WO2021029127A1 - 易接着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

易接着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
WO2021029127A1
WO2021029127A1 PCT/JP2020/022415 JP2020022415W WO2021029127A1 WO 2021029127 A1 WO2021029127 A1 WO 2021029127A1 JP 2020022415 W JP2020022415 W JP 2020022415W WO 2021029127 A1 WO2021029127 A1 WO 2021029127A1
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Prior art keywords
easy
adhesion
film
adhesive
fine particles
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PCT/JP2020/022415
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English (en)
French (fr)
Japanese (ja)
Inventor
そら 道下
雅 品川
果令 糸永
洋 近野
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日東電工株式会社
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Priority to CN202080056610.7A priority Critical patent/CN114207485A/zh
Priority to KR1020217043203A priority patent/KR102607551B1/ko
Publication of WO2021029127A1 publication Critical patent/WO2021029127A1/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
    • G02B5/3025—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
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • 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
    • C09D201/00—Coating compositions 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
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • 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
    • C09J7/50—Adhesives in the form of films or foils characterised by a primer layer between the carrier and the adhesive
    • G—PHYSICS
    • G02—OPTICS
    • 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
    • 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
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/42—Polarizing, birefringent, filtering
    • 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
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
    • 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
    • C09J2433/00—Presence of (meth)acrylic polymer
    • C09J2433/006—Presence of (meth)acrylic polymer in the substrate
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light

Definitions

  • the present invention relates to an easy-adhesive film provided with an easy-adhesive layer on the surface of a transparent film base material and a method for producing the same. Further, the present invention relates to a polarizing plate in which an easily adhesive film is bonded to the surface of a polarizing element, 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. Due to the display principle of the liquid crystal display device, a polarizing plate is arranged on the visible surface of the liquid crystal cell. In a transmissive liquid crystal display device, polarizing plates are arranged on both sides of the liquid crystal cell. In an organic EL display device, in order to prevent external light from being reflected by a metal electrode (cathode) and visually recognized as a mirror surface, a circularly polarizing plate (typically, a polarizing plate and 1 /) are formed on the viewing side surface. A laminated body of four wave plates) may be arranged.
  • the polarizing plate is provided with a transparent film (polarizer protective film) for the purpose of protecting the polarizing element on one side or both sides of the polarizer.
  • polarizer protective film a transparent film
  • PVA polyvinyl alcohol
  • a cellulose-based film such as cellulose acetate is widely used because of its excellent adhesion to the PVA-based polarizer.
  • a transparent protective film a film made of a resin material such as acrylic, polyester, polycarbonate, or cyclic polyolefin has also been used. Films made of these resin materials have lower moisture permeability than cellulosic films, and polarizing plates with a low moisture permeability resin film bonded to the surface of the polarizer are subject to long-term exposure to a high humidity environment. However, the change in optical characteristics is small, and it tends to be excellent in durability.
  • films made of resin materials such as acrylic, polyester, polycarbonate, and cyclic polyolefin tend to have lower adhesiveness to PVA-based polarizers than cellulose-based films. Therefore, a method has been proposed in which an easy-adhesion layer is provided on the surface of a transparent film used as a polarizer protective film to improve the adhesiveness with a polarizer.
  • an easy-adhesive film provided with an easy-adhesive layer containing fine particles and a binder resin on the surface of an acrylic film has excellent adhesiveness to a polarizer and is used when the film is wound into a roll. It is described that blocking can be suppressed.
  • Patent Document 2 describes that the blocking resistance is improved when the average primary particle diameter of the fine particles contained in the easy-adhesion layer is larger than 200 nm.
  • the polarizing plate using the easy-adhesion film described in Patent Document 1 and Patent Document 2 as the polarizer protective film has excellent adhesiveness between the polarizer and the polarizer protective film, and has high adhesive reliability.
  • the polarizing plate using these easy-adhesive films as a polarizer protective film may cause unevenness and deterioration of display characteristics when exposed to a high humidity environment for a long time.
  • the present invention has excellent adhesion to a polarizer or the like, blocking is unlikely to occur, and even when exposed to a high temperature and high humidity environment for a long time, optical defects such as unevenness are unlikely to occur.
  • the purpose is to provide a film.
  • alkaline components such as ammonia and amines added to the easy-adhesion composition for the purpose of improving the dispersibility of fine particles remain in the easy-adhesion layer. It has been found that this is one of the causes of the decrease in durability in a humid environment, and the above problem can be solved by setting the amount of residual alkali in the easy-adhesion layer within a predetermined range.
  • the present invention relates to an easy-adhesive film provided with an easy-adhesive layer on the surface of a transparent film base material and a method for producing the same.
  • the easy-adhesion layer contains a binder resin and fine particles.
  • the thickness of the easy-adhesion layer is preferably 120 to 260 nm.
  • the average primary particle diameter of the fine particles contained in the easy-adhesion layer is preferably 0.1 to 0.9 times the thickness of the easy-adhesion layer.
  • the average primary particle size of the fine particles is 10 nm or more, preferably 100 to 200 nm.
  • the content of the alkaline component of the easy-adhesion layer is preferably 200 ppm or less, and the total content of amine and ammonia is preferably 200 ppm or less.
  • Acrylic film or the like is used as the transparent film base material.
  • Urethane-based resin or the like is used as the binder resin for the easy-adhesion layer.
  • the content of the fine particles in the easy-adhesion layer is preferably about 8 to 50% by weight.
  • the fine particles of the easy-adhesion layer may be embedded in the transparent film base material.
  • the easy-adhesion layer is formed by applying the easy-adhesion composition to the surface of the transparent film base material and heating it.
  • the easy-adhesion composition contains a binder resin or a precursor thereof, fine particles, an alkaline component and a solvent. Since the easy-adhesion composition contains an alkaline component, the dispersibility of the fine particles is improved, and an easy-adhesion film having excellent slipperiness can be obtained.
  • the alkaline component can also act as a catalyst for promoting the reaction of the binder resin (precursor). From the viewpoint of promoting volatilization of the alkaline component by heating, the boiling point of the alkaline component is preferably 150 ° C. or lower. Examples of the alkaline component include amine and ammonia.
  • the easy-adhesion composition may be heated at a temperature higher than the glass transition temperature of the transparent film substrate by 10 ° C. or more.
  • the heating temperature By increasing the heating temperature, a region in which fine particles of the easy-adhesion layer are embedded in the transparent film base material is likely to be formed, and the adhesion between the transparent film base material and the easy-adhesion layer tends to be improved.
  • stretching may be performed while heating the transparent film base material.
  • stretching the transparent film base material while heating the easy-adhesion composition at a temperature 10 ° C. or higher higher than the glass transition temperature of the transparent film base material the adhesion between the transparent film base material and the easy-adhesion layer is improved. Tend to do.
  • the above-mentioned easy-adhesive film has excellent adhesiveness to other films, glass substrates, etc.
  • the easy-adhesive film can be used, for example, as a polarizer protective film.
  • a polarizing plate can be obtained by adhering an easy-adhesive film to the surface of a polyvinyl alcohol-based polarizer via an adhesive layer.
  • An image display device can be formed by arranging a polarizing plate on the surface of an image display cell such as a liquid crystal display cell or an organic EL cell.
  • the easy-adhesive film of the present invention is less likely to cause blocking and is less likely to cause optical defects even when exposed to a high temperature and high humidity environment for a long time. Therefore, it is suitably used as a film for a display device such as a polarizer protective film. Be done.
  • FIG. 1 is a schematic cross-sectional view showing a configuration example of an easily adhesive film according to an embodiment of the present invention.
  • the easy-adhesion film 1 is provided with an easy-adhesion layer 15 on at least one surface of the film base material 11. Easy-adhesion layers may be provided on both sides of the film substrate.
  • the easy-adhesive film is used by being bonded to another film, a glass substrate, or the like.
  • FIG. 2 is a cross-sectional view showing a configuration example of a polarizing plate including the easy-adhesion film 1 as a polarizer protective film.
  • the polarizing plate 100 includes an easy-adhesion film 1 bonded to one surface (first main surface) of the polarizer 5 via an adhesive layer 6.
  • the easy-adhesion film 1 has an easy-adhesion layer 15 on the bonding surface of the film base material 11 with the polarizing element 5.
  • An easy-adhesion layer may be provided on the surface to which the polarizer 5 is not bonded.
  • a transparent protective film 2 is attached to the other surface (second main surface) of the polarizer 5 via an adhesive layer 7.
  • the easy-adhesion film 1 includes an easy-adhesion layer 15 on at least one surface of the film base material 11.
  • a transparent film is preferable as the film base material 11.
  • the total light transmittance of the transparent film substrate is preferably 80% or more, more preferably 85% or more, still more preferably 90% or more.
  • the resin material constituting the film base material 11 include acrylic resin, polyester resin, polycarbonate resin, polyolefin resin, cyclic polyolefin resin, polystyrene resin, polyamide resin, and polyimide resin.
  • an acrylic resin or a cyclic polyolefin resin is preferable as the resin material of the film base material 11 because the birefringence is small, and the acrylic resin is preferable. Especially preferable.
  • cyclic polyolefin resin examples include polynorbornene.
  • examples of commercially available cyclic polyolefin resins include Zeonoa and Zeonex manufactured by Zeon Corporation, Arton manufactured by JSR, Appel manufactured by Mitsui Chemicals, and Topas manufactured by TOPAS ADVANCED POLYMERS.
  • the cyclic polyolefin-based film preferably contains 50% by weight or more of the cyclic olefin-based resin.
  • acrylic resin examples include poly (meth) acrylic acid esters such as polymethyl methacrylate, methyl methacrylate- (meth) acrylic acid copolymers, methyl methacrylate- (meth) acrylic acid ester copolymers, and methyl methacrylate.
  • polymer having alicyclic hydrocarbon group for example, methyl methacrylate-methacrylic acid
  • Cyclohexyl copolymer methyl methacrylate- (meth) acrylate norbornyl copolymer, etc.
  • (meth) acrylic means acrylic and / or methacrylic.
  • 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.
  • the acrylic resin As the acrylic resin, the acrylic resin having a glutaric anhydride structure described in JP-A-2006-283013, JP-A-2006-335902, JP-A-2006-274118, etc .; and / or JP-A.
  • Acrylic resins having a glutaric anhydride structure and acrylic resins having a lactone ring structure have high heat resistance, high transparency, and high mechanical strength, and thus have a high degree of polarization and excellent durability. Suitable for manufacturing.
  • the content of the acrylic resin in the film base material is preferably 50% by weight or more, more preferably 60 to 98% by weight, still more 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 isotropic properties 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-based polymers, vinyl halide-based polymers, polystyrene, styrene and acrylic monomer and copolymers, polyester, polyamide, polyacetal, polycarbonate, polyphenylene oxide, polyphenylene sulfide, and poly. Examples thereof include ether ether ketone, polysulfone, polyethersulfone, polyoxybenzylene, polyamideimide, and rubber-based polymers.
  • the film substrate 11 may contain additives such as antioxidants, stabilizers, reinforcing materials, ultraviolet absorbers, flame retardants, antistatic agents, colorants, fillers, plasticizers, lubricants and fillers.
  • additives such as antioxidants, stabilizers, reinforcing materials, ultraviolet absorbers, flame retardants, antistatic agents, colorants, fillers, plasticizers, lubricants and fillers.
  • the resin material and the additive or the like may be mixed to prepare a thermoplastic resin composition such as pellets in advance, and then filmed.
  • the thickness of the film base material 11 is about 5 to 200 ⁇ m. From the viewpoint of mechanical strength, transparency, handleability, etc., the thickness of the film base material 11 is preferably 10 to 100 ⁇ m, more preferably 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.
  • the film base material 11 is an acrylic film, as described above, by using an acrylic resin having a glutaric acid anhydride structure or an acrylic resin having a lactone ring structure as the acrylic resin, the acrylic film can be obtained. Tg can be increased and heat resistance can be improved.
  • the upper limit of Tg of the film base material 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 base material 11 include a solution casting method, a melt extrusion method, a calendar method, and a compression molding method.
  • the film base material 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 a biaxially stretched film is particularly preferable, 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 a small retardation and excellent optical isotropic properties can be obtained even when stretched.
  • the easy-adhesion layer 15 provided on the surface of the film base material 11 contains a binder resin and fine particles.
  • the adhesiveness to a film such as a polarizer, a glass substrate, or the like can be improved.
  • the easy-adhesion layer 15 contains fine particles, fine irregularities are formed on the surface of the easy-adhesion layer 15, and the slipperiness of the film is improved. Therefore, it contributes to the reduction of scratches when the easy-adhesive film 1 is conveyed in a roll and the suppression of blocking when the film is wound into a roll.
  • Binder resin As the binder resin, since it has excellent adhesion to a film base material such as an acrylic film, it has cross-linking properties such as polyurethane resin, epoxy resin, isocyanate resin, polyester resin, polymers containing an amino group in the molecule, and oxazoline group. A resin (polymer) having a reactive group such as an acrylic resin having a functional group is used. As the binder resin of the easy-adhesion layer 15, a polyurethane resin is particularly preferable. The easy-adhesion layer 15 containing the polyurethane resin binder has high adhesion to the film base material 11. Further, the easy-adhesive film 1 in which the easy-adhesive layer 15 contains a polyurethane resin binder tends to exhibit high adhesiveness when a film such as a polarizer is laminated via an adhesive layer.
  • Urethane resin is typically a reaction product of polyol and polyisocyanate.
  • a polymer polyol such as a polyacrylic polyol, a polyester polyol, or a polyether polyol is preferably used.
  • the polyacrylic polyol is typically obtained by polymerizing a (meth) acrylic acid ester and a hydroxyl group-containing monomer.
  • the (meth) acrylic acid ester include methyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate and the like.
  • the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and (meth).
  • Hydroxyalkyl esters of (meth) acrylic acids such as 4-hydroxybutyl acrylate and 2-hydroxypentyl (meth) acrylate; (meth) acrylic acid monoesters of polyhydric alcohols such as glycerin and trimethylpropane; N-methylol Examples include (meth) acrylamide.
  • the polyacrylic polyol may contain a monomer component other than the above.
  • Other monomer components include unsaturated monocarboxylic acids such as (meth) acrylic acid; unsaturated dicarboxylic acids such as maleic acid and their anhydrides and diesters; unsaturated nitriles such as (meth) acrylonitrile; (meth).
  • Unsaturated amides such as acrylamide and N-methylol (meth) acrylamide; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as methyl vinyl ether; ⁇ -olefins such as ethylene and propylene; vinyl chloride and vinylidene chloride Halogenized ⁇ , ⁇ -unsaturated aliphatic monomers such as styrene, ⁇ -unsaturated aromatic monomers such as styrene and ⁇ -methylstyrene, and the like.
  • the polyester polyol is typically obtained by the reaction of a polybasic acid with a polyol.
  • the polybasic acid include aromatics such as orthophthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, and tetrahydrophthalic acid.
  • Dicarboxylic acid oxalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decandicarboxylic acid, dodecandicarboxylic acid, octadecanedicarboxylic acid, tartaric acid, alkylsuccinic acid, linoleic acid , Maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid and other aliphatic dicarboxylic acids; hexahydrophthalic acid, tetrahydrophthalic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and other alicyclics.
  • the formula dicarboxylic acid; or a reactive derivative such as these acid anhydrides, alkyl esters, acid halides and the like can be mentioned.
  • polyol examples include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, 1,6-hexanediol, 1 , 8-octanediol, 1,10-decanediol, 1-methyl-1,3-butylene glycol, 2-methyl-1,3-butylene glycol, 1-methyl-1,4-pentylene glycol, 2-methyl -1,4-Pentylene glycol, 1,2-dimethyl-neopentyl glycol, 2,3-dimethyl-neopentyl glycol, 1-methyl-1,5-pentylene glycol, 2-methyl-1,5-penti Lene glycol, 3-methyl-1,5-pentylene glycol, 1,2-dimethylbutylene glycol, 1,3-dimethylbutylene glyco
  • the polyether polyol is typically obtained by ring-opening polymerization of an alkylene oxide on a polyhydric alcohol and adding it.
  • the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, and trimethylolpropane.
  • the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, and tetrahydrofuran.
  • polyisocyanate examples include tetramethylene diisocyanate, dodecamethylene diisocyanate, 1,4-butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate, 2.
  • 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-cyclohexanediisocyanate , Methylcycloheximethylene diisocyanate, alicyclic diisocyanates such as 1,3-bis (isocyanatemethyl) cyclohexane; tolylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate , 4,4'-Diphenyldimethylmethane diisocyanate, 4,4'-dibenzyldiisocyanate, 1,5-naph
  • the urethane resin constituting the easy-adhesion layer 15 preferably has a carboxy group. Since the urethane resin has a carboxy group, a crosslinked structure can be introduced, and the adhesive durability between the easy-adhesive film 1 and the polarizer or the like tends to be improved.
  • a urethane resin having a carboxy group can be obtained, for example, by reacting a chain lengthing agent having a free carboxy group in addition to a polyol and a polyisocyanate. Examples of the chain length agent having a free carboxy group include dihydroxycarboxylic acid and dihydroxysuccinic acid.
  • dihydroxycarboxylic acid examples include dialkylol alkanoic acids such as dimethylol alkanoic acid (for example, dimethylol acetic acid, dimethylol butanoic acid, dimethylol propionic acid, dimethylol butyric acid, and dimethylol pentanoic acid).
  • dialkylol alkanoic acids such as dimethylol alkanoic acid (for example, dimethylol acetic acid, dimethylol butanoic acid, dimethylol propionic acid, dimethylol butyric acid, and dimethylol pentanoic acid).
  • the method for producing the urethane resin is not particularly limited, and either a one-shot method in which the monomer components are reacted at once or a multi-step method in which the monomer components are reacted stepwise may be used.
  • a multi-step method is preferable.
  • a urethane reaction catalyst may be used if necessary.
  • the number average molecular weight of the urethane resin is preferably 5,000 to 600,000, more preferably 10,000 to 400,000.
  • the acid value of the urethane resin is preferably 10 to 50, more preferably 20 to 45.
  • the urethane resin may have a crosslinked structure.
  • a crosslinked structure By introducing a crosslinked structure into the urethane resin, the adhesive durability between the easy-adhesive film 1 and the polarizer or the like tends to be improved.
  • the cross-linking agent one capable of reacting with the cross-linking functional group of the urethane resin can be used without particular limitation.
  • a cross-linking agent containing an amino group, an oxazoline group, an epoxy group, a carbodiimide group and the like is used.
  • a cross-linking agent having an oxazoline group is preferable. Since the oxazoline group has low reactivity with the carboxy group at room temperature, it has a long pot life when mixed with a urethane resin, and can flexibly respond to the lead time of the process.
  • the cross-linking agent may be a low molecular weight compound or a polymer.
  • An acrylic polymer is preferable as the cross-linking agent because it has high solubility in an aqueous composition and excellent compatibility with urethane resin.
  • an acrylic polymer having an oxazoline group is used as the cross-linking agent, the adhesiveness between the easy-adhesive film 1 and a film such as a polarizer tends to be improved.
  • the amount of the cross-linking 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 size (average primary particle size) of the fine particles is preferably 0.1 times or more, more preferably 0.2 times or more the thickness of the easy-adhesion layer. , 0.3 times or more is more preferable.
  • the average primary particle diameter of the fine particles is preferably 0.9 times or less, more preferably 0.8 times or less the thickness of the easy-adhesion layer.
  • the haze of the easy-adhesion film is preferably less than 2%, preferably less than 1.5%. From the viewpoint of suppressing the increase in haze caused by the fine particles, the average particle size of the fine particles is preferably 250 nm or less, more preferably 200 nm or less. When the easy-adhesion layer having a small thickness is formed, the average particle size of the fine particles is preferably in the above range from the viewpoint of suppressing the fine particles from falling off from the surface of the easy-adhesion layer.
  • the average particle diameter of the fine particles is preferably 10 nm or more, more preferably 15 nm or more, still more preferably 20 nm or more.
  • the average particle size of the fine particles is preferably 50 nm or more, and particularly preferably larger than 100 nm. preferable.
  • the fine particles of the easy-adhesion layer 15 may be either inorganic fine particles or organic fine particles.
  • Inorganic fine particles are preferable as the fine particles because they are excellent in dispersibility and uniformity of particle size.
  • 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 preferable.
  • Examples of the organic fine particles include silicone-based resin, fluororesin, acrylic-based resin, and the like.
  • the difference in refractive index between the binder resin (generally about 1.5 refractive index) and the fine particles is small.
  • Silica particles are preferable as the fine particles of the easy-adhesion layer 15 because the difference in refractive index from the binder resin is small and the dispersibility is excellent.
  • the easy-adhesion layer 15 is formed from an aqueous composition
  • fine particles having high water dispersibility.
  • the aqueous dispersion of fine particles may be blended into the composition.
  • an alkaline component such as amine or ammonia to make the easy-adhesion composition weakly alkaline.
  • Colloidal silica is preferably used as the water-dispersible silica particles.
  • colloidal silica Quattron 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., and Seahorse Star manufactured by Nippon Shokubai Co., Ltd.
  • Commercially available products such as the KE series may be used.
  • the content of fine particles in the easy-adhesion layer 15 is preferably 3% by weight or more, preferably 4% by weight or more. Is more preferable.
  • the thickness of the easy-adhesion layer 15 is small (for example, when it is 260 nm or less)
  • the content of the fine particles is increased to increase the amount of fine particles (number density) per unit area, or the particle size of the fine particles is increased individually.
  • the slipperiness and blocking resistance tend to be improved.
  • the content of the fine particles in the easy-adhesion layer 15 is preferably 50% by weight or less, more preferably 40% by weight or less, and further preferably 30% by weight or less.
  • the content of the fine particles in the easy-adhesion layer 15 may be 20% by weight or less, 15% by weight or less, or 10% by weight or less.
  • the polarizer may be deteriorated, the degree of polarization of the polarizing plate may be lowered, or optical defects such as unevenness may occur.
  • the residual alkali amount of the easy-adhesive layer 15 is preferably 200 ppm or less, more preferably 150 ppm or less.
  • the smaller the residual alkali amount in the easy-adhesion layer 15, the more preferably, the residual alkali amount is preferably 100 ppm or less, and more preferably 75 ppm or less.
  • the amount of residual alkali may be 70 ppm or less, 60 ppm or less, or 55 ppm or less.
  • the residual alkali amount of the easy-adhesion layer 15 is preferably 3 ppm or more, more preferably 5 ppm or more, and even more preferably 10 ppm or more.
  • the amount of residual alkali may be 15 ppm or more, 20 ppm or more, or 25 ppm or more.
  • the residual alkaline component in the easy-adhesion layer include amines and ammonia, and it is preferable that the total content of amines and ammonia in the easy-adhesion layer is within the above range.
  • the amount of alkali in the easy-adhesion layer can be quantified by liquid chromatography, ion chromatography, or the like, depending on the type of alkaline component.
  • the alkaline component may be quantified by an analytical method (for example, LC / MS) that combines chromatography and mass spectrometry (MS).
  • an analytical method for example, LC / MS
  • MS mass spectrometry
  • the slipperiness and blocking resistance of the easy-adhesion film can be improved by increasing the content of the fine particles or increasing the particle size of the fine particles within a range that does not impair the dispersibility of the fine particles.
  • a method of using fine particles having a large particle diameter is preferable within a range not exceeding 0.9 times or 0.8 times the thickness of the easy-adhesion layer.
  • Fine particles having a particle size of more than 100 nm show good dispersibility even with a low amount of alkali, which is advantageous from the viewpoint of achieving both improvement in slipperiness and blocking resistance and improvement in durability of the polarizing plate.
  • the average primary particle diameter of the fine particles contained in the easy-adhesion layer is particularly preferably larger than 100 nm and 200 nm or less. ..
  • the method for forming the easy-adhesion layer 15 on the surface of the film base material 11 is not particularly limited.
  • the easy-adhesion layer 15 is formed by applying an easy-adhesion composition (coating liquid) containing a binder resin and fine particles on the film base material 11 and heating the film base material 11.
  • the easy-adhesion composition is preferably an aqueous composition using water as a solvent (and a dispersion medium for fine particles).
  • the concentration of the solid content (nonvolatile component) in the easy-adhesion composition is preferably 1 to 30% by weight, more preferably 2 to 20% by weight, still more preferably 3 to 15% by weight.
  • the water-based easy-adhesion composition contains water as a solvent (and a dispersion medium), a binder resin fat or a precursor thereof, and fine particles.
  • the easy-adhesion composition preferably further contains an alkaline component. As described above, the alkaline component has an action of promoting the dispersion of fine particles.
  • the alkali contained in the easy-adhesion composition may cause a decrease in the moisture and heat resistance of the polarizing plate.
  • a strong alkali such as caustic can cause deterioration of the polarizer even in a small amount. Therefore, as the alkaline component contained in the easy-adhesion composition, a weak alkaline component such as ammonia or amine is preferable.
  • the pH of the easy-adhesion composition (coating liquid) is preferably about 7.5 to 9 from the viewpoint of improving the dispersibility of the fine particles and preventing the deterioration of the polarizer.
  • the amount of the alkaline component contained in the easy-adhesion composition is preferably 100 ppm or more, more preferably 300 ppm or more, still more preferably 500 ppm or more, based on the solid content of the easy-adhesion composition.
  • the amount of the alkaline component contained in the easy-adhesion composition is determined by the solid content of the easy-adhesion composition.
  • 50,000 ppm or less is preferable, 10,000 ppm or less is more preferable, and 5,000 ppm or less is further preferable.
  • the amount of the alkaline component contained in the easy-adhesion composition may be 4000 ppm or less or 3500 ppm or less with respect to the solid content of the easy-adhesion composition.
  • specific examples of the alkaline component contained in the easy-adhesion composition include amine and ammonia, and it is preferable that the total content of these alkaline components is within the above range.
  • the alkaline component contained in the easy-adhesion composition may have a catalytic action or the like in addition to improving the dispersibility of the fine particles.
  • a tertiary amine such as triethylamine may be contained in the easy-adhesion composition as a urethanization catalyst for a polyurethane precursor (polypoly, isocyanate, etc.).
  • the alkaline component contained in the easy-adhesion composition preferably has a boiling point of 150 ° C. or lower.
  • the boiling point of the alkaline component is more preferably 130 ° C. or lower, further preferably 120 ° C. or lower, and particularly preferably 110 ° C. or lower.
  • the boiling point of the alkaline component may be 100 ° C. or lower or 90 ° C. or lower.
  • the boiling point of at least one alkaline component is preferably in the above range, and the boiling points of two or more alkaline components are preferably in the above range. It is preferable that the boiling point of the alkaline component of 50% by weight or more is in the above range with respect to the total amount of alkali contained in the easy-adhesion layer. Ideally, the boiling points of all alkaline components contained in the easy-adhesion composition are in the above range. For example, when the alkaline components are amine and ammonia, the boiling point of amine is preferably within the above range.
  • the easy-adhesion composition may contain a cross-linking agent in addition to the binder resin (or its precursor), fine particles and alkaline components.
  • the easy-adhesion composition includes catalysts such as cross-linking accelerators, antioxidants, ultraviolet absorbers, leveling agents, blocking inhibitors, antistatic agents, dispersion stabilizers, defoamers, thickeners, dispersants, and surfactants. , Additives such as lubricants may be included.
  • the surface treatment of the film substrate may be performed before the easy-adhesion composition is applied onto the film substrate 11.
  • the wetting tension of the film base material can be adjusted and the adhesion to the easy-adhesion layer 15 can be improved.
  • the surface treatment include corona treatment, plasma treatment, ozone spraying, ultraviolet irradiation, flame treatment, chemical treatment and the like. Among these, corona treatment or plasma treatment is preferable.
  • Examples of the method for applying the easy-adhesion composition 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 easy-adhesion layer 15 is formed by heating the easy-adhesion composition after coating to remove the solvent.
  • the precursor of the binder resin may be reacted and cured by heating.
  • the easy-adhesion composition contains a cross-linking agent, the cross-linking reaction can be promoted by heating.
  • the heating temperature at the time of forming the easy-adhesive layer is, for example, about 50 to 200 ° C.
  • the heating temperature is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, from the viewpoint of accelerating the curing reaction of the resin component in the easy-adhesion composition and efficiently volatilizing and removing the alkaline component contained in the easy-adhesion composition. 130 ° C. or higher is more preferable, and 135 ° C. or higher is particularly preferable. Further, the heating temperature is preferably higher than the boiling point of the alkaline component contained in the easy-adhesion composition.
  • the heating temperature at the time of forming the easy-adhesion layer is preferably higher than the glass transition temperature (Tg) of the film substrate.
  • Tg glass transition temperature
  • the heating temperature is preferably a temperature higher than Tg of the film substrate by 10 ° C. or more.
  • 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 for the film substrate.
  • the film substrate When the film substrate is heated at a temperature of Tg + 10 ° C. or higher, the film substrate changes from a glass state to a rubber state and the surface is easily deformed. Therefore, at the interface between the film substrate 11 and the easy-adhesion layer 15, the resin of the film substrate An interface layer in which the components and the constituent components of the easy-adhesion layer are mixed is likely to be formed. By forming the interface layer, the adhesion between the film base material 11 and the easy-adhesion layer 15 tends to be improved.
  • an easy-adhesion film having high adhesion between the film base material 11 and the easy-adhesion layer 15 can be obtained.
  • the fine particles are embedded in the film substrate in a rubber state in which the film substrate is heated to a temperature higher than Tg, and then the film substrate returns to the glass state, the fine particles embedded in the surface of the film substrate and their surroundings are present. It is considered that the binder resin adheres to the surface of the film base material, so that the adhesion between the film base material 11 and the easy-adhesion layer 15 is improved.
  • An easy-adhesion layer may be formed in the manufacturing process of the film base material. Further, the easy-adhesion layer may be formed by utilizing the heating at the time of forming the film base material. For example, when the film base material is a stretched film, the easy-adhesion composition is applied to the surface of the film before stretching or the film after longitudinal stretching, and heating during lateral stretching or simultaneous biaxial stretching by a tenter is used. Then, the solvent can be dried and the resin can be cured.
  • the draw ratio is preferably 5 times or less, more preferably 4 times or less, from the viewpoint of suppressing defects such as cracks in the easy-adhesion layer. It is more preferably 2 times or less, and particularly preferably 2.5 times or less.
  • the lower limit of the draw ratio is not particularly limited, but from the viewpoint of improving the film strength, the draw ratio is preferably 1.3 times or more, more preferably 1.5 times or more.
  • the film base material is an acrylic film, it is preferable to perform stretching at the above stretching ratios in each of the transport direction (MD) and the width direction (TD) from the viewpoint of improving the film strength.
  • the biaxial stretching may be sequential biaxial stretching or simultaneous biaxial stretching. Moreover, you may perform diagonal stretching.
  • sequential biaxial stretching as described above, the film is stretched in one direction (MD) by roll stretching, then the easy-adhesion composition is applied onto the film, and the easy-adhesion composition is heated during stretching with a tenter. May be done.
  • the stretching temperature is preferably higher than Tg of the film substrate, preferably Tg + 10 ° C. or higher, more preferably Tg + 15 ° C. or higher, and even more preferably Tg + 20 ° C. or higher as the heating temperature of the easy-adhesion layer.
  • Tg the film substrate
  • a region in which fine particles in the easy-adhesion composition are embedded is likely to be formed on the surface of the film base material, and the film base material 11 and the easy-adhesion layer 15 are formed. Adhesion tends to improve.
  • the reason why fine particles are easily embedded in the film base material by stretching at a high temperature is that when the film base material is stretched in a rubber state, the easy-adhesive composition easily wets and spreads when the film base material is deformed, and the surface irregularities formed at the time of deformation are formed. It can be mentioned that fine particles are likely to be fitted in the concave portion. Further, when cooling is performed while releasing stress after stretching, when the film base material shrinks, the particles fitted on the surface of the film base material are fixed, so that a region in which the fine particles are embedded is formed in the film base material. It is considered easy.
  • the thickness of the easy-adhesion layer 15 can be adjusted by adjusting the solid content concentration and the coating thickness of the easy-adhesion composition.
  • the thickness of the easy-adhesion layer 15 can be adjusted by the stretching ratio.
  • the thickness of the easy-adhesion layer 15 is not particularly limited, but is preferably 260 nm or less, more preferably 250 nm or less, from the viewpoint of promoting the removal of alkaline components by heating.
  • the thickness of the easy-adhesion layer may be 240 nm or less, 230 nm or less, or 220 nm or less.
  • the easy-adhesion film 1 is used as a polarizer protective film, the smaller the thickness of the easy-adhesion layer 15, the better the humidification durability of the polarizing plate, and the less the occurrence of optical defects such as streaky unevenness tends to occur. There is. Further, the smaller the thickness of the easy-adhesion layer 15, the more the decrease in the degree of polarization tends to be suppressed when the polarizing plate is exposed to a humidified environment.
  • the thickness of the easy-adhesion layer 15 is preferably 100 nm or more.
  • the thickness of the easy-adhesion layer 15 is preferably 120 nm or more.
  • the thickness of the easy-adhesion layer may be 130 nm or more, 140 nm or more, 150 nm or more, or 160 nm or more.
  • the polarizing plate may be provided with a transparent protective film on only one surface of the polarizing element, or may be provided with a transparent protective film on both sides of the polarizing element 5 as shown in FIG.
  • a polarizing plate having a transparent protective film on only one surface of the polarizer is formed.
  • a polarizing plate having a polarizing element protective film on both surfaces of the polarizing element may have the above-mentioned easy-adhesive film bonded to at least one surface of the polarizing element.
  • the polarizing plate may be one in which the above-mentioned easy-adhesion film is bonded to both sides of the polarizing element.
  • the polarizer 5 and the easy-adhesive film 1 are bonded to each other via the adhesive layer 6.
  • the polarizing element 5 is 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 oriented in one direction.
  • PVA polyvinyl alcohol
  • a system polarizer is used.
  • a PVA-based polarizer can be obtained by subjecting a polyvinyl alcohol-based film to iodine dyeing and stretching.
  • the polarizer 5 treatments such as washing with water, swelling, and crosslinking may be performed, if necessary. Stretching may be performed before or after iodine dyeing, or may be performed while dyeing. The stretching may be either stretching in the air (dry stretching) or stretching in water or an aqueous solution containing boric acid, potassium iodide and the like (wet stretching), and these may be used in combination.
  • the film thickness of the polarizer 5 is not particularly limited, but is generally about 1 to 50 ⁇ m.
  • a thin PVA-based polarizer having a thickness of 10 ⁇ m or less can also be used.
  • Examples of the thin polarizing element are described in JP-A-51-069644, JP-A-2000-338329, WO2010 / 100917 Pamphlet, Patent No. 46910205, Patent No. 4751481 and the like.
  • There are thin polarizers. These thin polarizers are obtained by a production method including a step of stretching a PVA-based resin layer and a drawing resin base material in a laminated state, and a step of iodine dyeing. With 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 resin base material for stretching.
  • the material of the adhesive layer 6 used for bonding the polarizer 5 and the easy-adhesion film 1 is not particularly limited as long as it is optically transparent, and is an epoxy resin, a silicone resin, an acrylic resin, or a polyurethane. , Polyamide, polyether, polyvinyl alcohol and the like.
  • 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 adherend, the material of the adhesive, and the like. When a curable adhesive that exhibits adhesiveness by a cross-linking reaction after coating is used, the thickness of the adhesive layer 6 is preferably 0.01 to 5 ⁇ m, more preferably 0.03 to 3 ⁇ m.
  • the adhesive various forms such as water-based adhesive, solvent-based adhesive, hot-melt adhesive-based adhesive, and active energy ray-curable adhesive are used.
  • a water-based adhesive or an active energy ray-curable adhesive is preferable because the thickness of the adhesive layer can be reduced.
  • Examples of the polymer component of the water-based adhesive include vinyl polymer, gelatin, vinyl latex, polyurethane, polyester, epoxy and the like.
  • a vinyl polymer is preferable, and a polyvinyl alcohol-based resin is particularly preferable, because the adhesiveness between the easy-adhesive film and the polarizer is excellent.
  • the polyvinyl alcohol-based resins an acetacetyl group-containing polyvinyl alcohol is preferable.
  • the average degree of polymerization of the polyvinyl alcohol-based resin is preferably about 100 to 5000, more preferably 1000 to 4000, from the viewpoint of adhesiveness.
  • the average degree of saponification of the polyvinyl alcohol-based resin is preferably 85 mol% or more, more preferably 90 mol% or more.
  • the water-based adhesive composition (solution) may contain a cross-linking agent in addition to a polymer such as a polyvinyl alcohol-based resin.
  • a cross-linking agent a compound having at least two functional groups in one molecule having reactivity with the polymer constituting the adhesive is used.
  • the cross-linking agent for the polyvinyl alcohol-based resin include alkylenediamines; isocyanates; epoxys; aldehydes; amino-formaldehydes such as methylol urea and methylol melamine. Of these, amino-formaldehyde is preferable.
  • the amino-formaldehyde resin a compound having a methylol group is preferable, and methylol melamine is particularly preferable.
  • the blending amount of the cross-linking agent in the adhesive composition is preferably about 10 to 60 parts by weight, more preferably 20 to 50 parts by weight, based on 100 parts by weight of the polyvinyl alcohol-based resin.
  • the active energy ray-curable adhesive is an adhesive capable of radical polymerization, cationic polymerization or anionic polymerization by irradiation with active energy rays such as electron beam and ultraviolet rays.
  • active energy rays such as electron beam and ultraviolet rays.
  • a photoradical polymerizable adhesive, a photocationic polymerizable adhesive, or a hybrid type adhesive in which photocationic polymerization and photoradical polymerization are used in combination is preferable because it can be cured with low energy. ..
  • Examples of the monomer of the radically polymerizable adhesive include a compound having a (meth) acryloyl group and a compound having a vinyl group. Of these, compounds having a (meth) acryloyl group are preferable.
  • Compounds 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; hydroxyl group. Containing (meth) acrylate; Examples thereof include epoxy group-containing (meth) acrylate 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, and (meth) acryloylmorpholin. It may contain a nitrogen-containing monomer such as.
  • the radically polymerizable adhesive contains tripropylene glycol diacrylate, 1,9-nonanediol diacrylate, tricyclodecanedimethanol diacrylate, cyclic trimethylolpropane formal acrylate, dioxane glycol diacrylate, and EO-modified diacrylate as cross-linking components. It may contain a polyfunctional monomer such as glycerin tetraacrylate.
  • 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 the molecule, and various generally known curable epoxy compounds are used.
  • Preferred epoxy compounds include a compound having at least two epoxy groups and at least one aromatic ring in the molecule (aromatic epoxy compound), and at least one of them having at least two epoxy groups in the molecule. Examples thereof include a compound formed between two adjacent carbon atoms constituting an alicyclic ring (alicyclic epoxy compound).
  • a hybrid adhesive can also be obtained by including a radically polymerizable compound such as a compound having a (meth) acryloyl group in the cationically polymerizable adhesive.
  • the photocurable adhesive preferably contains a photopolymerization initiator.
  • the photopolymerization initiator may be appropriately selected depending on the reaction species. For example, it is preferable to add a photoradical generator that generates radicals by light irradiation to the radically polymerizable adhesive as a photopolymerization initiator.
  • the cationically polymerizable adhesive is preferably blended with a photocationic polymerization initiator (photoacid generator) that generates a cationic species or Lewis acid by light irradiation as a photopolymerization initiator. It is preferable to add a photocationic polymerization initiator and a photoradical generator to the hybrid adhesive.
  • the content of the polymerization initiator is usually about 0.1 to 10 parts by weight, preferably 0.5 to 3 parts by weight, based on 100 parts by weight of the monomer.
  • a photopolymerization initiator is not particularly required.
  • a photosensitizer can be added to the active energy ray-curable adhesive, if necessary, in order to increase the curing rate and sensitivity.
  • the amount of the photosensitizer used is usually about 0.001 to 10 parts by weight, preferably 0.01 to 3 parts by weight, based on 100 parts by weight of the monomer.
  • the adhesive may contain an appropriate additive if necessary.
  • additives include silane coupling agents, coupling agents such as titanium coupling agents, adhesion promoters such as ethylene oxide, ultraviolet absorbers, deterioration inhibitors, dyes, processing aids, ion trap agents, and antioxidants.
  • Adhesive-imparting agent filler, plasticizer, leveling agent, foaming inhibitor, antistatic agent, heat-resistant stabilizer, hydrolysis-resistant stabilizer and the like.
  • a polarizing plate is manufactured by bonding the easy-adhesion film 1 to one surface (first main surface) of the polarizer 5 via an adhesive layer 6.
  • the easy-adhesive film 1 the easy-adhesive layer forming surface may be bonded to the polarizer 5 via the adhesive layer, and the non-adhesive layer non-forming surface may be bonded to the polarizer 5 via the adhesive layer. May be. As shown in FIG.
  • the polarizer and the polarizer protective film are attached to each other.
  • a polarizing plate having high adhesiveness and excellent mechanical strength and durability can be obtained.
  • the polarizer 5 and the easy-adhesive film 1 are attached. It is preferable to cure the adhesive by laminating with a roll laminator or the like.
  • the method for applying the adhesive composition to the polarizer 5 and / or the easy-adhesive film 1 include a roll method, a spray method, and a dipping method.
  • surface treatment such as corona treatment, plasma treatment, or saponification treatment may be performed.
  • the adhesive layer 6 is formed by curing the adhesive according to the type of the adhesive.
  • 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 ultraviolet rays.
  • the transparent protective film 2 may be attached to the second main surface of the polarizer 5 via the adhesive layer 7.
  • any suitable transparent film can be adopted.
  • the thickness of the transparent protective film 2 is about 5 to 200 ⁇ m. From the viewpoint of mechanical strength, transparency, handleability, etc., the thickness of the transparent protective film 2 is preferably 10 to 100 ⁇ m, more preferably 15 to 60 ⁇ m.
  • the thicknesses of the easy-adhesion film 1 and the transparent protective film 2 may be the same or different.
  • Materials for forming the transparent protective film 2 include polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN); cellulose-based polymers such as diacetyl cellulose and triacetyl cellulose; polystyrene and acrylonitrile. -Styrene-based polymers such as styrene copolymers; cyclic polyolefins such as polynorbornene; polycarbonate and the like can be mentioned.
  • polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN); cellulose-based polymers such as diacetyl cellulose and triacetyl cellulose; polystyrene and acrylonitrile.
  • -Styrene-based polymers such as styrene copolymers
  • cyclic polyolefins such as
  • the transparent protective film 2 may be provided with an easy-adhesion layer (not shown) on the surface to be bonded to the polarizer 5.
  • the transparent protective film 2 may be provided with an easy-adhesion layer similar to the easy-adhesion layer 15 of the easy-adhesion film 1.
  • the adhesive layer 7 used for bonding the polarizer 5 and the transparent protective film 2 has various forms such as a water-based adhesive, a solvent-based 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.
  • the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer those using a polymer such as acrylic polymer, silicone-based polymer, polyester, polyurethane, polyamide, polyether, fluorine-based or rubber-based polymer as a base polymer are appropriately selected and used. Can be done.
  • an acrylic pressure-sensitive adhesive is preferable because it is excellent in optical transparency, exhibits appropriate wettability and cohesiveness, and is excellent in weather resistance, heat resistance, and the like.
  • the pressure-sensitive adhesive layer can be attached to the polarizing plate by an appropriate method.
  • a method of transferring the pressure-sensitive adhesive layer formed in the above onto a polarizing plate include a method of transferring the pressure-sensitive adhesive layer formed in the above onto a polarizing plate.
  • Adhesive layers may be provided on both sides of the polarizing plate.
  • the composition and thickness of the pressure-sensitive adhesive layers on the front and back sides may be the same or different.
  • the thickness of the pressure-sensitive adhesive layer is generally about 5 to 500 ⁇ m.
  • a separator may be temporarily attached to the surface of the pressure-sensitive adhesive layer for the purpose of preventing contamination of the pressure-sensitive adhesive layer.
  • a separator one in which the surface of a plastic film is coated with a release agent such as a silicone-based release agent, a long-chain alkyl-based release agent, or a fluorine-based release agent is preferably used.
  • 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 improving film.
  • An image display device can be formed by attaching a polarizing plate to the surface of an image display cell such as a liquid crystal cell or an organic EL cell.
  • the liquid crystal display device is formed by appropriately assembling a liquid crystal cell, a polarizing plate, and, if necessary, components such as a lighting system, and incorporating a drive circuit.
  • a metal electrode or the like is formed by adhering a circular polarizing plate in which the polarizing plate of the present invention and a retardation film (typically a 1/4 wave plate) are attached to the surface of an organic EL cell. It is possible to improve the visibility by reducing the re-emission of the reflected light of the external light due to.
  • the easy-adhesion composition A was prepared by mixing 3.0 parts by weight of aqueous ammonia and 63.7 parts by weight of pure water.
  • This easy-adhesive composition contains polyurethane and an oxazoline group-containing polymer (crosslinking agent) as a resin content in a weight ratio of 84.3: 15.7, and has a solid content (total of resin content and particles) of 100 parts by weight.
  • aqueous solution having a concentration of 10% containing 15.3 parts by weight of silica particles, and the ammonia concentration in the aqueous solution was 300 ppm (3000 ppm with respect to the solid content).
  • ⁇ Easy Adhesive Compositions B to G> The type (particle size) and blending amount of the silica fine particles and the blending amount of the resin content (aqueous polyurethane resin and oxazoline-containing polymer as a cross-linking agent) were changed as shown in Table 1 to create an easy-adhesion composition having a concentration of 10%. The thing was prepared. In each composition, the amount of ammonia water added was adjusted so that the ammonia concentration in the solution was 300 ppm. The details of the silica particles are as follows. PL-3: 20% aqueous dispersion of spherical silica with an average primary particle diameter of 35 nm (Fuso Chemical Industries, Ltd.
  • KE-W10 15% aqueous dispersion of spherical silica with an average primary particle diameter of 110 nm (Nippon Shokubai "Sea Horse Star KE-W10")
  • Technochemical Spherical silica particles with an average primary particle diameter of 150 nm (Technochemical "Silica Microsphere Plain 24320-15”)
  • KE-W30 20% aqueous dispersion of spherical silica with an average primary particle diameter of 280 nm (Nippon Shokubai "Sea Horster KE-W30”)
  • Table 1 shows the compositions of the easy-adhesion compositions A to G (the content of each component with respect to 100 parts by weight of the total solid content, and the concentration of ammonia in the composition (aqueous solution)).
  • Example 1 An easy-adhesion film was produced using a film manufacturing apparatus equipped with a melt extrusion film forming apparatus, a gravure coater, a tenter type simultaneous biaxial stretching apparatus, and a winding apparatus.
  • the acrylic resin pellets of the same imidized MS resin (glass transition temperature: 120 ° C.) as those used for producing the “transparent protective film 1A” described in Examples of Japanese Patent Application Laid-Open No. 2017-26939 were used.
  • Acrylic resin is melt-extruded from a T-die to form a film with a thickness of 160 ⁇ m, the above-mentioned easy-adhesive composition C is applied to one surface of the film with a gravure coater to a wet thickness of about 9 ⁇ m, and heated at a temperature of 140 ° C.
  • Example 6 The acrylic resin was melt-extruded and simultaneously biaxially stretched in the same manner as in Example 1 except that the easy-adhesion composition was not applied to obtain an acrylic film having a thickness of 40 ⁇ m.
  • the above-mentioned easy-adhesive composition D is applied to one surface of an acrylic film with a wet thickness of about 2 ⁇ m and dried at 140 ° C. for 30 seconds to form an easy-adhesive layer having a thickness of 200 nm on one surface of the acrylic film. The formed easy-adhesive film was obtained.
  • ⁇ Amount of residual alkali in the easy-adhesion layer The amount of triethylamine and ammonia remaining in the easy-adhesion layer was quantified.
  • the residual amount of triethylamine was quantified by gas chromatography-mass spectrometry (GC / MS) method of the solution by weighing the powder obtained by scraping the easy-adhesion layer from the surface of the easy-adhesion film and dissolving it in methanol.
  • the residual amount of ammonia was determined by immersing the easy-adhesion film in pure water at 25 ° C., heat-extracting it with a dryer at 120 ° C. for 60 minutes, and quantifying the ammonia eluted in water by ion chromatography. The sum of the amount of triethylamine and the amount of ammonia was taken as the residual alkali amount.
  • ⁇ Presence / absence of interface layer> The cross section of the easy-adhesive film is observed with a transmission electron microscope (TEM), and at the interface between the acrylic film and the easy-adhesive layer, the region (interface layer) in which the particles in the easy-adhesive layer are embedded in the acrylic film. The presence was confirmed.
  • TEM transmission electron microscope
  • ⁇ Particle dispersibility> The surface of the easy-adhesion film was visually observed, and the presence or absence of local turbidity (increased haze) due to aggregation of silica particles was evaluated according to the following criteria. ⁇ : No aggregation of silica particles and good in-plane uniformity ⁇ : Slightly confirmed turbidity due to aggregation of silica particles ⁇ : Clearly confirmed turbidity due to aggregation of silica particles
  • ⁇ Particle fixation> The surface of the easy-adhesive film was visually observed, and the fixability of the particles was determined based on the following criteria based on the presence or absence of scratches and dents during roll transport due to the fallen particles. ⁇ : Scratches caused by the particles And no dents ⁇ : Scratches and / or dents due to the dropped particles
  • ⁇ Haze of easy-adhesive film The haze of the easy-adhesion film was measured using a haze meter (“HM-150” manufactured by Murakami Color Technology Research Institute), and less than 1.5% was set as “ ⁇ ” and 1.5% or more was set as “x”.
  • Adhesion of easy adhesive layer An adhesive tape (“No. 31B” manufactured by Nitto Denko) was crimped onto the surface of the easy-adhesive film on which the easy-adhesive layer was formed at a linear pressure of 8 kg / m and a crimping speed of 0.3 m / min, and stored at 50 ° C. for 48 hours. The tip of the adhesive tape was gripped and a 180 ° peel test was performed at a tensile speed of 30 m / min, and the adhesion of the easy-adhesive layer was determined according to the following criteria.
  • ⁇ The easy-adhesive layer did not peel off from the acrylic film and peeled off at the interface between the adhesive tape and the easy-adhesive layer.
  • ⁇ The easy-adhesive layer peeled off at the interface between the acrylic film and the easy-adhesive layer.
  • Table 2 shows a long roll of a polyvinyl alcohol (PVA) -based resin film (“PE4500” manufactured by Kuraray) having a thickness of 45 ⁇ m, which is uniaxially stretched in the longitudinal direction by a roll stretching machine so as to be 5.9 times in the longitudinal direction.
  • PVA polyvinyl alcohol
  • the swelling bath, the dyeing bath, the cross-linking bath 1, the cross-linking bath 2, and the washing bath shown were carried in this order and dried at 70 ° C. for 5 minutes to prepare a polarizer having a thickness of 18 ⁇ m.
  • the iodine concentration and potassium iodide concentration in the dyeing bath were adjusted so that the single transmittance of the polarizer was 43.4%.
  • UV curable adhesive contains 40 parts by weight of N-hydroxyethylacrylamide and 60 parts by weight of acryloylmorpholine as curable components, and 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (BASF) as a polymerization initiator.
  • BASF 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one
  • Irgacure 819 an ultraviolet curable adhesive containing 3 parts by weight was prepared.
  • the easy-adhesive film of each example and comparative example is used as the polarizer protective film on one side, and the biaxially stretched cyclic polyolefin film (“Zeonoa film ZF-14” manufactured by Nippon Zeon) is used as the polarizer protective film on the other side.
  • the above-mentioned ultraviolet curable adhesive is applied to the surface of the easy-adhesive film on which the easy-adhesive layer is formed and the surface of the Zeonoa film to a thickness of about 1 ⁇ m, and after being bonded to a polarizer with a roll laminator, the integrated light intensity is 1000 / mJ / cm.
  • the adhesive was cured by irradiating the ultraviolet rays of No. 2 to obtain a polarizing plate having an acrylic film (easy-adhesive film) on one surface of the polarizing element and a Zeonoa film on the other surface.
  • TG-1kN manufactured by Minebea
  • the adhesive strength of 2.4N / 20mm or more is " ⁇ "
  • the adhesive strength of 1.6N / 20mm or more and less than 2.4N / 20mm is " ⁇ ”
  • the adhesive strength is 1.6N / 20mm. Those that were less than were marked with "x”.
  • polarizing plate ⁇ Humidification durability of polarizing plate>
  • the polarizing plate was cut out to a size of 320 mm ⁇ 240 mm, and the surface on the cyclic polyolefin film side was bonded onto the glass via an acrylic adhesive having a thickness of 20 ⁇ m.
  • This sample was held in a constant temperature and humidity chamber at a temperature of 60 ° C. and a relative humidity of 90% for 500 hours to carry out a heating / humidification durability test.
  • Another polarizing plate is placed on the polarizing plate after the durability test with cross Nicol, and visually observed to confirm the presence or absence of streak-like unevenness and the uniformity of the entire surface (presence or absence of surface-like unevenness). It was evaluated according to the following criteria.
  • Preparation conditions for the easy-adhesive film of Examples and Comparative Examples type of easy-adhesive composition, timing of stretching (whether stretching was performed before or after application of the easy-adhesive composition), stretching temperature, thickness of easy-adhesive layer) , Evaluation result of easy-adhesion film (residual amount of alkali, presence / absence of interface layer, dispersibility and fixability of particles, haze, blocking resistance, adhesion), and evaluation result of polarizing plate (adhesion of polarizer and easy-adhesion film) The force and the presence or absence of unevenness after the durability test) are shown in Table 3.
  • Comparative Examples 1 to 3 in which the thickness of the easy-adhesion layer was 300 nm, streak-like unevenness was confirmed after the durability test of the polarizing plate.
  • Comparative Example 6 in which the easy-adhesive composition was applied to the stretched film to form an easy-adhesive layer, the amount of residual alkali was large, and the adhesive force between the easy-adhesive film and the polarizer was insufficient.
  • Comparative Example 6 in addition to the streak-like unevenness being observed in the polarizing plate after the durability test, the unevenness was generated in the entire in-plane. It is considered that the decrease in the adhesive strength and the unevenness after the durability test in Comparative Example 6 are both caused by the residual alkaline component in the easy-adhesive layer.
  • Comparative Example 4 in which particles having a particle diameter equivalent to the thickness of the easy-adhesion layer were used, dents having the same pitch as the circumference of the transport roll were confirmed on the easy-adhesion film. It is considered that this is due to process contamination by the fallen fine particles.
  • Comparative Example 5 in which particles having a particle diameter larger than the thickness of the easy-adhesion layer were used, pitch-like dents were confirmed as in Comparative Example 4.
  • Example 9 in which the easy-adhesion layer containing 5% by weight of particles having an average particle diameter of 35 nm was provided, the blocking resistance was lower than in other examples.
  • Examples 2, 3, 11 and 13 containing 5% by weight of particles having an average particle size of 150 nm and Examples 5 and 6 containing 5% by weight of particles having an average particle size of 110 nm showed excellent blocking resistance. ..
  • Examples 7 and 8 containing 15% by weight of particles having an average particle diameter of 35 nm also showed excellent blocking resistance. From these results, it can be seen that increasing the particle size of the particles in the easy-adhesion layer and increasing the content of the particles are useful for improving the blocking resistance.
  • Example 8 containing 15% of particles having an average particle diameter of 35 nm, a decrease in particle dispersibility was observed. It is considered that this is because particles having a small particle diameter have low dispersibility and are likely to aggregate as the content increases.
  • Example 7 in which the amount of residual alkali was increased by lowering the stretching temperature as compared with Example 8, the dispersibility of the particles was good.
  • the amount of residual alkali is large, there is a concern that it may cause deterioration of adhesiveness and appearance deterioration such as unevenness after the durability test. Further, it is necessary to keep the residual alkali amount at a predetermined value or more in order to secure the dispersibility of the particles, which may narrow the process window.

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