇ 90 nm to ⁇ 200 nm, particularly preferably ⁇ 100 nm to -180 nm.
  • Another retardation layer preferably consists of a film containing a liquid crystal material fixed in homeotropic alignment.
  • a liquid crystal material (liquid crystal compound) that can be homeotropically aligned may be a liquid crystal monomer or a liquid crystal polymer.
  • Specific examples of the method for forming the liquid crystal compound and the liquid crystal alignment fixed layer include the liquid crystal compound and the liquid crystal alignment fixed layer described in [0020] to [0028] of JP-A-2002-333642 (Patent No. 4174192).
  • the thickness of the separate retardation layer is preferably 0.5 ⁇ m to 10 ⁇ m, more preferably 0.5 ⁇ m to 8 ⁇ m, still more preferably 0.5 ⁇ m to 5 ⁇ m.
  • the storage elastic modulus G'-30 at -30 °C of the adhesive layer is 250 kPa or less, preferably 200 kPa or less.
  • the lower limit of the storage modulus G'- 30 of the adhesive layer can be, for example, 100 kPa.
  • the storage elastic modulus G'- 25 of the pressure-sensitive adhesive layer at 25°C is 100 kPa or less, preferably 50 kPa or less.
  • the lower limit of the storage modulus G'- 25 of the adhesive layer can be, for example, 10 kPa.
  • G'- 30 and G'25 preferably satisfy the following formula (1).
  • the pressure-sensitive adhesive layer having such a storage elastic modulus suppresses the occurrence of cracks during bending in a low-temperature environment.
  • the thickness of the adhesive layer is preferably 10 ⁇ m to 100 ⁇ m, more preferably 20 ⁇ m to 60 ⁇ m.
  • the adhesive forming the adhesive layer contains at least a base polymer.
  • the base polymer is an adhesive component that develops adhesiveness in the adhesive layer 40 .
  • Base polymers include, for example, acrylic polymers, silicone polymers, polyester polymers, polyurethane polymers, polyamide polymers, polyvinyl ether polymers, vinyl acetate/vinyl chloride copolymers, modified polyolefin polymers, epoxy polymers, fluoropolymers, and rubber polymers.
  • the base polymer may be used alone or in combination of two or more. From the viewpoint of ensuring good transparency and adhesiveness in the adhesive layer 40, an acrylic polymer is preferably used as the base polymer.
  • the acrylic polymer is a copolymer of monomer components containing 50% by mass or more of (meth)acrylic acid alkyl ester.
  • (Meth)acrylic acid means acrylic acid and/or methacrylic acid.
  • a (meth)acrylic acid alkyl ester having an alkyl group having 1 to 20 carbon atoms is preferably used, more preferably having an alkyl group having 10 to 20 carbon atoms.
  • Certain (meth)acrylic acid alkyl esters are preferably used.
  • the (meth)acrylic acid alkyl ester may have a linear or branched alkyl group, or may have a cyclic alkyl group such as an alicyclic alkyl group.
  • Examples of (meth)acrylic acid alkyl esters having a linear or branched alkyl group include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and isobutyl (meth)acrylate.
  • Examples of (meth)acrylic acid alkyl esters having an alicyclic alkyl group include (meth)acrylic acid cycloalkyl esters, (meth)acrylic acid esters having a bicyclic aliphatic hydrocarbon ring, and tricyclic (Meth)acrylic acid esters having the above aliphatic hydrocarbon ring can be mentioned.
  • Cycloalkyl (meth)acrylates include, for example, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, cycloheptyl (meth)acrylate, and cyclooctyl (meth)acrylate.
  • Examples of (meth)acrylic acid esters having a bicyclic aliphatic hydrocarbon ring include isobornyl (meth)acrylate.
  • (Meth)acrylic esters having a tricyclic or higher aliphatic hydrocarbon ring include, for example, dicyclopentanyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, tricyclopentanyl (meth)acrylate , 1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, and 2-ethyl-2-adamantyl (meth)acrylate.
  • an acrylate alkyl ester having an alkyl group having 3 to 15 carbon atoms is preferably used, and more preferably n-butyl acrylate, 2-ethylhexyl acrylate, and acrylic acid. At least one selected from the group consisting of dodecyl (ie, lauryl acrylate) is used.
  • the ratio of (meth)acrylic acid alkyl ester in the monomer component is preferably 60% by mass or more, more preferably 70% by mass or more, and still more preferably from the viewpoint of appropriately expressing basic properties such as adhesiveness in the adhesive layer. It is 80% by mass or more. The same ratio is, for example, 99% by mass or less.
  • the amount of the (meth)acrylic acid C 10-20 chain alkyl ester is preferably 1 to 40 parts by weight, more preferably 5 to 35 parts by weight, based on the total 100 parts by weight of the monomer components of the acrylic base polymer. In particular, it is preferable that the amount of lauryl acrylate is within the above range.
  • the monomer component may contain a copolymerizable monomer that can be copolymerized with the (meth)acrylic acid alkyl ester.
  • copolymerizable monomers include monomers having a polar group.
  • Polar group-containing monomers include, for example, nitrogen atom-containing ring-containing monomers, hydroxy group-containing monomers, and carboxy group-containing monomers.
  • the polar group-containing monomer is useful for modifying the acrylic polymer, such as introducing cross-linking points into the acrylic polymer and securing the cohesive strength of the acrylic polymer.
  • Examples of monomers having a nitrogen atom-containing ring include N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N-vinyloxazole, N-(meth)acryloyl-2-pyrrolidone, N-(meth)acryloylpiperidine, N-(meth)acryloylpyrrolidine, N-vinylmorpholine, N-vinyl -3-morpholinone, N-vinyl-2-caprolactam, N-vinyl-1,3-oxazin-2-one, N-vinyl-3,5-morpholinedione, N-vinylpyrazole, N-vinylisoxazole, N -vinylthiazole,
  • the ratio of the monomer having a nitrogen atom-containing ring in the monomer component is preferably 0.1% by mass or more from the viewpoint of ensuring the cohesive force in the adhesive layer and ensuring the adhesive strength of the adhesive layer to the adherend. , more preferably 0.3% by mass or more, and still more preferably 0.55% by mass or more.
  • the same ratio is preferably 10% by mass or less from the viewpoint of adjusting the glass transition temperature of the acrylic polymer and adjusting the polarity of the acrylic polymer (related to compatibility between various additive components and the acrylic polymer in the adhesive layer). , more preferably 5% by mass or less.
  • hydroxy group-containing monomers examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, ( 4-hydroxybutyl meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, and (4-hydroxymethylcyclohexyl)methyl (meth)acrylate.
  • 4-hydroxybutyl (meth)acrylate is preferably used, and 4-hydroxybutyl acrylate is more preferably used.
  • the ratio of the hydroxy group-containing monomer in the monomer component is preferably 0.1% by mass or more, more preferably 0.5% by mass, from the viewpoint of introducing a crosslinked structure into the acrylic polymer and ensuring cohesive force in the pressure-sensitive adhesive layer. % or more, more preferably 0.8 mass % or more. The same ratio is preferably 10% by mass or less, more preferably 8% by mass or less, from the viewpoint of adjusting the polarity of the acrylic polymer (related to compatibility between various additive components and the acrylic polymer in the adhesive layer 40). .
  • Carboxy group-containing monomers include, for example, acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid.
  • the ratio of the carboxyl group-containing monomer in the monomer component is preferable from the viewpoint of introducing a crosslinked structure into the acrylic polymer, ensuring cohesive force in the adhesive layer 40, and ensuring adhesion to the adherend in the adhesive layer 40. is 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 0.8% by mass or more.
  • the same ratio is preferably 30% by mass or less, more preferably 25% by mass or less, from the viewpoints of adjusting the glass transition temperature of the acrylic polymer and avoiding the risk of acid corrosion of the adherend.
  • the amount of the polar group-containing monomer relative to the total 100 parts by weight of the monomer components of the acrylic base polymer is preferably 5 parts by weight or more, and may be 6 parts by weight or more, 7 parts by weight or more, or 8 parts by weight or more.
  • the amount of the polar group-containing monomer is preferably 30 parts by weight or less, and may be 25 parts by weight or less, relative to the total 100 parts by weight of the monomer components of the acrylic base polymer.
  • the monomer component may contain other copolymerizable monomers.
  • Other copolymerizable monomers include, for example, acid anhydride monomers, sulfonic acid group-containing monomers, phosphoric acid group-containing monomers, epoxy group-containing monomers, cyano group-containing monomers, alkoxy group-containing monomers, and aromatic vinyl compounds. be done. These other copolymerizable monomers may be used alone, or two or more of them may be used in combination.
  • the base polymer has a crosslinked structure in this embodiment.
  • the base polymer having a functional group capable of reacting with the crosslinker and the crosslinker are blended in the adhesive composition, and the base polymer and the crosslinker are mixed in the adhesive layer 40.
  • Acrylic polymers can be formed by polymerizing monomer components.
  • Polymerization methods include, for example, solution polymerization, active energy ray polymerization (eg, UV polymerization), bulk polymerization, and emulsion polymerization.
  • Solution polymerization and UV polymerization are preferred from the viewpoints of transparency, water resistance, and cost of the pressure-sensitive adhesive layer 40 .
  • Ethyl acetate and toluene are used as solvents for solution polymerization.
  • a polymerization initiator for example, a thermal polymerization initiator and a photopolymerization initiator are used as a polymerization initiator.
  • the amount of the polymerization initiator to be used is, for example, 0.05 parts by weight or more and, for example, 1 part by weight or less with respect to 100 parts by weight of the monomer component.
  • the weight-average molecular weight of the acrylic polymer is preferably 100,000 or more, more preferably 300,000 or more, and still more preferably 500,000 or more, from the viewpoint of ensuring the cohesive force of the adhesive layer 40 .
  • the weight-average molecular weight is preferably 5 million or less, more preferably 3 million or less, still more preferably 2 million or less.
  • the weight average molecular weight of the acrylic polymer is calculated by measuring by gel permeation chromatography (GPC) and converting to polystyrene.
  • the glass transition temperature (Tg) of the base polymer is preferably 0°C or lower, more preferably -10°C or lower, and even more preferably -20°C or lower.
  • the glass transition temperature is, for example, ⁇ 80° C. or higher.
  • the adhesive composition may contain one or more oligomers in addition to the base polymer.
  • an acrylic polymer is used as the base polymer, preferably an acrylic oligomer is used as the oligomer.
  • the acrylic oligomer is a copolymer of monomer components containing 50% by mass or more of (meth)acrylic acid alkyl ester, and has a weight average molecular weight of, for example, 1,000 or more and 30,000 or less.
  • cross-linking agent examples include compounds that react with functional groups (hydroxy groups, carboxy groups, etc.) contained in the base polymer.
  • Such crosslinkers include, for example, isocyanate crosslinkers, peroxide crosslinkers, epoxy crosslinkers, oxazoline crosslinkers, aziridine crosslinkers, carbodiimide crosslinkers, and metal chelate crosslinkers.
  • the cross-linking agents may be used alone, or two or more of them may be used in combination.
  • an isocyanate cross-linking agent, a peroxide cross-linking agent, and an epoxy cross-linking agent are preferably used because they are highly reactive with the hydroxy groups and carboxy groups in the base polymer and facilitate the introduction of a cross-linked structure. be done.
  • the adhesive composition may contain a silane coupling agent.
  • the content of the silane coupling agent in the adhesive composition is preferably 0.1 parts by weight or more, more preferably 0.2 parts by weight or more, relative to 100 parts by weight of the base polymer.
  • the content is preferably 5 parts by weight or less, more preferably 3 parts by weight or less.
  • the adhesive composition may contain other components as necessary.
  • Other ingredients include, for example, tackifiers, plasticizers, softeners, antidegradants, fillers, colorants, UV absorbers, antioxidants, surfactants, and antistatic agents.
  • Adhesive composition A was applied onto the release-treated surface of the first release film, one surface of which had been subjected to silicone release treatment, to form a coating film.
  • the first release film is a polyethylene terephthalate (PET) film (trade name “Diafoil MRF #75”, thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) with one side subjected to silicone release treatment.
  • PET polyethylene terephthalate
  • the release-treated surface of the second release film having one surface subjected to silicone release treatment was attached to the coating film on the first release film.
  • the second release film is a PET film (trade name: "Diafoil MRF#75", thickness: 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) with one side subjected to silicone release treatment.
  • the coating film on the first release film was dried by heating at 100° C. for 1 minute and then heating at 150° C. for 3 minutes to form a transparent adhesive layer A with a thickness of 50 ⁇ m.
  • the thickness of the obtained adhesive layer A was 50 ⁇ m.
  • Adhesive composition B was applied onto the release-treated surface of the first release film, one surface of which had been subjected to silicone release treatment, to form a coating film.
  • the first release film is a polyethylene terephthalate (PET) film (trade name “Diafoil MRF #75”, thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) with one side subjected to silicone release treatment.
  • PET polyethylene terephthalate
  • the second release film is a PET film (trade name: "Diafoil MRF#75", thickness: 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) with one side subjected to silicone release treatment.
  • the coating film was irradiated with ultraviolet rays through the second release film to cure the coating film with ultraviolet rays. A black light was used for ultraviolet irradiation.
  • the irradiation intensity of ultraviolet rays was set to 5 mW/cm 2 .
  • the thickness of the obtained adhesive layer B was 50 ⁇ m.
  • Adhesive composition C was applied onto the release-treated surface of the first release film, one surface of which had been subjected to silicone release treatment, to form a coating film.
  • the first release film is a polyethylene terephthalate (PET) film (trade name “Diafoil MRF #75”, thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) with one side subjected to silicone release treatment.
  • PET polyethylene terephthalate
  • the second release film is a PET film (trade name: "Diafoil MRF#75", thickness: 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) with one side subjected to silicone release treatment.
  • the coating film was irradiated with ultraviolet rays through the second release film to cure the coating film with ultraviolet rays. A black light was used for ultraviolet irradiation.
  • the irradiation intensity of ultraviolet rays was set to 5 mW/cm 2 .
  • the thickness of the obtained adhesive layer C was 25 ⁇ m.
  • Adhesive Layer D The above acrylic adhesive composition is applied to the surface of a release film made of a polyethylene terephthalate film (PET film, transparent substrate) having a thickness of 38 ⁇ m treated with a silicone release agent, using a fountain coater. It was applied uniformly and dried in an air circulation type constant temperature oven at 155° C. for 2 minutes to form an adhesive layer D with a thickness of 50 ⁇ m.
  • PET film polyethylene terephthalate film
  • Adhesive Layer E The above acrylic adhesive composition is applied to the surface of a release film made of a polyethylene terephthalate film (PET film, transparent substrate) having a thickness of 38 ⁇ m treated with a silicone release agent, using a fountain coater. It was applied uniformly and dried in an air circulation type constant temperature oven at 155° C. for 2 minutes to form an adhesive layer E having a thickness of 50 ⁇ m.
  • PET film polyethylene terephthalate film
  • silicone release agent silicone release agent
  • Example 1 Production of Polarizer
  • a thermoplastic resin substrate a long amorphous isophthalic copolymerized polyethylene terephthalate film (thickness: 100 ⁇ m) having a water absorption of 0.75% and a Tg of about 75° C. was used. Corona treatment was applied to one side of the resin substrate.
  • Polyvinyl alcohol degree of polymerization: 4,200, degree of saponification: 99.2 mol% and acetoacetyl-modified PVA (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name "GOSEFIMER Z410") mixed at 9:1: 100 weight of PVA-based resin 13 parts by weight of potassium iodide was added to parts by weight, and dissolved in water to prepare an aqueous PVA solution (coating solution). The above PVA aqueous solution was applied to the corona-treated surface of the resin base material and dried at 60° C. to form a PVA-based resin layer having a thickness of 13 ⁇ m, thereby producing a laminate.
  • the obtained laminate was uniaxially stretched 2.4 times at the free end in the machine direction (longitudinal direction) between rolls with different peripheral speeds in an oven at 130° C. (in-air auxiliary stretching treatment).
  • the laminate was immersed in an insolubilizing bath (an aqueous boric acid solution obtained by mixing 4 parts by weight of boric acid with 100 parts by weight of water) at a liquid temperature of 40° C. for 30 seconds (insolubilizing treatment).
  • the finally obtained polarizer is added to a dyeing bath (iodine aqueous solution obtained by blending iodine and potassium iodide at a weight ratio of 1:7 with respect to 100 parts by weight of water) at a liquid temperature of 30 ° C.
  • the film was uniaxially stretched so that the total draw ratio was 5.5 times (underwater stretching treatment).
  • the laminate was immersed in a washing bath (aqueous solution obtained by blending 4 parts by weight of potassium iodide with 100 parts by weight of water) at a liquid temperature of 20° C. (washing treatment).
  • washing treatment aqueous solution obtained by blending 4 parts by weight of potassium iodide with 100 parts by weight of water
  • drying treatment while drying in an oven kept at 90° C., it was brought into contact with a heating roll made of SUS whose surface temperature was kept at 75° C. for about 2 seconds
  • the shrinkage ratio in the width direction of the laminate due to the drying shrinkage treatment was 5.2%.
  • a polarizer having a thickness of 5 ⁇ m was formed on the resin substrate.
  • the direction of the orientation treatment was set to be 15° from the direction of the absorption axis of the polarizer when viewed from the viewing side when attached to the polarizing plate.
  • the above liquid crystal coating solution was applied to the alignment-treated surface using a bar coater, and dried by heating at 90° C. for 2 minutes to align the liquid crystal compound.
  • the liquid crystal layer thus formed was irradiated with light of 1 mJ/cm 2 using a metal halide lamp to cure the liquid crystal layer, thereby forming the first liquid crystal alignment fixed layer on the PET film.
  • the first liquid crystal alignment fixed layer had a thickness of 2.5 ⁇ m and an in-plane retardation Re (550) of 270 nm.
  • a second liquid crystal alignment fixed layer was formed.
  • the second liquid crystal alignment fixed layer had a thickness of 1.5 ⁇ m and an in-plane retardation Re (550) of 140 nm.
  • Example 2 A polarizing plate with a retardation layer was obtained in the same manner as in Example 1, except that the thickness of the pressure-sensitive adhesive layer was 25 ⁇ m. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. Table 1 shows the results.
  • Example 3 The polarizing plate is subjected to the following procedure 1. and instead of the first liquid crystal alignment fixed layer and the second liquid crystal alignment fixed layer in Example 1, the following 2. and 3. A polarizing plate with a retardation layer was obtained in the same manner as in Example 1, except that a single layer of the liquid crystal alignment fixed layer and another retardation layer were produced according to the procedure. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. Table 1 shows the results.
  • polarizing plate 1 of Example 1 A HC-TAC film was attached to the surface of the polarizer obtained in 1. above with an ultraviolet curable adhesive. Specifically, the curable adhesive was applied so as to have a thickness of 1.0 ⁇ m, and was bonded using a roll machine. After that, UV light was applied from the HC-TAC film side to cure the adhesive.
  • the HC-TAC film is a film in which a hard coat (HC) layer (7 ⁇ m thick) is formed on a triacetyl cellulose (TAC) film (25 ⁇ m thick).
  • HC-TAC hard coat
  • TAC triacetyl cellulose
  • the resulting solution was filtered through a 0.20 ⁇ m membrane filter to obtain a polymerizable composition.
  • a polyimide solution for an alignment film was applied to a glass substrate having a thickness of 0.7 mm by spin coating, dried at 100° C. for 10 minutes, and then baked at 200° C. for 60 minutes to obtain a coating film. .
  • the resulting coating film was rubbed to form an alignment film. The rubbing treatment was performed using a commercially available rubbing device.
  • the polymerizable composition obtained above was applied to a substrate (substantially an alignment film) by a spin coating method and dried at 100° C. for 2 minutes.
  • the obtained coating film was cooled to room temperature, it was irradiated with ultraviolet rays for 30 seconds at an intensity of 30 mW/cm 2 using a high-pressure mercury lamp to obtain a first liquid crystal alignment fixed layer.
  • the in-plane retardation Re(550) of the first liquid crystal alignment fixed layer was 130 nm.
  • the Re(450)/Re(550) of the liquid crystal alignment fixed layer was 0.851, showing reverse dispersion wavelength characteristics.
  • the liquid crystal is formed by heating and drying at 80 ° C. for 4 minutes. Oriented.
  • a second liquid crystal alignment fixed layer (thickness: 0.58 ⁇ m) was formed on the substrate.
  • Example 4 A polarizing plate with a retardation layer was obtained in the same manner as in Example 1 except that the adhesive layer B obtained in Production Example 2 was used. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. Table 1 shows the results.
  • Example 1 A polarizing plate with a retardation layer was obtained in the same manner as in Example 1 except that the adhesive layer D obtained in Production Example 4 was used. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. Table 1 shows the results.
  • Comparative Example 2 A polarizing plate with a retardation layer was obtained in the same manner as in Comparative Example 1, except that the thickness of the pressure-sensitive adhesive layer was 25 ⁇ m. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. Table 1 shows the results.
  • Comparative Example 3 A polarizing plate with a retardation layer was obtained in the same manner as in Comparative Example 1, except that the thickness of the pressure-sensitive adhesive layer was 15 ⁇ m. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. Table 1 shows the results.
  • Example 4 A polarizing plate with a retardation layer was obtained in the same manner as in Example 1 except that the adhesive layer E obtained in Production Example 5 was used. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. Table 1 shows the results.
  • Example 5 A polarizing plate with a retardation layer was obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive layer C obtained in Production Example 3 was used and the thickness of the pressure-sensitive adhesive layer was 25 ⁇ m. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. Table 1 shows the results.
  • Example 6 A polarizer (12 ⁇ m thick) formed from a PVA-based resin film was used as the polarizer, and an inner protective layer (TAC film, 25 ⁇ m thick) was provided on the opposite side of the HC-TAC film of the polarizer. A polarizing plate with a retardation layer was obtained in the same manner as in Example 3 except that the retardation layer was provided. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. Table 1 shows the results.
  • Comparative Example 7 A polarizing plate with a retardation layer was obtained in the same manner as in Comparative Example 6, except that the thickness of the pressure-sensitive adhesive layer was 25 ⁇ m. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. Table 1 shows the results.
  • the retardation layer-attached polarizing plate of the present invention is suitably used for an organic EL display device.
  • polarizing plate 10 protective layer 20 polarizer 30 retardation layer 31 first liquid crystal alignment fixed layer 32 second liquid crystal alignment fixed layer 33 another retardation layer 40 adhesive layer 100 retardation layer attached polarizing plate 101 retardation layer attached polarizing plate

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WO2018062183A1 (ja) * 2016-09-30 2018-04-05 日東電工株式会社 有機ｅｌ表示装置
WO2021070525A1 (ja) * 2019-10-10 2021-04-15 日東電工株式会社 位相差層および粘着剤層付偏光板およびそれを用いた有機エレクトロルミネセンス表示装置

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