WO2020022269A1 - 光学フィルムおよびその製造方法、偏光板、ならびに画像表示装置 - Google Patents

光学フィルムおよびその製造方法、偏光板、ならびに画像表示装置 Download PDF

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Publication number
WO2020022269A1
WO2020022269A1 PCT/JP2019/028657 JP2019028657W WO2020022269A1 WO 2020022269 A1 WO2020022269 A1 WO 2020022269A1 JP 2019028657 W JP2019028657 W JP 2019028657W WO 2020022269 A1 WO2020022269 A1 WO 2020022269A1
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Prior art keywords
layer
optical film
film
fine particles
polarizer
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PCT/JP2019/028657
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English (en)
French (fr)
Japanese (ja)
Inventor
雅 品川
そら 道下
康彰 岡田
菁▲番▼ 徐
Original Assignee
日東電工株式会社
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Priority claimed from JP2019133317A external-priority patent/JP6644932B1/ja
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to CN202110950621.6A priority Critical patent/CN113635632B/zh
Priority to KR1020207011185A priority patent/KR102431158B1/ko
Priority to KR1020227018457A priority patent/KR20220079700A/ko
Priority to CN201980006223.XA priority patent/CN111448246B/zh
Publication of WO2020022269A1 publication Critical patent/WO2020022269A1/ja

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    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • 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
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    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B29D11/0074—Production of other optical elements not provided for in B29D11/00009- B29D11/0073
    • B29D11/00788—Producing optical films
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
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    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • 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
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    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers
    • 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
    • H10K59/50—OLEDs integrated with light modulating elements, e.g. with electrochromic elements, photochromic elements or liquid crystal elements
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Definitions

  • the present invention relates to an optical film having a lubricating layer on the surface of a transparent film substrate and a method for producing the same. Furthermore, the present invention relates to a polarizing plate in which an optical film having a lubricating layer is attached to the surface of a polarizer, and an image display device including the polarizing plate.
  • Liquid crystal display devices and organic EL display devices are widely used as various image display devices such as mobile devices, car navigation devices, personal computer monitors, and televisions.
  • a polarizing plate is disposed on the viewing side surface of the liquid crystal cell from the display principle.
  • polarizing plates are arranged on both sides of a liquid crystal cell.
  • a circularly polarizing plate typically, 1 / (A laminate of four wavelength plates).
  • a polarizing plate generally has a transparent film (polarizer protective film) for protecting a polarizer on one or both sides of the polarizer.
  • polarizer protective film a transparent film
  • a polarizer in which iodine is adsorbed on a polyvinyl alcohol (PVA) -based film and molecules are oriented by stretching or the like is widely used.
  • Patent Literature 1 describes that by providing a smooth layer containing fine particles and a binder resin on the surface of an acrylic film, blocking when the film is wound into a roll can be suppressed.
  • Patent Document 1 discloses a polarizer protective film in which an acrylic film is provided with a urethane resin layer having an average thickness of 400 nm (thickness range of 300 to 500 nm) containing silica fine particles of 1 to 7% by weight on the surface thereof. I have.
  • the polarizing plate provided with the polarizer protective film disclosed in Patent Document 1 has a problem that, when exposed to a high-humidity environment for a long time, optical defects such as streak-like unevenness may occur and display characteristics may be deteriorated. Newly found out.
  • an object of the present invention is to provide an optical film that is unlikely to cause blocking and hardly causes optical defects even when exposed to a high-temperature and high-humidity environment for a long time.
  • alkali components such as ammonia and amine added to the slippery layer forming composition for the purpose of improving the dispersibility of fine particles remain in the slippery layer.
  • alkali components such as ammonia and amine added to the slippery layer forming composition for the purpose of improving the dispersibility of fine particles remain in the slippery layer.
  • the present invention relates to an optical film having a lubricating layer on the surface of a transparent film substrate and a method for producing the same.
  • the slippery layer contains a binder resin and fine particles.
  • the average primary particle diameter of the fine particles is, for example, 10 to 250 nm, and preferably 10 to 100 nm.
  • the content of the alkali component in the slippery layer is preferably from 5 to 75 ppm.
  • the thickness of the slippery layer is preferably from 40 to 280 nm.
  • Acrylic film or the like is used as the transparent film substrate.
  • a urethane-based resin or the like is used as the binder resin for the slippery layer.
  • the content of the fine particles in the slippery layer is preferably about 3 to 50% by weight, more preferably 10 to 50% by weight.
  • the fine particles of the slippery layer may be embedded in the transparent film substrate.
  • the composition for forming a slippery layer is applied to the surface of the transparent film substrate and heated to form a slippery layer.
  • the composition for forming a slippery layer contains a binder resin or a precursor thereof, fine particles, an alkali component, and a solvent.
  • the alkali component can also act as a catalyst for accelerating the reaction of the binder resin (precursor). From the viewpoint of promoting the volatilization of the alkali component by heating, the boiling point of the alkali component is preferably 150 ° C. or lower. Examples of the alkali component include amine and ammonia.
  • the composition for forming a slippery layer may be heated at a temperature higher than the glass transition temperature of the transparent film substrate by 10 ° C. or more. By increasing the heating temperature, a region in which the fine particles of the slippery layer are embedded in the transparent film substrate is likely to be formed, and the adhesiveness between the transparent film substrate and the slippery layer tends to be improved.
  • the transparent film substrate may be stretched while being heated.
  • the composition for forming a lubricating layer at a temperature higher than the glass transition temperature of the transparent film substrate by 10 ° C. or more, the adhesion between the transparent film substrate and the lubricating layer is improved. Properties tend to improve.
  • the easy lubricating layer can also contribute to improving the adhesion to other films, glass substrates, and the like.
  • the optical film can be used, for example, as a polarizer protective film.
  • a polarizing plate can be obtained by attaching an optical film to the surface of a polyvinyl alcohol-based polarizer via an adhesive layer.
  • any surface of the surface on which the easy-adhesion layer is formed and the surface on which the easy-adhesion layer is not formed may be bonded to the polarizer.
  • An image display device can be formed by disposing a polarizing plate on the surface of an image display cell such as a liquid crystal display cell or an organic EL cell.
  • the optical film of the present invention is excellent in adhesiveness, hardly causes blocking, and even when exposed to a high-temperature and high-humidity environment for a long time, optical defects hardly occur. It is preferably used as
  • FIG. 1 is a schematic cross-sectional view showing a configuration example of an optical film according to an embodiment of the present invention.
  • the optical film 1 includes an easy-slip layer 15 on at least one surface of the film substrate 11.
  • a lubricating layer may be provided on both sides of the film substrate.
  • the optical film is used by being bonded to another film, a glass substrate, or the like.
  • a usage form of the optical film includes a polarizer protective film.
  • 2A and 2B are cross-sectional views illustrating a configuration example of a polarizing plate including the optical film 1 as a polarizer protective film.
  • the polarizing plate 100 shown in FIG. 2A and the polarizing plate 101 shown in FIG. 2B include the optical film 1 bonded to one surface (first main surface) of the polarizer 5 with an adhesive layer 6 interposed therebetween.
  • the optical film 1 has the easy-slip layer 15 on the surface of the film substrate 11 to be bonded to the polarizer 5.
  • the polarizer 5 is bonded to the surface of the optical film 1 where the slippery layer 15 is not provided.
  • the transparent protective film 2 is bonded to the other surface (second main surface) of the polarizer 5 with an adhesive layer 7 interposed therebetween.
  • the optical film 1 includes an easy-slip layer 15 on at least one surface of the film substrate 11.
  • a transparent film is preferable.
  • the total light transmittance of the transparent film substrate is preferably at least 80%, more preferably at least 85%, even more preferably at least 90%.
  • the resin material constituting the film substrate 11 include an acrylic resin, a polyester resin, a polycarbonate resin, a polyolefin resin, a cyclic polyolefin resin, a polystyrene resin, a polyamide resin, and a polyimide resin.
  • an acrylic resin or a cyclic polyolefin resin is preferable as the resin material of the film substrate 11, and an acrylic resin is particularly preferable. preferable.
  • cyclic polyolefin-based resin for example, polynorbornene can be mentioned.
  • Commercial products of the cyclic polyolefin-based resin include ZEONOR and ZEONEX manufactured by Nippon Zeon, ARTON manufactured by JSR, Apel manufactured by Mitsui Chemicals, and TOPAS manufactured by TOPAS ADVANCED POLYMERS.
  • the cyclic polyolefin-based film preferably contains at least 50% by weight of the cyclic olefin-based resin.
  • (meth) acryl means acryl and / or methacryl.
  • Acrylic resins include those containing acrylic acid or a derivative thereof as a constituent monomer component and those containing methacrylic acid or a derivative thereof as a constituent monomer component.
  • Acrylic resin having a glutaric anhydride structure and acrylic resin having a lactone ring structure have high heat resistance, high transparency, and high mechanical strength, and therefore have a high degree of polarization and excellent durability. Suitable for manufacturing.
  • the content of the acrylic resin in the film substrate is preferably 50% by weight or more, more preferably 60 to 98% by weight, and further preferably 70 to 97% by weight.
  • the acrylic film may contain a thermoplastic resin other than the acrylic resin. For example, by blending another thermoplastic resin, the birefringence of the acrylic resin is canceled, and an acrylic film having excellent optical isotropy can be obtained. Further, a thermoplastic resin other than the acrylic resin may be blended for the purpose of improving the mechanical strength of the film.
  • Thermoplastic resins other than acrylic resins include olefin polymers, vinyl halide polymers, polystyrene, copolymers of styrene and acrylic monomers, polyesters, polyamides, polyacetals, polycarbonates, polyphenylene oxides, polyphenylene sulfides, and polyphenylene sulfides.
  • examples include ether ether ketone, polysulfone, polyethersulfone, polyoxybenzylene, polyamideimide, and rubber-based polymers.
  • the film substrate 11 may contain additives such as an antioxidant, a stabilizer, a reinforcing material, an ultraviolet absorber, a flame retardant, an antistatic agent, a coloring agent, a filler, a plasticizer, a lubricant, and a filler.
  • additives such as an antioxidant, a stabilizer, a reinforcing material, an ultraviolet absorber, a flame retardant, an antistatic agent, a coloring agent, a filler, a plasticizer, a lubricant, and a filler.
  • a film may be formed by mixing a resin material and an additive and forming a thermoplastic resin composition such as a pellet in advance.
  • the thickness of the film substrate 11 is about 5 to 200 ⁇ m. From the viewpoints of mechanical strength, transparency, handleability, and the like, the thickness of the film substrate 11 is preferably from 10 to 100 ⁇ m, more preferably from 15 to 60 ⁇ m.
  • the glass transition temperature Tg of the film substrate 11 is preferably 100 ° C or higher, more preferably 110 ° C or higher.
  • Tg can be increased and heat resistance can be improved.
  • the upper limit of the Tg of the film substrate 11 is not particularly limited, but is preferably 170 ° C. or lower from the viewpoint of moldability and the like.
  • Examples of the method for producing the film substrate 11 include a solution casting method, a melt extrusion method, a calendering method, and a compression molding method.
  • the film substrate 11 may be either an unstretched film or a stretched film.
  • the acrylic film is preferably a stretched film stretched in at least one direction, and particularly preferably a biaxially stretched film, from the viewpoint of improving mechanical strength.
  • By blending another thermoplastic resin so as to cancel the birefringence of the acrylic resin an acrylic film having small retardation and excellent optical isotropy even when stretched can be obtained.
  • polyisocyanate examples include tetramethylene diisocyanate, dodecamethylene diisocyanate, 1,4-butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, Aliphatic diisocyanates such as -methylpentane-1,5-diisocyanate and 3-methylpentane-1,5-diisocyanate; isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4'-cyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate Alicyclic diisocyanates such as methylcyclohexylene diisocyanate and 1,3-bis (isocyanatomethyl) cyclohexane Tolylene diisocyanate, 2,2'-diphen
  • the urethane resin constituting the easy sliding layer 15 preferably has a carboxy group.
  • the urethane resin having a carboxy group is obtained, for example, by reacting a chain extender having a free carboxy group in addition to a polyol and a polyisocyanate.
  • Examples of the chain extender having a free carboxy group include dihydroxycarboxylic acid, dihydroxysuccinic acid and the like.
  • dihydroxycarboxylic acid examples include dialkylolalkanoic acids such as dimethylolalkanoic acid (for example, dimethylolacetic acid, dimethylolbutanoic acid, dimethylolpropionic acid, dimethylolbutyric acid, and dimethylolpentanoic acid).
  • dimethylolalkanoic acid for example, dimethylolacetic acid, dimethylolbutanoic acid, dimethylolpropionic acid, dimethylolbutyric acid, and dimethylolpentanoic acid.
  • the method for producing the urethane resin is not particularly limited, and may be either a one-shot method in which the monomer components are reacted at once, or a multi-stage method in which the components are reacted stepwise.
  • a carboxy group is introduced into a urethane resin using a chain extender having a free carboxy group, a multi-step method is preferred.
  • a urethane reaction catalyst may be used as necessary.
  • the number average molecular weight of the urethane resin is preferably from 5,000 to 600,000, more preferably from 10,000 to 400,000.
  • the acid value of the urethane resin is preferably from 10 to 50, and more preferably from 20 to 45.
  • the urethane resin may have a crosslinked structure.
  • the introduction of the crosslinked structure into the urethane resin tends to improve the adhesion between the lubricious layer 15 and the film substrate 11 and the hardness of the lubricious layer 15.
  • the crosslinking agent those capable of reacting with the crosslinking functional group of the urethane resin can be used without particular limitation.
  • a crosslinking agent containing an amino group, an oxazoline group, an epoxy group, a carbodiimide group or the like is used.
  • a crosslinking agent having an oxazoline group is preferable.
  • the oxazoline group has a low reactivity with the carboxy group at room temperature, so that the oxazoline group has a long pot life when mixed with the urethane resin, and can flexibly cope with the lead time of the process.
  • the crosslinking agent may be a low molecular compound or a polymer.
  • An acrylic polymer is preferable as the crosslinking agent, and an acrylic polymer having an oxazoline group is particularly preferable, since it has high solubility in an aqueous composition and excellent compatibility with a urethane resin.
  • the amount of the crosslinking agent used is preferably 1 to 30 parts by weight, more preferably 3 to 20 parts by weight, based on 100 parts by weight of the urethane resin.
  • the particle diameter (average primary particle diameter) of the fine particles is preferably 10 nm or more, more preferably 15 nm or more, and even more preferably 20 nm or more.
  • the average primary particle diameter of the fine particles is preferably smaller than the thickness of the lubricating layer. When the particle diameter of the fine particles is smaller than the thickness of the slippery layer, the fine particles can be prevented from falling off the slippery layer.
  • the particle diameter of the fine particles is preferably 250 nm or less, more preferably 200 nm or less.
  • the average primary particle diameter of the fine particles is smaller than the wavelength of visible light, scattering of visible light at the interface between the binder resin and the fine particles can be suppressed.
  • the particle diameter of the fine particles is preferably 100 nm or less, more preferably 80 nm or less, further preferably 60 nm or less, and particularly preferably 50 nm or less.
  • the fine particles of the easy-adhesion layer 15 may be either inorganic fine particles or organic fine particles.
  • inorganic fine particles are preferable because of excellent dispersibility and uniformity of the particle diameter.
  • the inorganic fine particles include inorganic oxides such as titania, alumina and zirconia; calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate, calcium phosphate and the like. Of these, inorganic oxides are preferred.
  • the organic fine particles include a silicone resin, a fluorine resin, and an acrylic resin.
  • the difference in the refractive index between the binder resin (generally, the refractive index is about 1.5) and the fine particles is small. Since the difference in refractive index from the binder resin is small and the dispersibility is excellent, silica particles are preferable as the fine particles of the slippery layer 15.
  • the slippery layer 15 In the case of forming the slippery layer 15 from a water-based composition, it is preferable to use fine particles having high water dispersibility. An aqueous dispersion of fine particles may be incorporated into the composition. In order to enhance the dispersibility of the fine particles, it is preferable to add an alkali component such as an amine or ammonia to make the composition for forming a slippery layer weakly alkaline.
  • an alkali component such as an amine or ammonia
  • Colloidal silica is preferably used as the water-dispersible silica particles.
  • colloidal silica Quartron PL series manufactured by Fuso Chemical Industry Co., Ltd., Snowtex series manufactured by Nissan Chemical Industry Co., Ltd., AERODISP series and AEROSIL series manufactured by Nippon Aerosil Co., Ltd., Seahorse Star manufactured by Nippon Shokubai Co., Ltd.
  • Commercial products such as the KE series may be used.
  • the content of the fine particles in the easy sliding layer 15 is preferably 3% by weight or more, more preferably 5% by weight or more.
  • the surface of the slippery layer 15 is increased by increasing the content of the fine particles to increase the amount (number density) of the fine particles per unit area. It is preferable to form unevenness uniformly in the inside.
  • the content of the fine particles in the slippery layer 15 is preferably 8% by weight or more, more preferably 10% by weight or more, and further preferably 12% by weight or more.
  • composition for easy slip layer formation is preferably an aqueous composition using water as a solvent (and a dispersion medium for fine particles).
  • concentration of the solid content (non-volatile component) in the composition for forming a slippery layer is preferably 1 to 30% by weight, more preferably 2 to 20% by weight, and still more preferably 3 to 15% by weight.
  • the amount of the alkali component contained in the composition for forming a smooth layer is preferably 300 ppm or more, more preferably 500 ppm or more, based on the solid content of the composition for forming a smooth layer.
  • the content of the alkali component is excessively large, it may be difficult to reduce the amount of the remaining alkali, and therefore, the amount of the alkali component contained in the composition for forming a slippery layer may be reduced. It is preferably 50,000 ppm or less, more preferably 10,000 ppm or less, still more preferably 5,000 ppm or less, based on the solid content of the composition.
  • specific examples of the alkali component contained in the composition for forming a slippery layer include amine and ammonia, and the total content of these alkali components is preferably within the above range.
  • the boiling point of at least one alkali component is preferably in the above range, and the boiling points of two or more alkali components are preferably in the above range. It is preferable that the boiling point of 50% by weight or more of the alkali component is in the above range based on 100 parts by weight of the total amount of the alkali contained in the lubricating layer. Ideally, the boiling points of all the alkali components contained in the composition for forming a slippery layer are within the above range.
  • Examples of the method for applying the composition for forming an easily slippery layer include a bar coating method, a roll coating method, a gravure coating method, a rod coating method, a slot orifice coating method, a curtain coating method, and a fountain coating method.
  • the lubricating layer 15 is formed by heating the composition for forming the lubricating layer after application and removing the solvent.
  • the precursor of the binder resin may be reacted and cured by heating.
  • the crosslinking reaction can be promoted by heating.
  • the heating temperature at the time of forming the easy lubricating layer is preferably higher than the glass transition temperature (Tg) of the film substrate.
  • Tg glass transition temperature
  • the heating temperature is preferably at least 10 ° C. higher than the Tg of the film substrate.
  • the heating temperature is preferably Tg + 10 ° C. or higher, more preferably Tg + 15 ° C. or higher, and even more preferably Tg + 20 ° C. or higher.
  • the draw ratio is preferably 5 times or less, more preferably 4 times or less, from the viewpoint of suppressing problems such as crack generation in the slippery layer. It is preferably 3 times or less, more preferably 2.5 times or less.
  • the lower limit of the stretching ratio is not particularly limited, but from the viewpoint of improving the film strength, the stretching ratio is preferably 1.3 times or more, more preferably 1.5 times or more.
  • the film substrate is an acrylic film, it is preferable to perform stretching at the above-described stretching ratio in each of the transport direction (MD) and the width direction (TD) from the viewpoint of improving the film strength.
  • the reason that the fine particles are easily buried in the film substrate by stretching at a high temperature is that when the stretching is performed in a rubber state, the composition for forming a slippery layer easily spreads when the film substrate is deformed and is formed at the time of deformation. That is, the fine particles are likely to be fitted in the concave portions of the surface irregularities. Further, if cooling is performed while releasing the stress after stretching, when the film substrate contracts, the particles fitted on the surface of the film substrate are fixed, so that a region in which the fine particles are embedded in the film substrate is formed. It is considered easy.
  • the thickness of the slippery layer 15 can be adjusted by adjusting the solid concentration and the coating thickness of the slippery layer forming composition. In the case where the film base material is stretched after the application of the composition for forming a slippery layer, the thickness of the slippery layer 15 can be adjusted by the stretching ratio.
  • the thickness of the slippery layer 15 is not particularly limited, but is preferably 280 nm or less, more preferably 250 nm or less, and still more preferably 230 nm or less from the viewpoint of promoting the removal of alkali components by heating.
  • the optical film 1 is used as a polarizer protective film, the humidification durability of the polarizing plate tends to improve as the thickness of the slippery layer 15 decreases.
  • the thickness of the slippery layer 15 is preferably 40 nm or more, more preferably 50 nm or more, further preferably 80 nm or more, and particularly preferably 100 nm or more.
  • the thickness of the slippery layer may be 110 nm or more, 120 nm or more, 130 nm or more, 140 nm or more, or 150 nm or more.
  • the polarizing plate may have a transparent protective film on only one surface of the polarizer, or may have a transparent protective film on both surfaces of the polarizer 5 as shown in FIGS. 2A and 2B.
  • a polarizing plate having a transparent protective film only on one surface of the polarizer is formed.
  • the polarizing plate having the polarizer protective films on both surfaces of the polarizer may be any one as long as the optical film is attached to at least one surface of the polarizer.
  • the polarizing plate may be one in which the above-mentioned optical film is bonded to both surfaces of a polarizer.
  • the polarizer 5 and the optical film 1 are bonded via an adhesive layer 6.
  • polarizer polyvinyl alcohol (PVA) in which a dichroic substance such as iodine or a dichroic dye is adsorbed on a polyvinyl alcohol-based film such as polyvinyl alcohol or partially formalized polyvinyl alcohol and is oriented in one direction.
  • PVA polyvinyl alcohol
  • a system polarizer is used.
  • a PVA-based polarizer can be obtained by performing iodine dyeing and stretching on a polyvinyl alcohol-based film.
  • a thin PVA-based polarizer having a thickness of 10 ⁇ m or less can be used.
  • the thin polarizer include those described in, for example, JP-A-51-069694, JP-A-2000-338329, WO2010 / 100917, pamphlet No. 4691205, and Japanese Patent No. 4751481.
  • Thin polarizers. These thin polarizers are obtained by a manufacturing method including a step of stretching a PVA-based resin layer and a resin substrate for stretching in a laminate state, and a step of iodine dyeing. According to this manufacturing method, even if the PVA-based resin layer is thin, it can be stretched without any trouble such as breakage due to stretching because it is supported by the stretching resin base material.
  • the material of the adhesive layer 6 used for bonding the polarizer 5 and the optical film 1 is not particularly limited as long as it is optically transparent, and may be an epoxy resin, a silicone resin, an acrylic resin, a polyurethane, Examples include polyamide, polyether, and polyvinyl alcohol.
  • the thickness of the adhesive layer 6 is, for example, about 0.01 to 20 ⁇ m, and is appropriately set according to the type of the adherend and the material of the adhesive. In the case of using a curable adhesive exhibiting adhesiveness by a crosslinking reaction after application, the thickness of the adhesive layer 6 is preferably 0.01 to 5 ⁇ m, more preferably 0.03 to 3 ⁇ m.
  • the average degree of polymerization of the polyvinyl alcohol-based resin is preferably about 100 to 5,000, more preferably 1,000 to 4,000, from the viewpoint of adhesiveness.
  • the average degree of saponification of the polyvinyl alcohol-based resin is preferably at least 85 mol%, more preferably at least 90 mol%.
  • Examples of the monomer of the radical polymerizable adhesive include a compound having a (meth) acryloyl group and a compound having a vinyl group. Among them, compounds having a (meth) acryloyl group are preferred.
  • Examples of the compound having a (meth) acryloyl group include alkyl (meth) acrylates such as C 1-20 chain alkyl (meth) acrylate, alicyclic alkyl (meth) acrylate, and polycyclic alkyl (meth) acrylate; Included (meth) acrylates; epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate; Radical polymerizable adhesives include hydroxyethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, (meth) acrylamide, (meth) acrylo
  • Examples of the curable component of the cationically polymerizable adhesive include compounds having an epoxy group or an oxetanyl group.
  • the compound having an epoxy group is not particularly limited as long as it has at least two epoxy groups in a molecule, and various curable epoxy compounds generally known are used.
  • Preferred epoxy compounds include compounds having at least two epoxy groups and at least one aromatic ring in the molecule (aromatic epoxy compounds), and those having at least two epoxy groups in the molecule and at least one of them. Is a compound formed between two adjacent carbon atoms constituting an alicyclic ring (an alicyclic epoxy compound).
  • a hybrid adhesive can be obtained by adding a radically polymerizable compound such as a compound having a (meth) acryloyl group to the cationically polymerizable adhesive.
  • the photocurable adhesive preferably contains a photopolymerization initiator.
  • the photopolymerization initiator may be appropriately selected according to the reaction species. For example, it is preferable to mix a radically polymerizable adhesive with a photoradical generator that generates radicals by light irradiation as a photopolymerization initiator. It is preferable that a cationic photopolymerization initiator (photoacid generator) that generates a cationic species or a Lewis acid upon irradiation with light is added to the cationic polymerizable adhesive as a photopolymerization initiator. It is preferable to mix a photocationic polymerization initiator and a photoradical generator in the hybrid adhesive.
  • a polarizing plate is manufactured by attaching the optical film 1 to one surface (first main surface) of the polarizer 5 with the adhesive layer 6 interposed therebetween.
  • the optical film 1 may have a surface on which a slippery layer is formed bonded to the polarizer 5 via an adhesive layer, and as shown in FIG. It may be bonded to the polarizer 5 via an adhesive layer.
  • the polarizer 5 and the optical film 1 are bonded to a roll laminator or the like. It is preferable to bond together and cure the adhesive.
  • a method for applying the adhesive composition to the polarizer 5 and / or the optical film 1 include a roll method, a spray method, and a dipping method.
  • a surface treatment such as a corona treatment, a plasma treatment, or a saponification treatment may be performed.
  • the adhesive is cured according to the type of the adhesive, whereby the adhesive layer 6 is formed.
  • the adhesive is cured by heating and drying.
  • an active energy ray-curable adhesive the adhesive is cured by irradiation with an active energy ray such as an electron beam or an ultraviolet ray.
  • an active energy ray such as an electron beam or an ultraviolet ray.
  • the transparent protective film 2 may be bonded to the second main surface of the polarizer 5 via an adhesive layer 7.
  • any suitable transparent film can be adopted.
  • the thickness of the transparent protective film 2 is about 5 to 200 ⁇ m. In light of mechanical strength, transparency, handleability, and the like, the thickness of the transparent protective film 2 is preferably from 10 to 100 ⁇ m, and more preferably from 15 to 60 ⁇ m. The thicknesses of the optical film 1 and the transparent protective film 2 may be the same or different.
  • Examples of a material for forming the transparent protective film 2 include polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN); cellulose polymers such as diacetyl cellulose and triacetyl cellulose; polystyrene and acrylonitrile -Styrene-based polymers such as styrene copolymers; cyclic polyolefins such as polynorbornene; polycarbonates;
  • polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN); cellulose polymers such as diacetyl cellulose and triacetyl cellulose; polystyrene and acrylonitrile -Styrene-based polymers such as styrene copolymers; cyclic polyolefins such as polynorbornene; polycarbonates;
  • the transparent protective film 2 may have a lubricating layer (not shown).
  • the transparent protective film 2 may be provided with a slippery layer similar to the slippery layer 15 of the optical film 1.
  • the adhesive layer 7 used for bonding the polarizer 5 and the transparent protective film 2 includes various forms such as an aqueous adhesive, a solvent adhesive, a hot melt adhesive, and an active energy ray-curable adhesive. Is used.
  • the same adhesive composition may be used for the adhesive layer 6 and the adhesive layer 7.
  • the polarizing plate may be provided with an adhesive layer for bonding to a liquid crystal cell, an organic EL cell, or the like.
  • an acrylic polymer, a silicone-based polymer, a polyester, a polyurethane, a polyamide, a polyether, a fluorine-based or rubber-based polymer or the like as a base polymer is appropriately selected and used.
  • an acrylic pressure-sensitive adhesive is preferable because it is excellent in optical transparency, exhibits appropriate wettability and cohesion, and is excellent in weather resistance, heat resistance, and the like.
  • the attachment of the pressure-sensitive adhesive layer to the polarizing plate can be performed by an appropriate method.
  • a pressure-sensitive adhesive solution having a solid concentration of about 10 to 40% by weight in which a base polymer or the like is dissolved or dispersed in a solvent such as toluene or ethyl acetate is prepared and attached to a polarizing plate, or an appropriate base material is prepared.
  • the polarizing plate may be a laminated polarizing plate laminated with another optical layer.
  • the optical layer include a retardation plate, a viewing angle compensation film, and a brightness enhancement film.
  • composition for easy slip layer formation 20.6 parts by weight of a 34% solids aqueous polyurethane ("Superflex 210R” manufactured by Daiichi Kogyo Seiyaku) containing polyester urethane and isophorone diisocyanate as a resin component, and further containing triethylamine as a curing catalyst and methyl ethyl ketone as a dispersion medium; Oxazoline-containing polymer aqueous solution having a solid content of 25% (Nippon Shokubai "Epocross WS-700") 5.2 parts by weight, 1% by weight 2.8 parts by weight of ammonia water, 20% water of colloidal silica having an average primary particle diameter of 35 nm 7.5 parts by weight of a dispersion ("Quatron PL-3" manufactured by Fuso Chemical Industries) and 63.9 parts by weight of pure water were mixed to prepare a composition for forming a slippery layer.
  • This composition was a 9.8% aqueous solution containing 15.3
  • the film was stretched twice in the longitudinal direction (MD) and in the width direction (TD) by a simultaneous biaxial stretching tenter to obtain an optical film having a 50-nm-thick smooth layer on one surface of an acrylic film having a thickness of 40 ⁇ m. .
  • Example 2 to 4 and Comparative Examples 1 and 2 An optical film was obtained in the same manner as in Example 1 except that the coating thickness of the composition for forming a slippery layer was changed.
  • the thickness (after stretching) of the slippery layer was as shown in Table 2.
  • Example 5 and 6 and Comparative Examples 3 to 5 The furnace temperature (stretching temperature) during tenter stretching was changed as shown in Table 2. An optical film was obtained in the same manner as in Example 1 except that the stretching temperature was changed.
  • ⁇ Adhesion of lubricious layer> An adhesive tape (“No. 31B” manufactured by Nitto Denko Corporation) is pressure-bonded to the surface of the optical film on which the slippery layer is formed at a linear pressure of 8 kg / m and a pressure-bonding speed of 0.3 m / min, and stored at 50 ° C. for 48 hours. The tip of the tape was gripped and a 180 ° peel test was performed at a pulling speed of 30 m / min, and the adhesion of the slippery layer was determined according to the following criteria. ⁇ : Peeling off at the interface between the adhesive tape and the lubricating layer without peeling of the lubricating layer from the acrylic film ⁇ : Peeling off at the interface between the acrylic film and the lubricating layer
  • FIG. 3 shows a TEM observation image of Example 3 (with an interface layer)
  • FIG. 4 shows a TEM observation image of Comparative Example 4 (without an interface layer).
  • polarizing plate ⁇ Humidification durability of polarizing plate>
  • the polarizing plate was cut into a size of 320 mm ⁇ 240 mm, and the surface on the side of the cyclic polyolefin film was bonded to glass via an acrylic adhesive having a thickness of 20 ⁇ m.
  • This sample is placed in a thermo-hygrostat at a temperature of 60 ° C. and a relative humidity of 90% (condition 1) or a thermo-hygrostat at a temperature of 85 ° C. and a relative humidity of 85% (condition 2), and held for 500 hours for heating and heating.
  • a humidification durability test was performed.
  • the optical films of Examples 1 to 4 in which a 50-250 nm smooth layer was formed at a stretching temperature of 140 ° C. did not show white turbidity due to aggregation of fine particles and had a good appearance.
  • the optical film of Example 1 had fine scratches on the surface where the easy-slip layer was not formed, the optical film was buried with an adhesive or an adhesive at the time of lamination with another member, resulting in an optical defect. It was a level of scratch that did not happen.
  • the polarizing plates using the optical films of Examples 1 to 4 were superior to the polarizing plate using the optical film of Comparative Example 2 in humidification durability, and generation of streaks was suppressed.
  • Example 5 in which a 200-nm-thick smooth layer was formed at a stretching temperature of 160 ° C. or 180 ° C., as in Example 3, the appearance of the optical film and the humidification durability of the polarizing plate were excellent.
  • Comparative Examples 3 to 5 in which a 200-nm-thick slippery layer was formed at a stretching temperature of 80 to 120 ° C., the amount of alkali remaining in the slippery layer was large. Was confirmed.

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