WO2016088633A1 - Highly-adhesive composition, optical film using same, and production method therefor - Google Patents

Highly-adhesive composition, optical film using same, and production method therefor Download PDF

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Publication number
WO2016088633A1
WO2016088633A1 PCT/JP2015/083161 JP2015083161W WO2016088633A1 WO 2016088633 A1 WO2016088633 A1 WO 2016088633A1 JP 2015083161 W JP2015083161 W JP 2015083161W WO 2016088633 A1 WO2016088633 A1 WO 2016088633A1
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Prior art keywords
water
film
urethane resin
easy
dispersible urethane
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PCT/JP2015/083161
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French (fr)
Japanese (ja)
Inventor
正浩 吉澤
匡弘 松本
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大倉工業株式会社
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Application filed by 大倉工業株式会社 filed Critical 大倉工業株式会社
Priority to JP2016562399A priority Critical patent/JP6664333B2/en
Priority to KR1020177012074A priority patent/KR102382903B1/en
Priority to CN201580065341.XA priority patent/CN107001853B/en
Publication of WO2016088633A1 publication Critical patent/WO2016088633A1/en

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    • 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
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—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
    • 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
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • 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
    • 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
    • C09J7/245—Vinyl resins, e.g. polyvinyl chloride [PVC]
    • 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

Definitions

  • the present invention relates to an easy-adhesion composition and an optical film having an easy-adhesion layer composed of the easy-adhesion composition. Furthermore, this invention relates to the manufacturing method of this optical film, a polarizing plate provided with this optical film, and an image display apparatus.
  • Acrylic resin films formed from (meth) acrylic polymers typified by polymethyl methacrylate are known to have excellent optical properties such as light transmittance, as well as excellent balance between mechanical strength and moldability. ing. For this reason, the acrylic resin film is applied to an optical film incorporated in an image display device such as a liquid crystal display device (LCD), a plasma display panel (PDP), or an organic EL display device (OLED).
  • LCD liquid crystal display device
  • PDP plasma display panel
  • OLED organic EL display device
  • the optical film is usually used in a state where it is laminated with another functional film.
  • an optical film is used as a polarizer protective film, it is laminated on at least one surface of the polarizer via a hydrophilic adhesive layer.
  • the obtained polarizing plate is used for an image display device or the like. In this case, it is important that the adhesion between the optical film and the polarizer is good.
  • the acrylic resin film is inferior in adhesiveness with a hydrophilic adhesive and has a problem that adhesiveness with a polarizer is not sufficient.
  • a method has been proposed in which an easy-adhesion layer mainly composed of an auxiliary-adhesive resin such as polyester, acrylic, or urethane is provided on the surface of the acrylic resin film to impart easy adhesion to the acrylic resin film.
  • portable devices using an image display device such as an LCD are recently used in various environments, indoors or outdoors, and may require moisture and heat resistance that can withstand high-temperature and high-humidity environments.
  • a polarizing plate used for such an application is required to have high adhesion that does not cause delamination even under high temperature and high humidity.
  • JP 2009-274390 A discloses an aqueous structure containing an acid structure on the surface of an acrylic resin film as a laminated film having good thermal adhesion when exposed to high temperatures and having good adhesion to a polarizer. It describes that an easy-adhesion layer containing an aqueous urethane resin formed by neutralizing a part of an acid structure contained in a urethane resin with a nonvolatile base is described.
  • Japanese Patent Application Laid-Open No. 2009-205135 emulsifies a monomer composition containing polyalkylene glycol (meth) acrylate on the surface of an acrylic resin film as a polarizer protective film having excellent adhesion to a polarizer under high temperature and high humidity. It describes that an easy-adhesion layer is formed with an aqueous (meth) acrylic resin dispersion obtained by polymerization.
  • the optical film having an easy-adhesion layer disclosed in the above document initially exhibits good adhesion, a decrease in adhesion with a polarizer is inevitable when used for a long time under high temperature and high humidity. There is a problem that the initial performance (initial adhesion) is not maintained for a long time. Furthermore, the optical film having an easy-adhesion layer disclosed in the above-mentioned document can be used for a long time under high temperature (for example, 80 ° C.) or high temperature and high humidity (for example, 40 to 60 ° C., 60 to 95% RH). Although the heat-and-moisture resistance is satisfactory, the heat-and-moisture resistance in a harsher environment (for example, 80 ° C. and 90% RH) is not satisfactory.
  • the present invention has been made in view of such problems, and is an easy-adhesive composition that can suppress deterioration in initial performance in long-term use under high temperature and high humidity, and can also satisfy moisture and heat resistance in a harsh environment.
  • An object is to provide an optical film using the same.
  • An easy-adhesive composition comprising resin (B) is provided, (2) The easy-adhesion composition according to (1), wherein the weight ratio of the water-dispersible urethane resin (A) to the water-dispersible urethane resin (B) is in the range of 95: 5 to 40:60.
  • the easy-adhesion composition of the present invention having the above-described configuration suppresses deterioration of initial performance under high temperature and high humidity, and is excellent in heat and humidity resistance under a harsher environment.
  • the term “(meth) acryl” is used as a general term for methacryl, acryl, or both. The same applies to the term “(meth) acrylonitrile”.
  • the easy-adhesion composition of the present invention comprises a water-dispersible urethane resin (A) having a glass transition point (hereinafter referred to as Tg) of less than 60 ° C., a weight increase rate in a hot water resistance test with a Tg of 60 ° C. to 120 ° C. Containing 20% or less of a water-dispersible urethane resin (B).
  • Tg glass transition point
  • B a water-dispersible urethane resin
  • Tg of the water dispersible urethane resin (A) is less than 60 ° C.
  • Tg is preferably ⁇ 25 ° C. or higher and lower than 60 ° C., more preferably ⁇ 15 ° C. or higher and lower than 50 ° C., and further preferably ⁇ 15 ° C. or higher and lower than 45 ° C. If Tg of water-dispersible urethane resin (A) is the said range, it will be excellent in initial stage adhesiveness with a thermoplastic resin film.
  • Tg means a temperature at which the loss elastic modulus (E ′′) has a maximum in dynamic viscoelasticity measurement. More specifically, a dynamic viscoelasticity measuring device (Rheogel- manufactured by UBM Co., Ltd.) E4000) was used to measure the temperature dependence of the loss modulus E ′′ under the conditions of a frequency of 10 Hz and a heating rate of 3 ° C./min. The temperature at which the obtained E ′′ curve becomes a maximum was determined as the glass transition temperature ( ° C).
  • the water dispersible urethane resin (A) preferably has a breaking elongation of 300% or less.
  • the breaking elongation is more preferably 100% or less, and further preferably 50% or less.
  • the adhesiveness with the thermoplastic resin film is excellent.
  • the breaking elongation is measured by the following method.
  • an aqueous dispersion of a water-dispersible urethane resin is prepared so as to have a solid content of 35% by weight, separated into containers such as a petri dish so that the thickness of the urethane resin after drying is about 500 ⁇ m, and dried at room temperature for 15 hours. Then, it is dried at 80 ° C. for 6 hours and further at 120 ° C. for 20 minutes to produce a urethane resin film.
  • the urethane resin film is cut into a size of 15 mm ⁇ 200 mm to cut out a sample, and then a sample in which marks are written at intervals of 50 mm in the center is created.
  • the sample is attached to a tensile tester, the distance between the grips of the tester is set to 100 mm, the sample is measured until it breaks at a speed of 200 mm / min, and is calculated by the following calculation method.
  • the measurement temperature is 23 ° C.
  • Elongation at break (%) ((Distance between gauge points at break-Distance between gauge points before test) / (Distance between gauge points before test)) x 100
  • the water-dispersible urethane resin (B) has a Tg of 60 ° C. or more and 120 ° C. or less and a weight increase rate of 20% or less in the hot water resistance test.
  • the Tg of the water dispersible urethane resin (B) is preferably 65 ° C. or higher and 115 ° C. or lower, more preferably 70 ° C. or higher and 110 ° C. or lower, and further preferably 75 ° C. or higher and 105 ° C. or lower.
  • the weight increase rate in a warm water-resistant test is 15% or less, More preferably, it is 10% or less.
  • the breaking elongation of the water dispersible urethane resin (B) is preferably 100% or less.
  • the breaking elongation is more preferably 50% or less, and further preferably 20% or less.
  • the adhesiveness with the thermoplastic resin film is excellent.
  • the method for measuring the elongation at break is as described above.
  • the weight ratio (A / B) to (B) is preferably 95: 5 to 40:60.
  • the weight ratio (A / B) is more preferably 85:15 to 50:50, still more preferably 80:20 to 60:40, because more excellent adhesion can be obtained.
  • the water-dispersible urethane resins (A) and (B) are not particularly limited as long as they are water-dispersible urethane resins having the above-described characteristics.
  • the organic solvent is inert to isocyanate and compatible with water.
  • a linear urethane prepolymer obtained by reacting a polyisocyanate with a polyol to form an isocyanate group-terminated prepolymer and then reacting with a chain extender having a free carboxyl group in water
  • a chain extender having a free carboxyl group in water
  • water-based as used herein means that the resin is stably dispersed or emulsified in water. Moreover, it is preferable that water-dispersible urethane resin (A) and (B) has a carboxyl group in a molecule
  • polyisocyanates 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.
  • Aliphatic diisocyanates such as 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate; isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4'-cyclohexylmethane diisocyanate, 1,4- Cycloaliphatic diisocyanate, methylcyclohexylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane Socyanate; tolylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, 1 , 5-naphthylene diisocyanate, xylylene
  • the polyol is not particularly limited as long as it has two or more hydroxyl groups in the molecule, and any appropriate polyol can be adopted.
  • polyalkylene glycol, polyacryl polyol, polyester polyol, polyether polyol, polyether ester polyol, polycarbonate polyol and the like can be mentioned. These can be used alone or in combination of two or more.
  • Examples of the chain extender having a free carboxyl group include dihydroxycarboxylic acid and dihydroxysuccinic acid.
  • Examples of the dihydroxycarboxylic acid include dialkyrol alkanoic acids such as dimethylol alkanoic acid (for example, dimethylol acetic acid, dimethylol butanoic acid, dimethylol propionic acid, dimethylol butyric acid, dimethylol pentanoic acid). These can be used alone or in combination of two or more.
  • neutralizing agent examples include ammonia, N-methylmorpholine, triethylamine, dimethylethanolamine, methyldiethanolamine, triethanolamine, morpholine, tripropylamine, ethanolamine, triisopropanolamine, 2-amino-2-methyl-1 -Propanol and the like. These can be used alone or in combination of two or more.
  • chain extenders include low molecular weight diol compounds such as ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, furan methanol, diethylene glycol, triethylene glycol, tetraethylene glycol, and the like.
  • Polyether diol compounds obtained by addition polymerization of ethylene oxide, propylene oxide, tetrahydrofuran, etc .; obtained from the above low molecular weight diol compounds and dicarboxylic acids such as (anhydrous) succinic acid, adipic acid, (anhydrous) phthalic acid, and their anhydrides Polyester diols having a hydroxyl group at the terminal; polyhydric alcohols such as trimethylolethane and trimethylolpropane; amino alcohols such as monoethanolamine, diethanolamine and triethanolamine Lumpur ethylenediamine, propylene diamine, butylene diamine, hexamethylene diamine, phenylene diamine, toluene diamine, xylene diamine, diamine compounds such as isophoronediamine; water, ammonia, hydrazine, may be mentioned dibasic acid hydrazide and the like. These can be used alone or in combination of two or more.
  • the number average molecular weight of the water-dispersible urethane resins (A) and (B) is preferably 5000 to 600000, more preferably 10,000 to 400000.
  • the acid value of the water-dispersible urethane resin is preferably 10 or more, more preferably 10 to 50, and particularly preferably 20 to 45.
  • the easy-adhesion composition may be diluted with an aqueous solvent from the viewpoint of workability when forming the easy-adhesion layer.
  • aqueous solvent include water or water and hydrophilic organic solvents (for example, alcohol solvents such as methanol, ethanol, isopropyl alcohol, ethylene glycol, and propylene glycol; ester solvents such as ethyl acetate, butyl acetate, and ⁇ -butyrolactone; A mixed solvent with a ketone solvent such as acetone; an ether solvent such as tetrahydrofuran or dioxane; an aprotic polar solvent such as N-methylpyrrolidone) can be used, but water is particularly preferable.
  • alcohol solvents such as methanol, ethanol, isopropyl alcohol, ethylene glycol, and propylene glycol
  • ester solvents such as ethyl acetate, butyl acetate, and ⁇ -butyrolactone
  • the content of the water-dispersible urethane resins (A) and (B) in the easy-adhesive composition is not particularly limited, and may be appropriately set in consideration of application workability and the like, for example, 1 to 25% by weight is preferable. More preferably, it is 3 to 20% by weight, still more preferably 5 to 15% by weight. If the water-dispersible urethane resins (A) and (B) in the easy-adhesive composition are in the above ranges, it is preferable because workability at the time of forming the easy-adhesive layer is excellent.
  • the solid content of the easy-adhesive composition may be appropriately set in consideration of application workability and the like, but is preferably 1 to 30% by weight, more preferably 2 to 25% by weight, and further preferably 3 to 20% by weight. %.
  • the easy-adhesion composition can contain any appropriate fine particles, preferably water-dispersible fine particles, in accordance with a desired function.
  • the fine particles either inorganic fine particles or organic fine particles can be used.
  • the inorganic fine particles include inorganic oxides such as silica, titania, alumina, zirconia, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate, calcium phosphate, and the like.
  • the organic fine particles include silicone resins, fluorine resins, (meth) acrylic resins, (meth) acrylonitrile resins, and the like.
  • silica or (meth) acrylonitrile resin is preferable. Fine particles made of silica or (meth) acrylonitrile-based resin are excellent in blocking suppression ability, excellent in transparency, do not cause haze, and are not colored, so that the easy-contact layer has less influence on optical properties. In addition, the strength and adhesion of the easy-adhesion layer are reduced by adding fine particles, but the easy-adhesion layer containing fine particles made of (meth) acrylonitrile resin is the strength and adhesion of the easy-adhesion layer. It is particularly preferable because it is possible to suppress the decrease in the thickness.
  • the average particle diameter of the fine particles is not particularly limited, but is preferably 1 to 500 nm, more preferably 50 to 350 nm, and still more preferably 100 to 300 nm from the viewpoint of maintaining the transparency of the easy-adhesion layer.
  • the above average particle diameter means a median diameter (d50) measured by laser diffraction / scattering particle size distribution measurement.
  • the content of the fine particles is preferably 0.1 to 15 parts by weight with respect to a total of 100 parts by weight of the water-dispersible urethane resins (A) and (B) in terms of solid content. More preferred is 0.3 to 5 parts by weight, still more preferred is 0.5 to 3 parts by weight. In addition, what is necessary is just to mix
  • the easy-adhesion composition may be blended with a crosslinking agent in order to improve heat and humidity resistance under high temperature and high humidity.
  • a crosslinking agent can be adopted as the crosslinking agent, and examples thereof include urea, epoxy, melamine, isocyanate, oxazoline, silanol, and carbodiimide.
  • the easy-adhesion composition can further contain any appropriate additive.
  • the additive include a dispersion stabilizer, a thixotropic agent, an antioxidant, an ultraviolet absorber, an antifoaming agent, a thickener, a dispersant, a surfactant, a catalyst, a lubricant, and an antistatic agent.
  • FIG. 1 shows an example of the optical film of the present invention.
  • An optical film 1 shown in FIG. 1 has an easy adhesion layer 3 formed from the above-mentioned easy adhesion composition on one surface of a thermoplastic resin film 2.
  • an easy adhesion layer may be formed on both surfaces of the thermoplastic resin film.
  • thermoplastic resin constituting the thermoplastic resin film examples include cellulose resins such as triacetyl cellulose, polyester resins, polyether sulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, Examples include cyclic polyolefin resins, (meth) acrylic resins, polyarylate resins, polystyrene resins, and polyvinyl alcohol resins. These can be used alone or in combination of two or more. Among these, the (meth) acrylic resin (hereinafter sometimes abbreviated as ACR) is inferior in adhesiveness with a hydrophilic adhesive, and therefore the effect of the present invention is particularly remarkable when ACR is used.
  • ACR the (meth) acrylic resin
  • the TCR of ACR is preferably 115 ° C. or higher, more preferably 120 ° C. or higher, and further preferably 125 ° C. or higher.
  • the thermoplastic resin film can be made excellent in durability by containing ACR having a Tg of 115 ° C. or higher as a main component.
  • the upper limit of Tg is not particularly limited, but is preferably 170 ° C. or lower from the viewpoint of moldability and the like.
  • ACR 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 an alicyclic hydrocarbon group for example, methyl methacrylate-methacrylic acid
  • Acid cyclohexyl copolymer resistance methyl methacrylate- (meth) acrylate norbornyl copolymer, etc.
  • poly (meth) acrylate C1-6 alkyl such as poly (meth) acrylate is preferable, and methacrylic acid having methyl methacrylate as a main component (50 to 100% by weight, preferably 70 to 100% by weight) is preferable.
  • An acid methyl resin is more preferable.
  • ACR include, for example, “Acrypet (registered trademark) VH”, “Acrypet (registered trademark) VRL20A” manufactured by Mitsubishi Rayon Co., Ltd., high Tg (meta) obtained by intramolecular crosslinking and intramolecular cyclization reaction.
  • An acrylic resin is mentioned.
  • the ACR preferably has a ring structure in the main chain in that it has high heat resistance, high transparency, and high mechanical strength.
  • the ACR having a ring structure in the main chain include a resin having a glutaric anhydride structure or a glutarimide structure (WO2007 / 26659, WO2005 / 108438), a maleic anhydride structure or an N-substituted maleimide structure. Resins (Japanese Patent Laid-Open Nos. 57-153008 and 2007-31537) and resins having a lactone ring structure (Japanese Patent Laid-Open Nos. 2006-96960, 2006-171464, and 2007-63541) JP, 2008-191426, A).
  • the thermoplastic resin film may contain an additive.
  • additives include hindered phenol-based, phosphorus-based and sulfur-based antioxidants; light-resistant stabilizers, weather-resistant stabilizers, heat stabilizers and other stabilizers; reinforcing materials such as glass fibers and carbon fibers; ultraviolet rays Absorbers; Near infrared absorbers; Flame retardants; Antistatic agents such as anionic, cationic and nonionic surfactants; Colorants such as inorganic pigments, organic pigments and dyes; Organic fillers and inorganic fillers; Resin modification Agents; organic fillers and inorganic fillers; plasticizers; lubricants; antistatic agents; flame retardants;
  • thermoplastic resin film is not particularly limited.
  • the thermoplastic resin and other polymers and additives are sufficiently mixed by any appropriate mixing method and heated in advance. From the plastic resin composition, it can be formed into a film.
  • the thermoplastic resin and other polymers, additives, and the like may be made into separate solutions and mixed to form a uniform mixed solution, and then formed into a film.
  • the film raw material is pre-blended with any appropriate mixer such as an omni mixer, and then the obtained mixture is extruded and kneaded.
  • the kneader used for extrusion kneading is not particularly limited.
  • any suitable mixer such as an extruder such as a single screw extruder or a twin screw extruder or a pressure kneader may be used. Can do.
  • the film forming method examples include any appropriate film forming method such as a solution casting method (solution casting method), a melt extrusion method, a calendar method, and a compression molding method. Of these film forming methods, the melt extrusion method is preferred.
  • melt extrusion method examples include a T-die method and an inflation method.
  • the molding temperature is preferably 150 to 350 ° C, more preferably 200 to 300 ° C.
  • a T-die When forming a film by the T-die method, a T-die is attached to the tip of a known single-screw extruder or twin-screw extruder, a film is formed by the T die, and then the film is wound to form a roll. A film can be obtained.
  • the thermoplastic resin film may be an unstretched film or a stretched film.
  • a stretched film either a uniaxially stretched film or a biaxially stretched film may be used.
  • a biaxially stretched film either a simultaneous biaxially stretched film or a sequential biaxially stretched film may be used.
  • biaxial stretching the mechanical strength is improved and the film performance is improved.
  • the stretching temperature is preferably in the vicinity of the glass transition temperature of the thermoplastic resin composition that is a film raw material, specifically, preferably (Tg-30 ° C) to (Tg + 100 ° C), more preferably (Tg-20). ° C) to (Tg + 80 ° C). If the stretching temperature is less than (Tg-30 ° C.), a sufficient stretching ratio may not be obtained. On the other hand, when the stretching temperature exceeds (Tg + 100 ° C.), the resin composition may flow and stable stretching may not be performed.
  • the draw ratio defined by the area ratio is preferably 1.1 to 25 times, more preferably 1.3 to 10 times. There exists a possibility that it may not lead to the improvement of the toughness accompanying extending
  • the stretching speed is unidirectional, preferably 10 to 20,000% / min, more preferably 100 to 10,000% / min. When the stretching speed is less than 10% / min, it takes time to obtain a sufficient stretching ratio, and the production cost may increase. If the stretching speed exceeds 20,000% / min, the stretched film may be broken.
  • thermoplastic resin film can be subjected to a heat treatment (annealing) or the like after the stretching treatment in order to stabilize its optical isotropy and mechanical properties.
  • Arbitrary appropriate conditions can be employ
  • the thickness of the thermoplastic resin film is preferably 5 to 200 ⁇ m, more preferably 10 to 100 ⁇ m. If the thickness is less than 5 ⁇ m, sufficient strength as an optical film may not be obtained. When the thickness exceeds 200 ⁇ m, the transparency is lowered and there is a possibility that it is not suitable for use as an optical film.
  • the thickness of the easy-adhesion layer can be set to any appropriate value.
  • the thickness is preferably 0.1 to 10 ⁇ m, more preferably 0.1 to 5 ⁇ m, and particularly preferably 0.2 to 1 ⁇ m. By setting to such a range, it is excellent in adhesiveness with another functional film, and it can suppress that a phase difference expresses in an easily bonding layer.
  • the functional layer is, for example, an antistatic layer, an adhesive layer, an adhesive layer, an easy adhesion layer, an antiglare layer (non-glare) layer, an antifouling layer such as a photocatalyst layer, an antireflection layer, a hard coat layer, an ultraviolet shielding layer, A heat ray shielding layer, an electromagnetic wave shielding layer, a gas barrier layer, etc. are mentioned.
  • the optical film can be used as, for example, a polarizer protective film, a retardation film, a viewing angle compensation film, a light diffusion film, a reflection film, an antireflection film, an antiglare film, a brightness enhancement film, and a conductive film for a touch panel.
  • a polarizer protective film is particularly preferable.
  • a polarizing plate 10 shown in FIG. 2 has an adhesive 5 on the surface of the optical film 1 having the easy adhesion layer 3 formed from the above-mentioned easy adhesion composition on one surface of the thermoplastic resin film 2.
  • the polarizer 6 has a stacked structure.
  • the polarizing plate 10 may have a protective film laminated via an adhesive layer on the opposite side of the polarizer 6 from the optical film 1.
  • any appropriate polarizer can be adopted depending on the purpose.
  • dichroic substances such as iodine and dichroic dyes are adsorbed on hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and ethylene-vinyl acetate copolymer partially saponified films.
  • polyene-based oriented films such as a uniaxially stretched product, a polyvinyl alcohol dehydrated product and a polyvinyl chloride dehydrochlorinated product.
  • a polarizer obtained by adsorbing a dichroic substance such as iodine on a polyvinyl alcohol film and uniaxially stretching is particularly preferable because of its high polarization dichroic ratio.
  • the thickness of these polarizers is not particularly limited, but is generally about 1 to 80 ⁇ m.
  • the adhesive layer is formed from an adhesive composition containing a polyvinyl alcohol-based resin.
  • Arbitrary appropriate protective films can be employ
  • the image display apparatus of the present invention includes the polarizing plate described above.
  • Specific examples of the image display device include a self-luminous display device such as an electroluminescence (EL) display, a plasma display (PD), a field emission display (FED), and a liquid crystal display (LCD). .
  • EL electroluminescence
  • PD plasma display
  • FED field emission display
  • LCD liquid crystal display
  • An easy-adhesive composition containing a water-dispersible urethane resin (B) having a weight increase rate of 20% or less in a warm water resistance test is applied to at least one surface of a thermoplastic resin film.
  • a film is formed (application process), and then the coating film is dried to form an easy-adhesion layer (drying process).
  • any appropriate method can be adopted as a method of applying the easy-adhesion composition in the application step.
  • Examples thereof 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 thickness of the coating film formed in the coating process can be appropriately adjusted according to the thickness required when the coating film becomes an easy-adhesion layer.
  • the surface of the thermoplastic resin film to which the easy-adhesion composition is applied is preferably subjected to a surface treatment.
  • the surface treatment is preferably corona discharge treatment or plasma treatment.
  • the drying process is not particularly limited, and a conventionally known method can be used.
  • the drying temperature is typically 50 ° C. or higher, preferably 90 ° C. or higher, more preferably 110 ° C. or higher. By setting the drying temperature in such a range, an optical film excellent in color resistance (particularly under high temperature and high humidity) can be obtained.
  • the upper limit of the drying temperature is preferably 200 ° C. or lower, more preferably 180 ° C. or lower.
  • the stretching may be performed before the formation of the easy-adhesion layer or after the formation of the easy-adhesion layer. Moreover, you may perform formation of an easily bonding layer and extending
  • the thermoplastic resin film on which the coating film of the easy-adhesive composition is formed may be stretched in a heated atmosphere. Due to the heat applied to the film for stretching, the coating film of the easy-adhesive composition formed on the surface of the thermoplastic resin film is dried to form an easy-adhesive layer. If it does in this way, the extending
  • Table 1 shows the glass transition temperature, elongation at break, and weight increase rate of the hot water resistance test for the characteristic values of the water-dispersible urethane resins (A) and (B).
  • Examples 1 to 4 and Comparative Examples 1 to 8 Manufacture of an easily bonding composition
  • the said raw material emulsion was selected and mixed so that each component shown in Table 2 might contain the solid content amount (unit is a weight part) shown in Table 2, and the easily bonding composition was manufactured.
  • ion exchange water was used as an aqueous solvent, and the solid content of the easy-adhesion composition was adjusted to 8% by weight.
  • the polyvinyl alcohol-type adhesive composition was apply
  • peel adhesion strength was evaluated according to the following criteria. ⁇ : Peeling adhesive strength is superior to the reference polarizing plate ⁇ : Peeling adhesive strength is equivalent to the reference polarizing plate ⁇ : Peeling adhesive strength is inferior to the reference polarizing plate ⁇ : Not measured and cannot be measured (2) Moist heat resistance (60 ° C, 90% RH) The measurement sample obtained in the same manner as described above was put in a constant temperature and humidity chamber at a temperature of 60 ° C. and a humidity of 90% RH, and was subjected to a heat treatment that was allowed to stand for 250 hours and 500 hours. The peel adhesion strength was measured. From the measurement results, the peel adhesion strength was evaluated according to the following criteria.
  • Comparative Examples 7 and 8 containing only the water-dispersible urethane resin (B) having a Tg of 60 ° C. or more and 120 ° C. or less and a weight increase rate of 20% or less in the hot water resistance test are high temperature and high humidity treatments. Although the later adhesion was improved, the results showed inferior initial adhesion.

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Abstract

The purpose of the present invention is to provide: a highly-adhesive composition that suppresses reduction in initial performance when used for long period in a high-temperature, high-humidity environment and that can also obtain satisfactory moist-heat resistance in an even harsher environment; and an optical film using same. [Solution] A highly-adhesive composition including: a water-dispersible urethane resin (A) having a glass transition temperature of less than 60°C; and a water-dispersible urethane resin (B) having a glass transition temperature of 60-120°C and a weight gain of no more than 20% in a warm water resistance test. An optical film having a highly-adhesive layer comprising this highly-adhesive composition, provided on at least one surface of a thermoplastic resin film.

Description

易接着組成物、及びこれを用いた光学フィルムとその製造方法Easy-adhesive composition, optical film using the same, and method for producing the same
　本発明は、易接着組成物、及び易接着組成物から構成された易接着層を有する光学フィルムに関する。さらに、本発明は、該光学フィルムの製造方法および該光学フィルムを備えた偏光板及び画像表示装置に関する。 The present invention relates to an easy-adhesion composition and an optical film having an easy-adhesion layer composed of the easy-adhesion composition. Furthermore, this invention relates to the manufacturing method of this optical film, a polarizing plate provided with this optical film, and an image display apparatus.
　ポリメタクリル酸メチルに代表される（メタ）アクリル重合体から形成されるアクリル系樹脂フィルムは、光線透過率などの光学特性に優れるとともに、機械的強度および成形加工性のバランスに優れることが知られている。このため、アクリル系樹脂フィルムは、液晶表示装置（ＬＣＤ）、プラズマディスプレイパネル（ＰＤＰ）、有機ＥＬ表示装置（ＯＬＥＤ）のような画像表示装置に組み込まれる光学フィルムに応用されている。 Acrylic resin films formed from (meth) acrylic polymers typified by polymethyl methacrylate are known to have excellent optical properties such as light transmittance, as well as excellent balance between mechanical strength and moldability. ing. For this reason, the acrylic resin film is applied to an optical film incorporated in an image display device such as a liquid crystal display device (LCD), a plasma display panel (PDP), or an organic EL display device (OLED).
　光学フィルムは、通常、他の機能性フィルムと積層された状態で使用される。例えば、光学フィルムは、偏光子保護フィルムとして使用される場合、偏光子の少なくとも一方の面に親水性接着剤層を介して積層される。得られた偏光板は画像表示装置等に使用される。この場合、光学フィルムと偏光子との密着性が良好であることが重要である。 The optical film is usually used in a state where it is laminated with another functional film. For example, when an optical film is used as a polarizer protective film, it is laminated on at least one surface of the polarizer via a hydrophilic adhesive layer. The obtained polarizing plate is used for an image display device or the like. In this case, it is important that the adhesion between the optical film and the polarizer is good.
　しかしながら、アクリル系樹脂フィルムは、親水性接着剤との接着性に劣り、偏光子との密着性が十分でないという問題がある。そこで、アクリル系樹脂フィルムの表面にポリエステル、アクリル、ウレタン等の助接着性の樹脂を主成分とする易接着層を設け、アクリル系樹脂フィルムに易接着性を付与する方法が提案されている。 However, the acrylic resin film is inferior in adhesiveness with a hydrophilic adhesive and has a problem that adhesiveness with a polarizer is not sufficient. In view of this, a method has been proposed in which an easy-adhesion layer mainly composed of an auxiliary-adhesive resin such as polyester, acrylic, or urethane is provided on the surface of the acrylic resin film to impart easy adhesion to the acrylic resin film.
　一方、ＬＣＤ等の画像表示装置を用いた携帯用機器などは、近年、屋内、屋外を問わず種々の環境で用いられ、高温高湿環境にも耐えうる耐湿熱性が要求される場合がある。このような用途に使用される偏光板は高温高湿下においても層間剥離が起きない高い密着性が求められる。 On the other hand, portable devices using an image display device such as an LCD are recently used in various environments, indoors or outdoors, and may require moisture and heat resistance that can withstand high-temperature and high-humidity environments. A polarizing plate used for such an application is required to have high adhesion that does not cause delamination even under high temperature and high humidity.
　そこで、特開２００９－２７４３９０号公報には、高温下に曝された熱履歴を有しても偏光子との密着性が良好である積層フィルムとして、アクリル系樹脂フィルムの表面に酸構造含有水系ウレタン樹脂に含まれる酸構造の一部を不揮発性塩基により中和してなる水系ウレタン樹脂を含む易接着層を形成することが記載されている。特開２００９－２０５１３５号公報には、高温高湿下における偏光子との密着性に優れる偏光子保護フィルムとして、アクリル系樹脂フィルムの表面にポリアルキレングリコール（メタ）アクリレートを含むモノマー組成物を乳化重合させてなる水性（メタ）アクリル系樹脂分散体で易接着層を形成することが記載されている。 Therefore, JP 2009-274390 A discloses an aqueous structure containing an acid structure on the surface of an acrylic resin film as a laminated film having good thermal adhesion when exposed to high temperatures and having good adhesion to a polarizer. It describes that an easy-adhesion layer containing an aqueous urethane resin formed by neutralizing a part of an acid structure contained in a urethane resin with a nonvolatile base is described. Japanese Patent Application Laid-Open No. 2009-205135 emulsifies a monomer composition containing polyalkylene glycol (meth) acrylate on the surface of an acrylic resin film as a polarizer protective film having excellent adhesion to a polarizer under high temperature and high humidity. It describes that an easy-adhesion layer is formed with an aqueous (meth) acrylic resin dispersion obtained by polymerization.
　しかしながら、上記文献に開示される易接着層を有する光学フィルムは、当初は良好な密着性を示すものの、高温高湿下での長時間使用においては偏光子との密着性の低下は避けられず、初期性能（初期密着性）が長時間維持されないという問題がある。さらに、上記文献に開示される易接着層を有する光学フィルムは、高温下（例えば、８０℃）或いは高温高湿下（例えば、４０～６０℃、６０～９５％ＲＨ）での長時間使用における耐湿熱性は満足するものの、より過酷な環境下（例えば、８０℃、９０％ＲＨ）における耐湿熱性は満足し得るものではなかった。 However, although the optical film having an easy-adhesion layer disclosed in the above document initially exhibits good adhesion, a decrease in adhesion with a polarizer is inevitable when used for a long time under high temperature and high humidity. There is a problem that the initial performance (initial adhesion) is not maintained for a long time. Furthermore, the optical film having an easy-adhesion layer disclosed in the above-mentioned document can be used for a long time under high temperature (for example, 80 ° C.) or high temperature and high humidity (for example, 40 to 60 ° C., 60 to 95% RH). Although the heat-and-moisture resistance is satisfactory, the heat-and-moisture resistance in a harsher environment (for example, 80 ° C. and 90% RH) is not satisfactory.
　本発明はこのような問題に鑑みなされたもので、高温高湿下での長時間使用における初期性能の低下を抑制するとともに、より過酷な環境下における耐湿熱性をも満足し得る易接着組成物、及びこれを用いた光学フィルムを提供することを課題とする。 The present invention has been made in view of such problems, and is an easy-adhesive composition that can suppress deterioration in initial performance in long-term use under high temperature and high humidity, and can also satisfy moisture and heat resistance in a harsh environment. An object is to provide an optical film using the same.
　本発明によれば、
（１）ガラス転移温度が６０℃未満の水分散性ウレタン樹脂（Ａ）と、ガラス転移温度が６０℃以上１２０℃以下かつ耐温水性試験における重量増加率が２０％以下である水分散性ウレタン樹脂（Ｂ）とを含む易接着組成物が提供され、
（２）　前記水分散性ウレタン樹脂（Ａ）と前記水分散性ウレタン樹脂（Ｂ）との重量比が９５：５～４０：６０の範囲である（１）記載の易接着組成物が提供され、
（３）前記水分散性ウレタン樹脂（Ａ）のガラス転移温度が、－２５℃以上である（１）又は（２）記載の易接着組成物が提供され、
（４）前記水分散性ウレタン樹脂（Ａ）の破断伸度が、３００％以下である（１）乃至（３）のいずれか記載の易接着組成物が提供され、
（５）前記水分散性ウレタン樹脂（Ｂ）の破断伸度が、１００％以下である（１）乃至（４）のいずれか記載の易接着組成物が提供され、
（６）さらに微粒子を水分散性ウレタン樹脂（Ａ）及び（Ｂ）の合計１００重量部に対して、０．１～１５重量部含む（１）乃至（５）のいずれか記載の易接着組成物が提供され、
（７）熱可塑性樹脂フィルムと、該熱可塑性樹脂フィルムの少なくとも一方の表面に設けられた易接着層とを備えた光学フィルムであって、該易接着層が（１）乃至（６）のいずれか記載の易接着組成物から形成されていることを特徴とする光学フィルムが提供され、
（８）前記樹脂フィルムは、（メタ）アクリル系樹脂からなる（７）記載の光学フィルムが提供され、
（９）（７）又は（８）記載の光学フィルムと、接着剤層と、偏光子とが、前記易接着層が該接着剤層に接するようにして、この順に積層されて構成された偏光板が提供され、
（１０）水系溶媒で希釈された、ガラス転移温度が６０℃未満の水分散性ウレタン樹脂（Ａ）と、ガラス転移温度が６０℃以上１２０℃以下かつ耐温水性試験における重量増加率が２０％以下である水分散性ウレタン樹脂（Ｂ）とを含む易接着組成物を、熱可塑性樹脂フィルムの少なくとも一方の表面に塗布して塗膜を形成する工程と、前記塗膜を乾燥して易接着層を形成する工程からなる光学フィルムの製造方法が提供される。 According to the present invention,
(1) A water dispersible urethane resin (A) having a glass transition temperature of less than 60 ° C. and a water dispersible urethane having a glass transition temperature of 60 ° C. or more and 120 ° C. or less and a weight increase rate in a warm water resistance test of 20% or less. An easy-adhesive composition comprising resin (B) is provided,
(2) The easy-adhesion composition according to (1), wherein the weight ratio of the water-dispersible urethane resin (A) to the water-dispersible urethane resin (B) is in the range of 95: 5 to 40:60. ,
(3) The easy-adhesion composition according to (1) or (2), wherein the water-dispersible urethane resin (A) has a glass transition temperature of −25 ° C. or higher.
(4) The easy-adhesion composition according to any one of (1) to (3), wherein the elongation at break of the water-dispersible urethane resin (A) is 300% or less,
(5) The easily adhesive composition according to any one of (1) to (4), wherein the elongation at break of the water-dispersible urethane resin (B) is 100% or less,
(6) The easy-adhesive composition according to any one of (1) to (5), further comprising 0.1 to 15 parts by weight of fine particles with respect to a total of 100 parts by weight of the water-dispersible urethane resins (A) and (B) Things are provided,
(7) An optical film including a thermoplastic resin film and an easy adhesion layer provided on at least one surface of the thermoplastic resin film, wherein the easy adhesion layer is any one of (1) to (6) An optical film characterized in that it is formed from the easy-adhesive composition described above,
(8) The optical film according to (7), wherein the resin film is made of a (meth) acrylic resin,
(9) Polarized light in which the optical film, the adhesive layer, and the polarizer according to (7) or (8) are laminated in this order so that the easy-adhesion layer is in contact with the adhesive layer Board is provided,
(10) A water-dispersible urethane resin (A) diluted with an aqueous solvent and having a glass transition temperature of less than 60 ° C., a glass transition temperature of 60 ° C. to 120 ° C., and a weight increase rate of 20% in a warm water resistance test Applying an easy-adhesive composition containing the water-dispersible urethane resin (B) below to at least one surface of a thermoplastic resin film to form a coating film, and drying the coating film to facilitate adhesion A method for producing an optical film comprising a step of forming a layer is provided.
　上記の構成を有する本発明の易接着組成物は、高温高湿下における初期性能の低下を抑制するとともに、より過酷な環境下における耐湿熱性に優れている。なお、本明細書において、「（メタ）アクリル」の用語はメタクリル、アクリル又はこれら両方の総称として使用している。「（メタ）アクリロニトリル」の用語も同様である。 The easy-adhesion composition of the present invention having the above-described configuration suppresses deterioration of initial performance under high temperature and high humidity, and is excellent in heat and humidity resistance under a harsher environment. In the present specification, the term “(meth) acryl” is used as a general term for methacryl, acryl, or both. The same applies to the term “(meth) acrylonitrile”.
本発明の光学フィルムの一例を模式的に示す断面図である。It is sectional drawing which shows an example of the optical film of this invention typically. 本発明の偏光板の一例を模式的に示す断面図である。It is sectional drawing which shows typically an example of the polarizing plate of this invention.
　［易接着組成物］
　本発明の易接着組成物は、ガラス転移点（以下Ｔｇと呼ぶ）が６０℃未満の水分散性ウレタン樹脂（Ａ）と、Ｔｇが６０℃以上１２０℃以下かつ耐温水性試験における重量増加率が２０％以下である水分散性ウレタン樹脂（Ｂ）と、を含有する。本発明の易接着組成物は、このような特性を満足するウレタン樹脂を配合することにより、高温高湿下での長時間使用における密着性に優れる。 [Easily adhesive composition]
The easy-adhesion composition of the present invention comprises a water-dispersible urethane resin (A) having a glass transition point (hereinafter referred to as Tg) of less than 60 ° C., a weight increase rate in a hot water resistance test with a Tg of 60 ° C. to 120 ° C. Containing 20% or less of a water-dispersible urethane resin (B). The easy-adhesion composition of this invention is excellent in the adhesiveness in long-time use under high temperature, high humidity by mix | blending the urethane resin which satisfies such a characteristic.
　水分散性ウレタン樹脂（Ａ）のＴｇは、６０℃未満である。Ｔｇは－２５℃以上６０℃未満であることが好ましく、より好ましくは－１５℃以上５０℃未満、さらに好ましくは－１５℃以上４５℃未満である。水分散性ウレタン樹脂（Ａ）のＴｇが上記範囲であれば、熱可塑性樹脂フィルムとの初期密着性に優れる。 The Tg of the water dispersible urethane resin (A) is less than 60 ° C. Tg is preferably −25 ° C. or higher and lower than 60 ° C., more preferably −15 ° C. or higher and lower than 50 ° C., and further preferably −15 ° C. or higher and lower than 45 ° C. If Tg of water-dispersible urethane resin (A) is the said range, it will be excellent in initial stage adhesiveness with a thermoplastic resin film.
　本明細書においては、Ｔｇは、動的粘弾性測定において損失弾性率（Ｅ″）が極大を示す温度を意味する。より詳しくは、動的粘弾性測定装置（株式会社ユービーエム社製　Rheogel-E4000）を使用して、周波数１０Hz、昇温速度３℃／minの条件下で損失弾性率Ｅ″の温度依存性を測定し、得られたＥ″曲線が極大となる温度をガラス転移温度（℃）とする。 In this specification, Tg means a temperature at which the loss elastic modulus (E ″) has a maximum in dynamic viscoelasticity measurement. More specifically, a dynamic viscoelasticity measuring device (Rheogel- manufactured by UBM Co., Ltd.) E4000) was used to measure the temperature dependence of the loss modulus E ″ under the conditions of a frequency of 10 Hz and a heating rate of 3 ° C./min. The temperature at which the obtained E ″ curve becomes a maximum was determined as the glass transition temperature ( ° C).
　水分散性ウレタン樹脂（Ａ）は、破断伸度が３００％以下であることが好ましい。破断伸度は、１００％以下であることがより好ましく、５０％以下であることがさらに好ましい。水分散性ウレタン樹脂（Ａ）の破断伸度が上記範囲であれば、熱可塑性樹脂フィルムとの密着性に優れる。 The water dispersible urethane resin (A) preferably has a breaking elongation of 300% or less. The breaking elongation is more preferably 100% or less, and further preferably 50% or less. When the elongation at break of the water-dispersible urethane resin (A) is in the above range, the adhesiveness with the thermoplastic resin film is excellent.
　破断伸度については、以下の方法により測定する。先ず、水分散性ウレタン樹脂の水分散体を固形分３５重量％となるよう調製し、乾燥後のウレタン樹脂の膜厚が約５００μｍになるようシャーレ等の容器に取り分け、室温で１５時間乾燥後、８０℃で６時間、さらに１２０℃で２０分間乾燥させ、ウレタン樹脂フィルムを作製する。次いで、このウレタン樹脂フィルムを１５ｍｍ×２００ｍｍの大きさに切断してサンプルを切出した後、中央部に５０ｍｍの間隔で標点を記載したサンプルを作成する。そして、当該サンプルを引っ張り試験機に取り付け、試験機のつかみの間隔を１００ｍｍとし、２００ｍｍ／分の速さで破断するまで測定し、下記の計算方法により算出する。測定温度は２３℃である。
　破断伸度（％）＝（（破断時の標点間距離－試験前の標点間距離）／（試験前の標点間距離））×１００ The breaking elongation is measured by the following method. First, an aqueous dispersion of a water-dispersible urethane resin is prepared so as to have a solid content of 35% by weight, separated into containers such as a petri dish so that the thickness of the urethane resin after drying is about 500 μm, and dried at room temperature for 15 hours. Then, it is dried at 80 ° C. for 6 hours and further at 120 ° C. for 20 minutes to produce a urethane resin film. Next, the urethane resin film is cut into a size of 15 mm × 200 mm to cut out a sample, and then a sample in which marks are written at intervals of 50 mm in the center is created. Then, the sample is attached to a tensile tester, the distance between the grips of the tester is set to 100 mm, the sample is measured until it breaks at a speed of 200 mm / min, and is calculated by the following calculation method. The measurement temperature is 23 ° C.
Elongation at break (%) = ((Distance between gauge points at break-Distance between gauge points before test) / (Distance between gauge points before test)) x 100
　水分散性ウレタン樹脂（Ｂ）は、Ｔｇが６０℃以上１２０℃以下かつ耐温水性試験における重量増加率が２０％以下である。水分散性ウレタン樹脂（Ｂ）のＴｇは６５℃以上１１５℃以下であることが好ましく、より好ましくは７０℃以上１１０℃以下、さらに好ましくは７５℃以上１０５℃以下である。また、耐温水性試験における重量増加率は１５％以下であることが好ましく、より好ましくは１０％以下である。水分散性ウレタン樹脂（Ｂ）のＴｇと重量増加率とが上記範囲であれば、高温高湿下での長時間使用における密着性に優れる。 The water-dispersible urethane resin (B) has a Tg of 60 ° C. or more and 120 ° C. or less and a weight increase rate of 20% or less in the hot water resistance test. The Tg of the water dispersible urethane resin (B) is preferably 65 ° C. or higher and 115 ° C. or lower, more preferably 70 ° C. or higher and 110 ° C. or lower, and further preferably 75 ° C. or higher and 105 ° C. or lower. Moreover, it is preferable that the weight increase rate in a warm water-resistant test is 15% or less, More preferably, it is 10% or less. When the Tg and the weight increase rate of the water-dispersible urethane resin (B) are in the above ranges, the adhesiveness for long time use under high temperature and high humidity is excellent.
　耐温水性試験における重量増加率は、以下の方法により測定する。先ず、水分散性ウレタン樹脂の水分散体を固形分３５重量％となるよう調製し、乾燥後のウレタン樹脂の膜厚が約５００μｍになるようシャーレ等の容器に取り分け、室温で１５時間乾燥後、８０℃で６時間、さらに１２０℃で２０分間乾燥させ、ウレタン樹脂フィルムを作製する。次いで、このウレタン樹脂フィルムを２０ｍｍ×４０ｍｍの大きさに切断してサンプルを切出し、サンプルの重量（Ｗ０）を測定する。その後、当該サンプルを４０℃の温水に２４時間浸漬し、浸漬後のサンプル重量（Ｗ１）を測定し、下記の計算方法により算出する。
　重量増加率（％）＝（（Ｗ１－Ｗ０）／Ｗ０）×１００ The weight increase rate in the hot water resistance test is measured by the following method. First, an aqueous dispersion of a water-dispersible urethane resin is prepared so as to have a solid content of 35% by weight, separated into containers such as a petri dish so that the thickness of the urethane resin after drying is about 500 μm, and dried at room temperature for 15 hours. Then, it is dried at 80 ° C. for 6 hours and further at 120 ° C. for 20 minutes to produce a urethane resin film. Next, the urethane resin film is cut into a size of 20 mm × 40 mm to cut out a sample, and the weight (W0) of the sample is measured. Thereafter, the sample is immersed in warm water at 40 ° C. for 24 hours, the sample weight (W1) after the immersion is measured, and the following calculation method is used.
Weight increase rate (%) = ((W1-W0) / W0) × 100
　水分散性ウレタン樹脂（Ｂ）の破断伸度は、１００％以下であることが好ましい。破断伸度は、５０％以下であることがより好ましく、２０％以下であることがさらに好ましい。水分散性ウレタン樹脂（Ｂ）の破断伸度が上記範囲であれば、熱可塑性樹脂フィルムとの密着性に優れる。なお、破断伸度の測定方法については上述のとおりである。 The breaking elongation of the water dispersible urethane resin (B) is preferably 100% or less. The breaking elongation is more preferably 50% or less, and further preferably 20% or less. When the elongation at break of the water-dispersible urethane resin (B) is in the above range, the adhesiveness with the thermoplastic resin film is excellent. The method for measuring the elongation at break is as described above.
　易接着層が優れた初期密着性および優れた高温高湿下での長時間使用における密着性を発揮するために、易接着層を構成する水分散性ウレタン樹脂（Ａ）と水分散性ウレタン樹脂（Ｂ）との重量比（Ａ／Ｂ）は、９５：５～４０：６０であることが好ましい。更に優れた密着性が得られるという理由で、重量比（Ａ／Ｂ）は、より好ましくは８５：１５～５０：５０、さらに好ましくは８０：２０～６０：４０である。 The water-dispersible urethane resin (A) and the water-dispersible urethane resin that constitute the easy-adhesion layer in order to exhibit excellent initial adhesion and excellent adhesion in long-term use under high temperature and high humidity. The weight ratio (A / B) to (B) is preferably 95: 5 to 40:60. The weight ratio (A / B) is more preferably 85:15 to 50:50, still more preferably 80:20 to 60:40, because more excellent adhesion can be obtained.
　水分散性ウレタン樹脂（Ａ）及び（Ｂ）は、上述した特性を有する水分散性のウレタン樹脂であれば特に限定されず、例えば、イソシアネートに対して不活性で、水と相溶する有機溶剤中でポリイソシアネートとポリオールとを反応させてイソシアネート基末端プレポリマーを形成した後、遊離のカルボキシル基を有する鎖伸長剤と反応させて得られる線状ウレタンプレポリマーを、中和剤の存在下水中で、水で鎖伸長させると同時に水性化して得ることができる。なお、ここでいう水性化とは、樹脂を水中に安定に分散若しくは乳化させることを指す。また、水分散性ウレタン樹脂（Ａ）及び（Ｂ）は、分子中にカルボキシル基を有することが好ましく、カルボキシル基を有することにより、高温高湿下での長時間使用における密着性に優れる。 The water-dispersible urethane resins (A) and (B) are not particularly limited as long as they are water-dispersible urethane resins having the above-described characteristics. For example, the organic solvent is inert to isocyanate and compatible with water. In the presence of a neutralizing agent, a linear urethane prepolymer obtained by reacting a polyisocyanate with a polyol to form an isocyanate group-terminated prepolymer and then reacting with a chain extender having a free carboxyl group in water Thus, it can be obtained by making it chain-extending with water and at the same time making it aqueous. The term “water-based” as used herein means that the resin is stably dispersed or emulsified in water. Moreover, it is preferable that water-dispersible urethane resin (A) and (B) has a carboxyl group in a molecule | numerator, and it is excellent in the adhesiveness in long-time use under high temperature, high humidity by having a carboxyl group.
　ポリイソシアネートとしては、例えば、テトラメチレンジイソシアネート、ドデカメチレンジイソシアネート、１，４－ブタンジイソシアネート、ヘキサメチレンジイソシアネート、２，２，４－トリメチルヘキサメチレンジイソシアネート、２，４，４－トリメチルヘキサメチレンジイソシアネート、リジンジイソシアネート、２－メチルペンタン－１，５－ジイソシアネート、３－メチルペンタン－１，５－ジイソシアネート等の脂肪族ジイソシアネート；イソホロンジイソシアネート、水添キシリレンジイソシアネート、４，４′－シクロヘキシルメタンジイソシアネート、１，４－シクロヘキサンジイソシアネート、メチルシクロヘキシレンジイソシアネート、１，３－ビス（イソシアネートメチル）シクロヘキサン等の脂環族ジイソシアネート；トリレンジイソシアネート、２，２′－ジフェニルメタンジイソシアネート、２，４′－ジフェニルメタンジイソシアネート、４，４′－ジフェニルメタンジイソシアネート、４，４′－ジフェニルジメチルメタンジイソシアネート、４，４′－ジベンジルジイソシアネート、１，５－ナフチレンジイソシアネート、キシリレンジイソシアネート、１，３－フェニレンジイソシアネート、１，４－フェニレンジイソシアネート等の芳香族ジイソシアネート；ジアルキルジフェニルメタンジイソシアネート、テトラアルキルジフェニルメタンジイソシアネート、α，α，α，α－テトラメチルキシリレンジイソシアネート等の芳香脂肪族ジイソシアネート等が挙げられる。これらは単独、或いは２種以上を組み合わせて用いることができる。 Examples of polyisocyanates include tetramethylene diisocyanate, dodecamethylene diisocyanate, 1,4-butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate. Aliphatic diisocyanates such as 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate; isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4'-cyclohexylmethane diisocyanate, 1,4- Cycloaliphatic diisocyanate, methylcyclohexylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane Socyanate; tolylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, 1 , 5-naphthylene diisocyanate, xylylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate and other aromatic diisocyanates; dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, α, α, α, α-tetramethylxylylene Examples include aromatic aliphatic diisocyanates such as range isocyanate. These can be used alone or in combination of two or more.
　ポリオールとしては、分子中にヒドロキシル基を２個以上有するものであれば特に限定されず、任意の適切なポリオールを採用することができる。例えば、ポリアルキレングリコール、ポリアクリルポリオール、ポリエステルポリオール、ポリエーテルポリオール、ポリエーテル・エステルポリオール、ポリカーボネートポリオール等が挙げられる。これらは単独、或いは２種以上を組み合わせて用いることができる。 The polyol is not particularly limited as long as it has two or more hydroxyl groups in the molecule, and any appropriate polyol can be adopted. For example, polyalkylene glycol, polyacryl polyol, polyester polyol, polyether polyol, polyether ester polyol, polycarbonate polyol and the like can be mentioned. These can be used alone or in combination of two or more.
　遊離のカルボキシル基を有する鎖伸長剤としては、例えば、ジヒドロキシカルボン酸、ジヒドロキシスクシン酸等が挙げられる。ジヒドロキシカルボン酸としては、例えば、ジメチロールアルカン酸（例えば、ジメチロール酢酸、ジメチロールブタン酸、ジメチロールプロピオン酸、ジメチロール酪酸、ジメチロールペンタン酸）等のジアルキロールアルカン酸が挙げられる。これらは単独、或いは２種以上を組み合わせて用いることができる。 Examples of the chain extender having a free carboxyl group include dihydroxycarboxylic acid and dihydroxysuccinic acid. Examples of the dihydroxycarboxylic acid include dialkyrol alkanoic acids such as dimethylol alkanoic acid (for example, dimethylol acetic acid, dimethylol butanoic acid, dimethylol propionic acid, dimethylol butyric acid, dimethylol pentanoic acid). These can be used alone or in combination of two or more.
　中和剤としては、例えば、アンモニア、Ｎ－メチルモルホリン、トリエチルアミン、ジメチルエタノールアミン、メチルジエタノールアミン、トリエタノールアミン、モルホリン、トリプロピルアミン、エタノールアミン、トリイソプロパノールアミン、２－アミノ－２－メチル－１－プロパノール等が挙げられる。これらは単独、或いは２種以上を組み合わせて用いることができる。 Examples of the neutralizing agent include ammonia, N-methylmorpholine, triethylamine, dimethylethanolamine, methyldiethanolamine, triethanolamine, morpholine, tripropylamine, ethanolamine, triisopropanolamine, 2-amino-2-methyl-1 -Propanol and the like. These can be used alone or in combination of two or more.
　更に、他の使用可能な鎖伸長剤としては、エチレングリコール、プロピレングリコール、１，４－ブタンジオール、ネオペンチルグリコール、フランジメタノール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール等の低分子量ジオール化合物及びこれらにエチレンオキサイド、プロピレンオキサイド、テトラヒドロフラン等を付加重合させたポリエーテルジオール化合物；上記低分子量ジオール化合物と（無水）コハク酸、アジピン酸、（無水）フタル酸等のジカルボン酸及びこれらの無水物から得られる末端に水酸基を有するポリエステルジオール；トリメチロールエタン、トリメチロールプロパン等の多価アルコール；モノエタノールアミン、ジエタノールアミン、トリエタノールアミン等のアミノアルコール；エチレンジアミン、プロピレンジアミン、ブチレンジアミン、ヘキサメチレンジアミン、フェニレンジアミン、トルエンジアミン、キシレンジアミン、イソホロンジアミン等のジアミン化合物；水、アンモニア、ヒドラジン、二塩基酸ヒドラジド等を挙げることができる。これらは単独、或いは２種以上を組み合わせて用いることができる。 Further, other usable chain extenders include low molecular weight diol compounds such as ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, furan methanol, diethylene glycol, triethylene glycol, tetraethylene glycol, and the like. Polyether diol compounds obtained by addition polymerization of ethylene oxide, propylene oxide, tetrahydrofuran, etc .; obtained from the above low molecular weight diol compounds and dicarboxylic acids such as (anhydrous) succinic acid, adipic acid, (anhydrous) phthalic acid, and their anhydrides Polyester diols having a hydroxyl group at the terminal; polyhydric alcohols such as trimethylolethane and trimethylolpropane; amino alcohols such as monoethanolamine, diethanolamine and triethanolamine Lumpur ethylenediamine, propylene diamine, butylene diamine, hexamethylene diamine, phenylene diamine, toluene diamine, xylene diamine, diamine compounds such as isophoronediamine; water, ammonia, hydrazine, may be mentioned dibasic acid hydrazide and the like. These can be used alone or in combination of two or more.
　水分散性ウレタン樹脂（Ａ）及び（Ｂ）の数平均分子量は、好ましくは５０００～６０００００、さらに好ましくは１００００～４０００００である。水分散性ウレタン樹脂の酸価は、好ましくは１０以上、さらに好ましくは１０～５０、特に好ましくは２０～４５である。 The number average molecular weight of the water-dispersible urethane resins (A) and (B) is preferably 5000 to 600000, more preferably 10,000 to 400000. The acid value of the water-dispersible urethane resin is preferably 10 or more, more preferably 10 to 50, and particularly preferably 20 to 45.
　易接着組成物は、易接着層形成時の作業性から水系溶媒で希釈されていても良い。水系溶媒としては、水もしくは水と親水性の有機溶剤（例えば、メタノール、エタノール、イソプロピルアルコール、エチレングリコール、プロピレングリコール等のアルコール系溶剤；酢酸エチル、酢酸ブチル、γ－ブチロラクトン等のエステル系溶剤；アセトン等のケトン系溶剤；テトラヒドロフラン、ジオキサン等のエーテル系溶剤；Ｎ－メチルピロリドン等の非プロトン性極性溶媒）との混合溶媒を用いることができるが、特に水が好ましい。 The easy-adhesion composition may be diluted with an aqueous solvent from the viewpoint of workability when forming the easy-adhesion layer. Examples of the aqueous solvent include water or water and hydrophilic organic solvents (for example, alcohol solvents such as methanol, ethanol, isopropyl alcohol, ethylene glycol, and propylene glycol; ester solvents such as ethyl acetate, butyl acetate, and γ-butyrolactone; A mixed solvent with a ketone solvent such as acetone; an ether solvent such as tetrahydrofuran or dioxane; an aprotic polar solvent such as N-methylpyrrolidone) can be used, but water is particularly preferable.
　易接着組成物における水分散性ウレタン樹脂（Ａ）及び（Ｂ）の含有量は、特に限定されず、塗布作業性等を考慮して適宜設定すれば良く、例えば、１～２５重量％が好ましく、より好ましくは３～２０重量％、さらに好ましくは、５～１５重量％である。易接着組成物における水分散性ウレタン樹脂（Ａ）及び（Ｂ）が上記範囲であれば、易接着層形成時の作業性に優れることから好ましい。また、易接着組成物の固形分量は、塗布作業性等を考慮して適宜設定すれば良いが、１～３０重量％が好ましく、より好ましくは２～２５重量％、さらに好ましくは３～２０重量％である。 The content of the water-dispersible urethane resins (A) and (B) in the easy-adhesive composition is not particularly limited, and may be appropriately set in consideration of application workability and the like, for example, 1 to 25% by weight is preferable. More preferably, it is 3 to 20% by weight, still more preferably 5 to 15% by weight. If the water-dispersible urethane resins (A) and (B) in the easy-adhesive composition are in the above ranges, it is preferable because workability at the time of forming the easy-adhesive layer is excellent. The solid content of the easy-adhesive composition may be appropriately set in consideration of application workability and the like, but is preferably 1 to 30% by weight, more preferably 2 to 25% by weight, and further preferably 3 to 20% by weight. %.
　易接着組成物は、所望の機能に合わせて任意の適切な微粒子、好ましくは水分散性の微粒子を含有することができる。微粒子としては、無機系微粒子、有機系微粒子のいずれも用いることができる。無機系微粒子としては、例えば、シリカ、チタニア、アルミナ、ジルコニア等の無機酸化物、炭酸カルシウム、タルク、クレイ、焼成カオリン、焼成珪酸カルシウム、水和珪酸カルシウム、珪酸アルミニウム、珪酸マグネシウム、燐酸カルシウム等が挙げられる。有機系微粒子としては、例えば、シリコーン系樹脂、フッ素系樹脂、（メタ）アクリル系樹脂、（メタ）アクリロニトリル系樹脂等が挙げられる。これらの中でも、好ましくは、シリカ或いは（メタ）アクリロニトリル系樹脂である。シリカ或いは（メタ）アクリロニトリル系樹脂からなる微粒子は、ブロッキング抑制能に優れ、かつ、透明性に優れ、ヘイズを生じず、着色もないので、易接層が光学特性に与える影響がより小さい。また、易接着層の強度及び密着性は、微粒子を配合することにより低下するものであるが、（メタ）アクリロニトリル系樹脂からなる微粒子を配合した易接着層は、易接着層の強度及び密着性の低下を抑制し得ることから特に好ましい。 The easy-adhesion composition can contain any appropriate fine particles, preferably water-dispersible fine particles, in accordance with a desired function. As the fine particles, either inorganic fine particles or organic fine particles can be used. Examples of the inorganic fine particles include inorganic oxides such as silica, titania, alumina, zirconia, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate, calcium phosphate, and the like. Can be mentioned. Examples of the organic fine particles include silicone resins, fluorine resins, (meth) acrylic resins, (meth) acrylonitrile resins, and the like. Among these, silica or (meth) acrylonitrile resin is preferable. Fine particles made of silica or (meth) acrylonitrile-based resin are excellent in blocking suppression ability, excellent in transparency, do not cause haze, and are not colored, so that the easy-contact layer has less influence on optical properties. In addition, the strength and adhesion of the easy-adhesion layer are reduced by adding fine particles, but the easy-adhesion layer containing fine particles made of (meth) acrylonitrile resin is the strength and adhesion of the easy-adhesion layer. It is particularly preferable because it is possible to suppress the decrease in the thickness.
　微粒子の平均粒子径は、特に限定するものではないが、易接着層の透明性を維持する観点から、好ましくは１～５００ｎｍ、より好ましくは５０～３５０ｎｍ、さらに好ましくは１００～３００ｎｍである。このような粒子径の微粒子を用いることにより、易接着層表面に適切に凹凸を形成して、熱可塑性樹脂フィルムと易接着層および／または易接着層どうしの接触面における摩擦力を効果的に低減することができ、ブロッキングを抑制することができる。上記の平均粒子径とは、レーザ回折/散乱式粒度分布測定にて測定されるメジアン径（ｄ５０）を意味する。 The average particle diameter of the fine particles is not particularly limited, but is preferably 1 to 500 nm, more preferably 50 to 350 nm, and still more preferably 100 to 300 nm from the viewpoint of maintaining the transparency of the easy-adhesion layer. By using fine particles of such a particle size, irregularities are appropriately formed on the surface of the easy-adhesion layer, and the frictional force at the contact surface between the thermoplastic resin film and the easy-adhesion layer and / or the easy-adhesion layer is effectively reduced. It can reduce and blocking can be suppressed. The above average particle diameter means a median diameter (d50) measured by laser diffraction / scattering particle size distribution measurement.
　微粒子の含有量は、固形分換算で、水分散性ウレタン樹脂（Ａ）及び（Ｂ）の合計１００重量部に対して、０．１～１５重量部であることが好ましい。より好ましくは０．３～５重量部、さらに好ましくは０．５～３重量部である。なお、水分散性ウレタン樹脂（Ａ）及び（Ｂ）以外の他の成分を含む場合、他の成分をも含めた固形分に対して、微粒子を配合すれば良い。 The content of the fine particles is preferably 0.1 to 15 parts by weight with respect to a total of 100 parts by weight of the water-dispersible urethane resins (A) and (B) in terms of solid content. More preferred is 0.3 to 5 parts by weight, still more preferred is 0.5 to 3 parts by weight. In addition, what is necessary is just to mix | blend microparticles | fine-particles with respect to solid content also including other components, when other components other than water-dispersible urethane resin (A) and (B) are included.
　易接着組成物は、高温高湿下における耐湿熱性を向上させるため、架橋剤を配合しても良い。架橋剤としては、任意の適切な架橋剤を採用することができ、例えば、尿素系、エポキシ系、メラミン系、イソシアネート系、オキサゾリン系、シラノール系、カルボジイミド系等が挙げられる。また、架橋反応を促進させるため、触媒等を必要に応じて適宜使用しても良い。 The easy-adhesion composition may be blended with a crosslinking agent in order to improve heat and humidity resistance under high temperature and high humidity. Any appropriate crosslinking agent can be adopted as the crosslinking agent, and examples thereof include urea, epoxy, melamine, isocyanate, oxazoline, silanol, and carbodiimide. Moreover, in order to promote a crosslinking reaction, you may use a catalyst etc. suitably as needed.
　易接着組成物は、任意の適切な添加剤をさらに含むことができる。添加剤としては、例えば、分散安定剤、揺変剤、酸化防止剤、紫外線吸収剤、消泡剤、増粘剤、分散剤、界面活性剤、触媒、滑剤、帯電防止剤等が挙げられる。 The easy-adhesion composition can further contain any appropriate additive. Examples of the additive include a dispersion stabilizer, a thixotropic agent, an antioxidant, an ultraviolet absorber, an antifoaming agent, a thickener, a dispersant, a surfactant, a catalyst, a lubricant, and an antistatic agent.
　［光学フィルム］
　図１に本発明の光学フィルムの一例を示す。図１に示す光学フィルム１は、熱可塑性樹脂フィルム２の一方の表面に上述した易接着組成物から形成される易接着層３を有する。なお、本発明の光学フィルムは、熱可塑性樹脂フィルムの双方の表面に易接着層が形成されていても良い。 [Optical film]
FIG. 1 shows an example of the optical film of the present invention. An optical film 1 shown in FIG. 1 has an easy adhesion layer 3 formed from the above-mentioned easy adhesion composition on one surface of a thermoplastic resin film 2. In the optical film of the present invention, an easy adhesion layer may be formed on both surfaces of the thermoplastic resin film.
　熱可塑性樹脂フィルムを構成する熱可塑性樹脂としては、例えば、トリアセチルセルロースなどのセルロース系樹脂、ポリエステル系樹脂、ポリエーテルスルホン系樹脂、ポリカーボネート系樹脂、ポリアミド系樹脂、ポリイミド系樹脂、ポリオレフィン系樹脂、環状ポリオレフィン系樹脂、（メタ）アクリル系樹脂、ポリアリレート系樹脂、ポリスチレン系樹脂、ポリビニルアルコール系樹脂等が挙げられる。これらは単独、或いは２種以上を組み合わせて用いることができる。これらの中でも、（メタ）アクリル系樹脂(以下ＡＣＲと略すことが有る)は親水性接着剤との接着性に劣ることから、本発明の効果はＡＣＲを用いる場合に特に顕著である。 Examples of the thermoplastic resin constituting the thermoplastic resin film include cellulose resins such as triacetyl cellulose, polyester resins, polyether sulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, Examples include cyclic polyolefin resins, (meth) acrylic resins, polyarylate resins, polystyrene resins, and polyvinyl alcohol resins. These can be used alone or in combination of two or more. Among these, the (meth) acrylic resin (hereinafter sometimes abbreviated as ACR) is inferior in adhesiveness with a hydrophilic adhesive, and therefore the effect of the present invention is particularly remarkable when ACR is used.
　ＡＣＲのＴｇは、１１５℃以上であることが好ましく、より好ましくは１２０℃以上、さらに好ましくは１２５℃以上である。熱可塑性樹脂フィルムは、Ｔｇが１１５℃以上であるＡＣＲを主成分として含むことにより、耐久性に優れたものとすることができる。また、上記Ｔｇの上限値は特に制限するものではないが、成形性等の観点から、１７０℃以下であることが好ましい。 The TCR of ACR is preferably 115 ° C. or higher, more preferably 120 ° C. or higher, and further preferably 125 ° C. or higher. The thermoplastic resin film can be made excellent in durability by containing ACR having a Tg of 115 ° C. or higher as a main component. The upper limit of Tg is not particularly limited, but is preferably 170 ° C. or lower from the viewpoint of moldability and the like.
　ＡＣＲとしては、例えば、ポリメタクリル酸メチルなどのポリ（メタ）アクリル酸エステル、メタクリル酸メチル－（メタ）アクリル酸共重合体、メタクリル酸メチル－（メタ）アクリル酸エステル共重合体、メタクリル酸メチル－アクリル酸エステル－（メタ）アクリル酸共重合体、（メタ）アクリル酸メチル－スチレン共重合体（ＭＳ樹脂など）、脂環族炭化水素基を有する重合体、（例えば、メタクリル酸メチルーメタクリル酸シクロヘキシル共重合耐、メタクリル酸メチル－（メタ）アクリル酸ノルボルニル共重合体など）が挙げられる。上記の中でも、ポリ（メタ）アクリル酸メチルなどのポリ（メタ）アクリル酸Ｃ１－６アルキルが好ましく、メタクリル酸メチルを主成分（５０～１００重量％、好ましくは７０～１００重量％）とするメタクリル酸メチル系樹脂がより好ましい。 Examples of ACR 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. -Acrylic acid ester- (meth) acrylic acid copolymer, methyl (meth) acrylate-styrene copolymer (MS resin, etc.), polymer having an alicyclic hydrocarbon group (for example, methyl methacrylate-methacrylic acid) Acid cyclohexyl copolymer resistance, methyl methacrylate- (meth) acrylate norbornyl copolymer, etc.). Among them, poly (meth) acrylate C1-6 alkyl such as poly (meth) acrylate is preferable, and methacrylic acid having methyl methacrylate as a main component (50 to 100% by weight, preferably 70 to 100% by weight) is preferable. An acid methyl resin is more preferable.
　ＡＣＲの具体例としては、例えば、三菱レイヨン社製「アクリペット（登録商標）ＶＨ」、「アクリペット（登録商標）ＶＲＬ２０Ａ」、分子内架橋や分子内環化反応により得られる高Ｔｇ（メタ）アクリル系樹脂が挙げられる。 Specific examples of ACR include, for example, “Acrypet (registered trademark) VH”, “Acrypet (registered trademark) VRL20A” manufactured by Mitsubishi Rayon Co., Ltd., high Tg (meta) obtained by intramolecular crosslinking and intramolecular cyclization reaction. An acrylic resin is mentioned.
　ＡＣＲは、高い耐熱性、高い透明性、高い機械強度を有する点で、主鎖に環構造を有することが好ましい。主鎖に環構造を有するＡＣＲとしては、例えば、無水グルタル酸構造あるいはグルタルイミド構造を有する樹脂（ＷＯ２００７／２６６５９号公報、ＷＯ２００５／１０８４３８号公報）、無水マレイン酸構造あるいはＮ－置換マレイミド構造を有する樹脂（特開昭５７－１５３００８号公報、特開２００７－３１５３７号公報）、ラクトン環構造を有する樹脂（特開２００６－９６９６０号公報、特開２００６－１７１４６４号公報、特開２００７－６３５４１号公報、特開２００８－１９１４２６号公報）が挙げられる。 The ACR preferably has a ring structure in the main chain in that it has high heat resistance, high transparency, and high mechanical strength. Examples of the ACR having a ring structure in the main chain include a resin having a glutaric anhydride structure or a glutarimide structure (WO2007 / 26659, WO2005 / 108438), a maleic anhydride structure or an N-substituted maleimide structure. Resins (Japanese Patent Laid-Open Nos. 57-153008 and 2007-31537) and resins having a lactone ring structure (Japanese Patent Laid-Open Nos. 2006-96960, 2006-171464, and 2007-63541) JP, 2008-191426, A).
　熱可塑性樹脂フィルムは、添加剤を含有していてもよい。添加剤としては、例えば、ヒンダードフェノール系、リン系、イオウ系等の酸化防止剤；耐光安定剤、耐候安定剤、熱安定剤等の安定剤；ガラス繊維、炭素繊維等の補強材；紫外線吸収剤；近赤外線吸収剤；難燃剤；アニオン系、カチオン系、ノニオン系の界面活性剤等の帯電防止剤；無機顔料、有機顔料、染料等の着色剤；有機フィラーや無機フィラー；樹脂改質剤；有機充填剤や無機充填剤；可塑剤；滑剤；帯電防止剤；難燃剤；位相差低減剤等が挙げられる。 The thermoplastic resin film may contain an additive. Examples of additives include hindered phenol-based, phosphorus-based and sulfur-based antioxidants; light-resistant stabilizers, weather-resistant stabilizers, heat stabilizers and other stabilizers; reinforcing materials such as glass fibers and carbon fibers; ultraviolet rays Absorbers; Near infrared absorbers; Flame retardants; Antistatic agents such as anionic, cationic and nonionic surfactants; Colorants such as inorganic pigments, organic pigments and dyes; Organic fillers and inorganic fillers; Resin modification Agents; organic fillers and inorganic fillers; plasticizers; lubricants; antistatic agents; flame retardants;
　熱可塑性樹脂フィルムの製造方法としては、特に限定されるものではないが、例えば、熱可塑性樹脂と、その他の重合体や添加剤等を、任意の適切な混合方法で充分に混合し、予め熱可塑性樹脂組成物としてから、これをフィルム成形することができる。あるいは、熱可塑性樹脂と、その他の重合体や添加剤等を、それぞれ別々の溶液にしてから混合して均一な混合液とした後、フィルム成形してもよい。 The method for producing the thermoplastic resin film is not particularly limited. For example, the thermoplastic resin and other polymers and additives are sufficiently mixed by any appropriate mixing method and heated in advance. From the plastic resin composition, it can be formed into a film. Alternatively, the thermoplastic resin and other polymers, additives, and the like may be made into separate solutions and mixed to form a uniform mixed solution, and then formed into a film.
　熱可塑性樹脂組成物を製造するには、例えば、オムニミキサー等、任意の適切な混合機で上記のフィルム原料をプレブレンドした後、得られた混合物を押出混練する。この場合、押出混練に用いられる混練機は、特に限定されるものではなく、例えば、単軸押出機、二軸押出機等の押出機や加圧ニーダー等、任意の適切な混合機を用いることができる。 In order to produce a thermoplastic resin composition, for example, the film raw material is pre-blended with any appropriate mixer such as an omni mixer, and then the obtained mixture is extruded and kneaded. In this case, the kneader used for extrusion kneading is not particularly limited. For example, any suitable mixer such as an extruder such as a single screw extruder or a twin screw extruder or a pressure kneader may be used. Can do.
　フィルム成形の方法としては、例えば、溶液キャスト法（溶液流延法）、溶融押出法、カレンダー法、圧縮成形法等、任意の適切なフィルム成形法が挙げられる。これらのフィルム成形法のうち、溶融押出法が好ましい。 Examples of the film forming method include any appropriate film forming method such as a solution casting method (solution casting method), a melt extrusion method, a calendar method, and a compression molding method. Of these film forming methods, the melt extrusion method is preferred.
　溶融押出法としては、例えば、Ｔダイ法、インフレーション法等が挙げられる。成形温度は、好ましくは１５０～３５０℃、より好ましくは２００～３００℃である。 Examples of the melt extrusion method include a T-die method and an inflation method. The molding temperature is preferably 150 to 350 ° C, more preferably 200 to 300 ° C.
　Ｔダイ法でフィルム成形する場合は、公知の単軸押出機や二軸押出機の先端部にＴダイを取り付け、当該Ｔダイによりフィルムを製膜した後、フィルムを巻取ることでロール状のフィルムを得ることができる。 When forming a film by the T-die method, a T-die is attached to the tip of a known single-screw extruder or twin-screw extruder, a film is formed by the T die, and then the film is wound to form a roll. A film can be obtained.
　熱可塑性樹脂フィルムは、未延伸フィルムまたは延伸フィルムのいずれでもよい。延伸フィルムである場合は、１軸延伸フィルムまたは２軸延伸フィルムのいずれでもよい。２軸延伸フィルムである場合は、同時２軸延伸フィルムまたは逐次２軸延伸フィルムのいずれでもよい。２軸延伸した場合は、機械的強度が向上し、フィルム性能が向上する。 The thermoplastic resin film may be an unstretched film or a stretched film. In the case of a stretched film, either a uniaxially stretched film or a biaxially stretched film may be used. In the case of a biaxially stretched film, either a simultaneous biaxially stretched film or a sequential biaxially stretched film may be used. In the case of biaxial stretching, the mechanical strength is improved and the film performance is improved.
　延伸温度は、フィルム原料である熱可塑性樹脂組成物のガラス転移温度近傍であることが好ましく、具体的には、好ましくは（Ｔｇ－３０℃）～（Ｔｇ＋１００℃）、より好ましくは（Ｔｇ－２０℃）～（Ｔｇ＋８０℃）の範囲内である。延伸温度が（Ｔｇ－３０℃）未満であると、充分な延伸倍率が得られないおそれがある。逆に、延伸温度が（Ｔｇ＋１００℃）超えると、樹脂組成物の流動（フロー）が起こり、安定な延伸が行えないおそれがある。 The stretching temperature is preferably in the vicinity of the glass transition temperature of the thermoplastic resin composition that is a film raw material, specifically, preferably (Tg-30 ° C) to (Tg + 100 ° C), more preferably (Tg-20). ° C) to (Tg + 80 ° C). If the stretching temperature is less than (Tg-30 ° C.), a sufficient stretching ratio may not be obtained. On the other hand, when the stretching temperature exceeds (Tg + 100 ° C.), the resin composition may flow and stable stretching may not be performed.
　面積比で定義した延伸倍率は、好ましくは１．１～２５倍、より好ましくは１．３～１０倍である。延伸倍率が１．１倍未満であると、延伸に伴う靭性の向上につながらないおそれがある。延伸倍率が２５倍を超えると、延伸倍率を上げるだけの効果（靱性の向上）が認められないおそれがある。 The draw ratio defined by the area ratio is preferably 1.1 to 25 times, more preferably 1.3 to 10 times. There exists a possibility that it may not lead to the improvement of the toughness accompanying extending | stretching that a draw ratio is less than 1.1 times. When the draw ratio exceeds 25 times, there is a possibility that the effect of only increasing the draw ratio (improvement of toughness) is not recognized.
　延伸速度は、一方向で、好ましくは１０～２０，０００％／ｍｉｎ、より好ましく１００～１０，０００％／ｍｉｎである。延伸速度が１０％／ｍｉｎ未満であると、充分な延伸倍率を得るために時間がかかり、製造コストが高くなるおそれがある。延伸速度が２０，０００％／ｍｉｎを超えると、延伸フィルムの破断等が起こるおそれがある。 The stretching speed is unidirectional, preferably 10 to 20,000% / min, more preferably 100 to 10,000% / min. When the stretching speed is less than 10% / min, it takes time to obtain a sufficient stretching ratio, and the production cost may increase. If the stretching speed exceeds 20,000% / min, the stretched film may be broken.
　熱可塑性樹脂フィルムは、その光学的等方性や機械的特性を安定化させるために、延伸処理後に熱処理（アニーリング）等を行うことができる。熱処理の条件は、任意の適切な条件を採用し得る。 The thermoplastic resin film can be subjected to a heat treatment (annealing) or the like after the stretching treatment in order to stabilize its optical isotropy and mechanical properties. Arbitrary appropriate conditions can be employ | adopted for the conditions of heat processing.
　熱可塑性樹脂フィルムの厚さは、好ましくは５～２００μｍ、より好ましくは１０～１００μｍである。厚さが５μｍ未満であると、光学フィルムとしての十分な強度が得られなくなるおそれがある。厚さが２００μｍを超えると、透明性が低下し、光学フィルムとしての使用に適さなくなるおそれがある。 The thickness of the thermoplastic resin film is preferably 5 to 200 μm, more preferably 10 to 100 μm. If the thickness is less than 5 μm, sufficient strength as an optical film may not be obtained. When the thickness exceeds 200 μm, the transparency is lowered and there is a possibility that it is not suitable for use as an optical film.
　易接着層の厚みは、任意の適切な値に設定することができる。好ましくは０．１～１０μｍ、さらに好ましくは０．１～５μｍ、特に好ましくは０．２～１μｍである。このような範囲に設定することにより、他の機能性フィルムとの密着性に優れ、易接着層に位相差が発現するのを抑制することができる。 The thickness of the easy-adhesion layer can be set to any appropriate value. The thickness is preferably 0.1 to 10 μm, more preferably 0.1 to 5 μm, and particularly preferably 0.2 to 1 μm. By setting to such a range, it is excellent in adhesiveness with another functional film, and it can suppress that a phase difference expresses in an easily bonding layer.
　光学フィルムにおける易接着層が形成されている表面と反対側の表面には、必要に応じて、各種の機能層が形成されていてもよい。機能層は、例えば、帯電防止層、粘接着剤層、接着層、易接着層、防眩（ノングレア）層、光触媒層などの防汚層、反射防止層、ハードコート層、紫外線遮蔽層、熱線遮蔽層、電磁波遮蔽層、ガスバリヤー層等が挙げられる。 Various functional layers may be formed on the surface of the optical film opposite to the surface on which the easy adhesion layer is formed, if necessary. The functional layer is, for example, an antistatic layer, an adhesive layer, an adhesive layer, an easy adhesion layer, an antiglare layer (non-glare) layer, an antifouling layer such as a photocatalyst layer, an antireflection layer, a hard coat layer, an ultraviolet shielding layer, A heat ray shielding layer, an electromagnetic wave shielding layer, a gas barrier layer, etc. are mentioned.
　光学フィルムは、例えば、偏光子保護フィルム、位相差フィルム、視野角補償フィルム、光拡散フィルム、反射フィルム、反射防止フィルム、防眩フィルム、輝度向上フィルム、タッチパネル用導電フィルムとして使用することができる。また、これらの中でも、偏光子保護フィルムとして使用することが特に好ましい。 The optical film can be used as, for example, a polarizer protective film, a retardation film, a viewing angle compensation film, a light diffusion film, a reflection film, an antireflection film, an antiglare film, a brightness enhancement film, and a conductive film for a touch panel. Of these, the use as a polarizer protective film is particularly preferable.
　［偏光板］
　次に、本発明の偏光板の一例を説明する。図２に示す偏光板１０は、熱可塑性樹脂フィルム２の一方の表面に上述した易接着組成物から形成される易接着層３を有する光学フィルム１の易接着層側の表面に接着剤５を介し、偏光子６が積層された構造を有する。なお、図示しないが、偏光板１０は、偏光子６の光学フィルム１と反対側に、接着剤層を介して積層された保護フィルムを有していても良い。 [Polarizer]
Next, an example of the polarizing plate of the present invention will be described. A polarizing plate 10 shown in FIG. 2 has an adhesive 5 on the surface of the optical film 1 having the easy adhesion layer 3 formed from the above-mentioned easy adhesion composition on one surface of the thermoplastic resin film 2. The polarizer 6 has a stacked structure. Although not shown, the polarizing plate 10 may have a protective film laminated via an adhesive layer on the opposite side of the polarizer 6 from the optical film 1.
　偏光子としては、目的に応じて任意の適切な偏光子を採用することができる。例えば、ポリビニルアルコール系フィルム、部分ホルマール化ポリビニルアルコール系フィルム、エチレン－酢酸ビニル共重合体系部分ケン化フィルム等の親水性高分子フィルムに、ヨウ素や二色性染料等の二色性物質を吸着させて一軸延伸したもの、ポリビニルアルコールの脱水処理物やポリ塩化ビニルの脱塩酸処理物等ポリエン系配向フィルム等が挙げられる。これらの中でも、ポリビニルアルコール系フィルムにヨウ素などの二色性物質を吸着させて一軸延伸した偏光子が、偏光二色比が高く特に好ましい。これら偏光子の厚さは特に制限されないが、一般的に、１～８０μｍ程度である。 As the polarizer, any appropriate polarizer can be adopted depending on the purpose. For example, dichroic substances such as iodine and dichroic dyes are adsorbed on hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and ethylene-vinyl acetate copolymer partially saponified films. And polyene-based oriented films such as a uniaxially stretched product, a polyvinyl alcohol dehydrated product and a polyvinyl chloride dehydrochlorinated product. Among these, a polarizer obtained by adsorbing a dichroic substance such as iodine on a polyvinyl alcohol film and uniaxially stretching is particularly preferable because of its high polarization dichroic ratio. The thickness of these polarizers is not particularly limited, but is generally about 1 to 80 μm.
　接着剤層を形成する接着剤としては、任意の適切な接着剤を採用することができる。好ましくは、接着剤層は、ポリビニルアルコール系樹脂を含む接着剤組成物から形成される。 Any appropriate adhesive can be adopted as the adhesive forming the adhesive layer. Preferably, the adhesive layer is formed from an adhesive composition containing a polyvinyl alcohol-based resin.
　偏光子６の光学フィルム１の反対側に設ける保護フィルムとしては、任意の適切な保護フィルムを採用することができ、上述した熱可塑性樹脂と同様の材料で形成されていてもよい。 Arbitrary appropriate protective films can be employ | adopted as a protective film provided in the other side of the optical film 1 of the polarizer 6, and it may be formed with the material similar to the thermoplastic resin mentioned above.
　［画像表示装置］
　本発明の画像表示装置は、上述した偏光板を備える。画像表示装置の具体例としては、エレクトロルミネッセンス（ＥＬ）ディスプレイ、プラズマディスプレイ（ＰＤ）、電界放出ディスプレイ（ＦＥＤ：Field Emission Display）のような自発光型表示装置、液晶表示装置（ＬＣＤ）が挙げられる。 [Image display device]
The image display apparatus of the present invention includes the polarizing plate described above. Specific examples of the image display device include a self-luminous display device such as an electroluminescence (EL) display, a plasma display (PD), a field emission display (FED), and a liquid crystal display (LCD). .
　［光学フィルムの製造方法］
　本発明の光学フィルムの好ましい製造方法においては、水系溶媒で希釈され、ガラス転移温度（Ｔｇ）が６０℃未満の水分散性ウレタン樹脂（Ａ）と、ガラス転移温度（Ｔｇ）が６０℃以上１２０℃以下かつ耐温水性試験における重量増加率が２０％以下である水分散性ウレタン樹脂（Ｂ）と、を含有する易接着組成物を、熱可塑性樹脂フィルムの少なくとも一方の表面に塗布して塗膜を形成（塗布工程）し、次いで塗膜を乾燥して易接着層を形成（乾燥工程）する。 [Method for producing optical film]
In a preferred method for producing the optical film of the present invention, a water-dispersible urethane resin (A) diluted with an aqueous solvent and having a glass transition temperature (Tg) of less than 60 ° C., and a glass transition temperature (Tg) of 60 ° C. or more and 120 ° C. An easy-adhesive composition containing a water-dispersible urethane resin (B) having a weight increase rate of 20% or less in a warm water resistance test is applied to at least one surface of a thermoplastic resin film. A film is formed (application process), and then the coating film is dried to form an easy-adhesion layer (drying process).
　塗布工程において易接着組成物を塗布する方法としては、任意の適切な方法を採用することができる。例えば、バーコート法、ロールコート法、グラビアコート法、ロッドコート法、スロットオリフィスコート法、カーテンコート法、ファウンテンコート法等が挙げられる。塗布工程において形成する塗布膜の厚さは、当該塗布膜が易接着層となるときに必要な厚さに応じて、適宜調整することができる。 Any appropriate method can be adopted as a method of applying the easy-adhesion composition in the application step. Examples thereof 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 thickness of the coating film formed in the coating process can be appropriately adjusted according to the thickness required when the coating film becomes an easy-adhesion layer.
　熱可塑性樹脂フィルムにおける易接着組成物が塗布される表面は、表面処理が施されていることが好ましい。表面処理としては、コロナ放電処理、プラズマ処理であることが好ましい。コロナ放電処理或いはプラズマ処理を施すことにより、熱可塑性樹脂フィルムと易接着層との密着性を向上させることができる。 The surface of the thermoplastic resin film to which the easy-adhesion composition is applied is preferably subjected to a surface treatment. The surface treatment is preferably corona discharge treatment or plasma treatment. By performing the corona discharge treatment or the plasma treatment, the adhesion between the thermoplastic resin film and the easy adhesion layer can be improved.
　乾燥工程は、特に制限するものではなく、従来公知の方法を用いることができる。乾燥温度としては、代表的には５０℃以上、好ましくは９０℃以上、さらに好ましくは１１０℃以上である。乾燥温度をこのような範囲とすることにより、耐色性（特に、高温高湿下における）に優れた光学フィルムとすることができる。乾燥温度の上限は、好ましくは２００℃以下、さらに好ましくは１８０℃以下である。 The drying process is not particularly limited, and a conventionally known method can be used. The drying temperature is typically 50 ° C. or higher, preferably 90 ° C. or higher, more preferably 110 ° C. or higher. By setting the drying temperature in such a range, an optical film excellent in color resistance (particularly under high temperature and high humidity) can be obtained. The upper limit of the drying temperature is preferably 200 ° C. or lower, more preferably 180 ° C. or lower.
　熱可塑性樹脂フィルムを延伸する場合、延伸は、易接着層の形成前に行っても良く、易接着層の形成後に行っても良い。また、易接着層の形成と、熱可塑性樹脂フィルムの延伸とを同時に行っても良い。 When the thermoplastic resin film is stretched, the stretching may be performed before the formation of the easy-adhesion layer or after the formation of the easy-adhesion layer. Moreover, you may perform formation of an easily bonding layer and extending | stretching of a thermoplastic resin film simultaneously.
　易接着層の形成と、熱可塑性樹脂フィルムの延伸とを同時に行う場合、例えば、塗布工程の後に、易接着組成物の塗布膜を形成した熱可塑性樹脂フィルムを加熱雰囲気下で延伸すればよい。延伸のために当該フィルムに加える熱により、熱可塑性樹脂フィルムの表面に形成された易接着組成物の塗布膜が乾燥し、易接着層となる。このようにすれば、フィルムの延伸処理と易接着組成物の乾燥とを同時に実施でき、生産性に優れることから好ましい。 When forming the easy-adhesion layer and stretching the thermoplastic resin film at the same time, for example, after the coating step, the thermoplastic resin film on which the coating film of the easy-adhesive composition is formed may be stretched in a heated atmosphere. Due to the heat applied to the film for stretching, the coating film of the easy-adhesive composition formed on the surface of the thermoplastic resin film is dried to form an easy-adhesive layer. If it does in this way, the extending | stretching process of a film and drying of an easily bonding composition can be implemented simultaneously, and it is preferable from having excellent productivity.
　以下、実施例により、本発明をさらに詳細に説明する。なお、本発明は、以下の実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to the following examples.
　原料としては下記のものを用いた。また、水分散性ウレタン樹脂（Ａ）及び（Ｂ）の特性値についてガラス転移温度、破断伸度、耐温水性試験の重量増加率を表１に記載する。
＜水分散性ウレタン樹脂（Ａ）＞
・水分散性ウレタン樹脂（Ａ－１）のエマルジョン［第一工業製薬社製、スーパーフレックス（登録商標）２１０、固形分３５重量％］
・水分散性ウレタン樹脂（Ａ－２）のエマルジョン［第一工業製薬社製、スーパーフレックス（登録商標）１５０、固形分３０重量％］
・水分散性ウレタン樹脂（Ａ－３）のエマルジョン［第一工業製薬社製、スーパーフレックス（登録商標）４２０、固形分３２重量％］
・水分散性ウレタン樹脂（Ａ－４）のエマルジョン［第一工業製薬社製、スーパーフレックス（登録商標）４６０、固形分３８重量％］
＜水分散性ウレタン樹脂（Ｂ）＞
・水分散性ウレタン樹脂（Ｂ－１）のエマルジョン［第一工業製薬社製、スーパーフレックス（登録商標）１３０、固形分３５重量％］
・水分散性ウレタン樹脂（Ｂ－２）のエマルジョン［第一工業製薬社製、スーパーフレックス（登録商標）８７０、固形分３０重量％］
＜微粒子＞
・アクリロニトリル系微粒子（PAN微粒子）を含むエマルジョン［積水化学工業社製、ＡＤＶＡＮＣＥＬＬ　ＮＳ　Ｋ－００１、平均粒子径１５０ｎｍ、固形分２０重量％］ The following were used as raw materials. Table 1 shows the glass transition temperature, elongation at break, and weight increase rate of the hot water resistance test for the characteristic values of the water-dispersible urethane resins (A) and (B).
<Water-dispersible urethane resin (A)>
-Water-dispersible urethane resin (A-1) emulsion [Daiichi Kogyo Seiyaku Co., Ltd., Superflex (registered trademark) 210, solid content: 35% by weight]
-Emulsion of water-dispersible urethane resin (A-2) [Daiichi Kogyo Seiyaku Co., Ltd., Superflex (registered trademark) 150, solid content: 30% by weight]
-Emulsion of water-dispersible urethane resin (A-3) [Daiichi Kogyo Seiyaku Co., Ltd., Superflex (registered trademark) 420, solid content: 32% by weight]
-Emulsion of water-dispersible urethane resin (A-4) [Daiichi Kogyo Seiyaku Co., Ltd., Superflex (registered trademark) 460, solid content: 38% by weight]
<Water-dispersible urethane resin (B)>
-Emulsion of water-dispersible urethane resin (B-1) [Daiichi Kogyo Seiyaku Co., Ltd., Superflex (registered trademark) 130, solid content 35% by weight]
-Emulsion of water-dispersible urethane resin (B-2) [Daiichi Kogyo Seiyaku Co., Ltd., Superflex (registered trademark) 870, solid content: 30% by weight]
<Fine particles>
・ Emulsion containing acrylonitrile-based fine particles (PAN fine particles) [manufactured by Sekisui Chemical Co., Ltd., ADVANCEL NS K-001, average particle size 150 nm, solid content 20% by weight]
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
実施例１～４及び比較例１～８
　１．易接着組成物の製造
　表２に示す各成分が、表２に示す固形分量（単位は重量部）含まれるように、上記原料エマルジョンを選択し混合して、易接着組成物を製造した。なお、水系溶媒としてイオン交換水を使用し、易接着組成物の固形分量を最終的に８重量％となるよう調製した。 Examples 1 to 4 and Comparative Examples 1 to 8
1. Manufacture of an easily bonding composition The said raw material emulsion was selected and mixed so that each component shown in Table 2 might contain the solid content amount (unit is a weight part) shown in Table 2, and the easily bonding composition was manufactured. In addition, ion exchange water was used as an aqueous solvent, and the solid content of the easy-adhesion composition was adjusted to 8% by weight.
　２．光学フィルムの製造
　メタクリル系樹脂［Ｔｇ：１３５℃、溶融粘度：７００Ｐａ・ｓ（温度２７０℃、せん断速度１００（１／ｓｅｃ））］のペレットを、単軸押出機（φ＝２０．０ｍｍ、Ｌ／Ｄ＝２５）及びコートハンガータイプＴダイ（幅１５０ｍｍ）を用いて２８０℃で溶融押出し、１１０℃に保持した冷却ロールに溶融状態の上記樹脂を吐出して、厚さ１００μｍのメタクリル系樹脂フィルムを形成した。次に、メタクリル系樹脂フィルムの一方の表面に、上記で得られた易接着組成物を、バーコーターを用いて塗布した後、熱風乾燥機に投入して１００℃で９０秒間乾燥した。そして、テーブル延伸機を用いて当該フィルムを一軸延伸（延伸倍率：２．５倍）し、厚さ４０μｍのメタクリル系樹脂フィルムの表面に、厚さ０．３μｍの易接着層を有する光学フィルムを製造した。 2. Production of optical film Pellets of methacrylic resin [Tg: 135 ° C., melt viscosity: 700 Pa · s (temperature: 270 ° C., shear rate: 100 (1 / sec))] were uniaxially extruded (φ = 20.0 mm, L / D = 25) and a coat hanger type T die (width: 150 mm), melt extruded at 280 ° C., and the molten resin is discharged onto a cooling roll held at 110 ° C. to obtain a methacrylic resin film having a thickness of 100 μm. Formed. Next, after applying the easy-adhesion composition obtained above on one surface of the methacrylic resin film using a bar coater, it was put into a hot air dryer and dried at 100 ° C. for 90 seconds. Then, the film is uniaxially stretched using a table stretching machine (stretching ratio: 2.5 times), and an optical film having an easy-adhesion layer having a thickness of 0.3 μm is formed on the surface of the methacrylic resin film having a thickness of 40 μm. Manufactured.
　３．偏光板の製造
　上記で得られた光学フィルムの易接着層側に、ポリビニルアルコール系接着剤組成物を塗布した。また、ケン化処理を施した厚さ４０μｍのトリアセチルセルロースフィルム（保護フィルム）の片側にポリビニルアルコール系接着剤組成物を塗布した。次に、厚さ３０μｍの偏光子の両側それぞれに光学フィルム及び保護フィルムをポリビニルアルコール系接着剤塗布層を介して積層し、得られた積層体を熱風乾燥機（７０℃）に投入して５分乾燥させて、偏光板を製造した。また、偏光子の両側がトリアセチルセルロース保護フィルムを設けた評価用の基準偏光板を同様に作成した。 3. Manufacture of a polarizing plate The polyvinyl alcohol-type adhesive composition was apply | coated to the easily bonding layer side of the optical film obtained above. Moreover, the polyvinyl alcohol-type adhesive composition was apply | coated to one side of the 40-micrometer-thick triacetylcellulose film (protective film) which performed the saponification process. Next, an optical film and a protective film are laminated on both sides of a polarizer having a thickness of 30 μm via a polyvinyl alcohol adhesive coating layer, and the obtained laminate is put into a hot air dryer (70 ° C.). It was made to dry for a while and the polarizing plate was manufactured. Further, a reference polarizing plate for evaluation in which both sides of the polarizer were provided with a triacetyl cellulose protective film was similarly prepared.
　上記で得られた偏光板について、以下に示す評価を行った。評価結果を表２に示す。
（１）初期密着性
　上記で得られた偏光板から２５ｍｍ×２５０ｍｍの寸法の試験片を切り出し、試験片の光学フィルムの表面に粘着加工を施した後、ガラス板に貼り付け測定用サンプルを得た。その後、サンプルの偏光子と光学フィルムとの間に切込みを入れ、偏光子と保護フィルムとを掴み、日本接着剤工業規格　ＪＡＩ　１３－１９９６の浮動ローラー法に準じて、９０度での剥離接着強さを測定した。なお、基準偏光板においても同様の条件で剥離接着強さを測定した。測定結果から、剥離接着強さを次の基準により評価した。
　◎：基準偏光板よりも剥離接着強さが優れる
　○：基準偏光板と剥離接着強さが同等
　△：基準偏光板よりも剥離接着強さが劣る
　×：密着しておらず測定不可
（２）耐湿熱性（６０℃、９０％ＲＨ）
　上記と同様にして得た測定用サンプルを温度６０℃、湿度９０％ＲＨの恒温恒湿機に入れ、２５０時間及び５００時間放置する熱処理を施した以外は、初期密着性の評価と同様にして、剥離接着強さを測定した。測定結果から剥離接着強さを次の基準により評価した。
　◎：基準偏光板よりも剥離接着強さが優れる
　○：基準偏光板と剥離接着強さが同等
　△：基準偏光板よりも剥離接着強さが劣る
　×：密着しておらず測定不可
（３）耐湿熱性（８０℃、９０％ＲＨ）
　上記と同様にして得た測定用サンプルを温度８０℃、湿度９０％ＲＨの恒温恒湿機に入れ、１００時間放置する熱処理を施した以外は、初期密着性の評価と同様にして、剥離接着強さを測定した。測定結果から剥離接着強さを次の基準により評価した。
　◎：基準偏光板よりも剥離接着強さが優れる
　○：基準偏光板と剥離接着強さが同等
　△：基準偏光板よりも剥離接着強さが劣る
　×：密着しておらず測定不可 The following evaluation was performed about the polarizing plate obtained above. The evaluation results are shown in Table 2.
(1) Initial adhesion After cutting out a test piece having a size of 25 mm × 250 mm from the polarizing plate obtained above, and applying an adhesive process to the surface of the optical film of the test piece, a sample for measurement was obtained by sticking to a glass plate. It was. After that, a notch is made between the sample polarizer and the optical film, the polarizer and the protective film are gripped, and the peel adhesion strength at 90 degrees according to the floating roller method of Japan Adhesive Industry Standard JAI 13-1996. Was measured. The peel adhesion strength was also measured under the same conditions for the reference polarizing plate. From the measurement results, the peel adhesion strength was evaluated according to the following criteria.
◎: Peeling adhesive strength is superior to the reference polarizing plate ○: Peeling adhesive strength is equivalent to the reference polarizing plate △: Peeling adhesive strength is inferior to the reference polarizing plate ×: Not measured and cannot be measured (2) Moist heat resistance (60 ° C, 90% RH)
The measurement sample obtained in the same manner as described above was put in a constant temperature and humidity chamber at a temperature of 60 ° C. and a humidity of 90% RH, and was subjected to a heat treatment that was allowed to stand for 250 hours and 500 hours. The peel adhesion strength was measured. From the measurement results, the peel adhesion strength was evaluated according to the following criteria.
◎: Peeling adhesive strength is superior to the reference polarizing plate ○: Peeling adhesive strength is equivalent to the reference polarizing plate △: Peeling adhesive strength is inferior to the reference polarizing plate ×: Not measured and cannot be measured (3) Moisture and heat resistance (80 ° C, 90% RH)
The sample for measurement obtained in the same manner as described above was put into a constant temperature and humidity chamber at a temperature of 80 ° C. and a humidity of 90% RH, and was subjected to a heat treatment that was allowed to stand for 100 hours. Strength was measured. From the measurement results, the peel adhesion strength was evaluated according to the following criteria.
◎: Peeling adhesive strength is superior to the reference polarizing plate ○: Peeling adhesive strength is equivalent to the reference polarizing plate △: Peeling adhesive strength is inferior to the reference polarizing plate
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表２に示すように、Ｔｇが６０℃未満である水分散性ウレタン樹脂（Ａ）とＴｇが６０℃以上１２０℃以下かつ耐温水性試験における重量増加率が２０％以下の水分散性ウレタン樹脂（Ｂ）とを含有する易接着層を使用した実施例１乃至４の光学フィルムは、初期密着性に優れ、高温高湿下での長時間使用における密着性においても優れる結果を示した。一方、表２に示すように、Ｔｇが６０℃未満である水分散性ウレタン樹脂（Ａ）のみを含有する比較例１乃至６の光学フィルムは、高温高湿下での長時間使用における密着性に劣る結果を示した。また、Ｔｇが６０℃以上１２０℃以下かつ耐温水性試験における重量増加率が２０％以下の水分散性ウレタン樹脂（Ｂ）のみを含有する比較例７及び８の光学フィルムは、高温高湿処理後の密着性が向上したが、初期密着性に劣る結果を示した。
 

  As shown in Table 2, a water dispersible urethane resin (A) having a Tg of less than 60 ° C. and a water dispersible urethane resin having a Tg of 60 ° C. or more and 120 ° C. or less and a weight increase rate in a warm water resistance test of 20% or less. The optical films of Examples 1 to 4 using the easy-adhesion layer containing (B) showed excellent results in initial adhesion and excellent adhesion in long-term use under high temperature and high humidity. On the other hand, as shown in Table 2, the optical films of Comparative Examples 1 to 6 containing only the water-dispersible urethane resin (A) having a Tg of less than 60 ° C. are adhesive in long-time use under high temperature and high humidity. Inferior results. Further, the optical films of Comparative Examples 7 and 8 containing only the water-dispersible urethane resin (B) having a Tg of 60 ° C. or more and 120 ° C. or less and a weight increase rate of 20% or less in the hot water resistance test are high temperature and high humidity treatments. Although the later adhesion was improved, the results showed inferior initial adhesion.


Claims (10)

  1. 　ガラス転移温度が６０℃未満の水分散性ウレタン樹脂（Ａ）と、ガラス転移温度が６０℃以上１２０℃以下かつ耐温水性試験における重量増加率が２０％以下である水分散性ウレタン樹脂（Ｂ）とを含む易接着組成物。 A water-dispersible urethane resin (A) having a glass transition temperature of less than 60 ° C. and a water-dispersible urethane resin (B) having a glass transition temperature of 60 ° C. or more and 120 ° C. or less and a weight increase rate in a warm water resistance test of 20% or less. ).
  2. 　前記水分散性ウレタン樹脂（Ａ）と前記水分散性ウレタン樹脂（Ｂ）との重量比が９５：５～４０：６０の範囲である請求項１記載の易接着組成物。 The easy-adhesion composition according to claim 1, wherein the weight ratio of the water-dispersible urethane resin (A) to the water-dispersible urethane resin (B) is in the range of 95: 5 to 40:60.
  3. 　前記水分散性ウレタン樹脂（Ａ）のガラス転移温度が、－２５℃以上である請求項１又は２記載の易接着組成物。 The easily adhesive composition according to claim 1 or 2, wherein the water-dispersible urethane resin (A) has a glass transition temperature of -25 ° C or higher.
  4. 　前記水分散性ウレタン樹脂（Ａ）の破断伸度が、３００％以下である請求項１乃至３のいずれか記載の易接着組成物。 The easily adhesive composition according to any one of claims 1 to 3, wherein the water-dispersible urethane resin (A) has a breaking elongation of 300% or less.
  5. 　前記水分散性ウレタン樹脂（Ｂ）の破断伸度が、１００％以下である請求項１乃至４のいずれか記載の易接着組成物。 The easily adhesive composition according to any one of claims 1 to 4, wherein the water-dispersible urethane resin (B) has a breaking elongation of 100% or less.
  6. 　さらに微粒子を水分散性ウレタン樹脂（Ａ）及び（Ｂ）の合計１００重量部に対して、０．１～１５重量部含む請求項１乃至５のいずれか記載の易接着組成物。 6. The easy-adhesion composition according to claim 1, further comprising 0.1 to 15 parts by weight of fine particles with respect to 100 parts by weight of the total of the water-dispersible urethane resins (A) and (B).
  7. 　熱可塑性樹脂フィルムと、該熱可塑性樹脂フィルムの少なくとも一方の表面に設けられた易接着層とを備えた光学フィルムであって、該易接着層が請求項１乃至６のいずれか記載の易接着組成物から形成されていることを特徴とする光学フィルム。 An easily adhesive layer according to any one of claims 1 to 6, wherein the easily adhesive layer is an optical film comprising a thermoplastic resin film and an easily adhesive layer provided on at least one surface of the thermoplastic resin film. An optical film formed from a composition.
  8. 　前記樹脂フィルムは、（メタ）アクリル系樹脂からなる請求項７記載の光学フィルム。 The optical film according to claim 7, wherein the resin film is made of a (meth) acrylic resin.
  9. 　請求項７又は８記載の光学フィルムと、接着剤層と、偏光子とが、前記易接着層が該接着剤層に接するようにして、この順に積層されて構成された偏光板。 A polarizing plate constituted by laminating the optical film according to claim 7 or 8, an adhesive layer, and a polarizer in this order so that the easy-adhesion layer is in contact with the adhesive layer.
  10. 　水系溶媒で希釈された、ガラス転移温度が６０℃未満の水分散性ウレタン樹脂（Ａ）と、ガラス転移温度が６０℃以上１２０℃以下かつ耐温水性試験における重量増加率が２０％以下である水分散性ウレタン樹脂（Ｂ）とを含む易接着組成物を、熱可塑性樹脂フィルムの少なくとも一方の表面に塗布して塗膜を形成する工程と、前記塗膜を乾燥して易接着層を形成する工程からなる光学フィルムの製造方法。

          A water-dispersible urethane resin (A) diluted with an aqueous solvent and having a glass transition temperature of less than 60 ° C., a glass transition temperature of 60 ° C. or more and 120 ° C. or less, and a weight increase rate in a warm water resistance test of 20% or less. Applying an easy-adhesive composition containing a water-dispersible urethane resin (B) to at least one surface of a thermoplastic resin film to form a coating film, and drying the coating film to form an easy-adhesion layer The manufacturing method of the optical film which consists of a process to do.

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019155791A1 (en) * 2018-02-07 2019-08-15 日東電工株式会社 Polarizing plate and image display device
JP2019139204A (en) * 2018-02-07 2019-08-22 日東電工株式会社 Polarizing plate and image display unit
JP2019183100A (en) * 2018-03-30 2019-10-24 株式会社日本触媒 Easily-adhesive base material
JP2020008861A (en) * 2018-07-09 2020-01-16 エスケイシー・カンパニー・リミテッドＳｋｃ Ｃｏ．， Ｌｔｄ． Optical multilayer film, optical component having the same, and display device
WO2022239648A1 (en) * 2021-05-08 2022-11-17 大倉工業株式会社 Optical film, polarizing plate, image display device, and method for manufacturing optical film
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CN110497672B (en) * 2018-07-25 2020-08-25 日东电工株式会社 Easy-to-adhere film, method for producing the same, polarizing plate, and image display device
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006124752A (en) * 2004-10-27 2006-05-18 Nippon Paint Co Ltd Chromium-free prime coat treating agent having excellent adhesion and corrosion resistance
JP2006247963A (en) * 2005-03-09 2006-09-21 Oji Paper Co Ltd Inkjet recording sheet
JP2009081394A (en) * 2007-09-27 2009-04-16 Toppan Printing Co Ltd Sheet for sealing rear surface of solar cell, and solar cell module using same
JP2009193061A (en) * 2008-01-17 2009-08-27 Nitto Denko Corp Polarizing plate and image display device using polarizing plate
JP2010262004A (en) * 2009-04-30 2010-11-18 Seiko Epson Corp Optical article and method for producing the same
JP2011183307A (en) * 2010-03-09 2011-09-22 Sumitomo Metal Ind Ltd Surface-treated steel plate having excellent resistance to dew condensation blushing and corrosion
WO2015098539A1 (en) * 2013-12-28 2015-07-02 大倉工業株式会社 Optical film and manufacturing method therefor

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4798156B2 (en) * 2008-03-17 2011-10-19 三菱樹脂株式会社 Laminated film
CN102648094B (en) * 2009-12-04 2015-04-08 东洋纺织株式会社 Highly adhesive thermoplastic resin film
CN103890113B (en) * 2012-05-30 2017-03-29 Lg化学株式会社 Waterborne compositions, the blooming comprising which, the Polarizer using the blooming and the liquid crystal display device using the Polarizer
KR102066640B1 (en) * 2016-09-20 2020-01-15 주식회사 엘지화학 Optical film with high adhesiveness, and polarizing plate comprising the same

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006124752A (en) * 2004-10-27 2006-05-18 Nippon Paint Co Ltd Chromium-free prime coat treating agent having excellent adhesion and corrosion resistance
JP2006247963A (en) * 2005-03-09 2006-09-21 Oji Paper Co Ltd Inkjet recording sheet
JP2009081394A (en) * 2007-09-27 2009-04-16 Toppan Printing Co Ltd Sheet for sealing rear surface of solar cell, and solar cell module using same
JP2009193061A (en) * 2008-01-17 2009-08-27 Nitto Denko Corp Polarizing plate and image display device using polarizing plate
JP2010262004A (en) * 2009-04-30 2010-11-18 Seiko Epson Corp Optical article and method for producing the same
JP2011183307A (en) * 2010-03-09 2011-09-22 Sumitomo Metal Ind Ltd Surface-treated steel plate having excellent resistance to dew condensation blushing and corrosion
WO2015098539A1 (en) * 2013-12-28 2015-07-02 大倉工業株式会社 Optical film and manufacturing method therefor

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019155791A1 (en) * 2018-02-07 2019-08-15 日東電工株式会社 Polarizing plate and image display device
JP2019139204A (en) * 2018-02-07 2019-08-22 日東電工株式会社 Polarizing plate and image display unit
JP2019183100A (en) * 2018-03-30 2019-10-24 株式会社日本触媒 Easily-adhesive base material
JP7257123B2 (en) 2018-03-30 2023-04-13 株式会社日本触媒 Adhesive base material
JP2020008861A (en) * 2018-07-09 2020-01-16 エスケイシー・カンパニー・リミテッドＳｋｃ Ｃｏ．， Ｌｔｄ． Optical multilayer film, optical component having the same, and display device
US11454753B2 (en) 2018-07-09 2022-09-27 Skc Co., Ltd. Optical multilayer film, and optical component and display device comprising the same
WO2022239648A1 (en) * 2021-05-08 2022-11-17 大倉工業株式会社 Optical film, polarizing plate, image display device, and method for manufacturing optical film
KR20230029528A (en) 2021-08-23 2023-03-03 오꾸라 고교 가부시키가이샤 Method for producing optical film

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