WO2023120157A1 - 防汚層付き光学フィルムおよびその製造方法 - Google Patents

防汚層付き光学フィルムおよびその製造方法 Download PDF

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Publication number
WO2023120157A1
WO2023120157A1 PCT/JP2022/044871 JP2022044871W WO2023120157A1 WO 2023120157 A1 WO2023120157 A1 WO 2023120157A1 JP 2022044871 W JP2022044871 W JP 2022044871W WO 2023120157 A1 WO2023120157 A1 WO 2023120157A1
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Prior art keywords
layer
film
antifouling layer
optical film
antifouling
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PCT/JP2022/044871
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English (en)
French (fr)
Japanese (ja)
Inventor
幸大 宮本
豊 角田
智剛 梨木
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Nitto Denko Corp
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Nitto Denko Corp
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Priority to KR1020237023118A priority Critical patent/KR20240131246A/ko
Priority to CN202280034167.2A priority patent/CN117295611A/zh
Priority to JP2023540467A priority patent/JP7373698B1/ja
Publication of WO2023120157A1 publication Critical patent/WO2023120157A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/28—Processes for applying liquids or other fluent materials performed by transfer from the surfaces of elements carrying the liquid or other fluent material, e.g. brushes, pads, rollers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
    • 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
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/56—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks
    • C23C14/562—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks for coating elongated substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2252/00—Sheets
    • B05D2252/02—Sheets of indefinite length

Definitions

  • the present invention relates to an optical film with an antifouling layer and a method for producing the same.
  • an optical film with an antifouling layer is attached to the outer surface of a display such as a touch panel display on the image display side.
  • An optical film with an antifouling layer includes a transparent substrate film and an antifouling layer disposed on the outermost surface on one side of the transparent substrate film.
  • the antifouling layer suppresses adhesion of contaminants such as oil from hands to the outer surface of the display, and facilitates removal of the adhering contaminants.
  • An optical film with an antifouling layer is manufactured, for example, by a roll-to-roll method from the viewpoint of manufacturing efficiency.
  • the antifouling layer forming step in the roll-to-roll method for example, while running a long transparent base film as a work film along the pass line in the same process, the base material is removed at a predetermined location in the pass line.
  • An antifouling layer is formed on one side in the thickness direction of the film.
  • the antifouling layer is formed from a highly water-repellent material by, for example, a wet coating method or a dry coating method.
  • the optical film with an antifouling layer (having an antifouling layer on its surface) is wound up by a take-up roller.
  • the antifouling layer on the outermost surface on one side of the transparent substrate film is in contact with the other side (back surface) of the same film.
  • a load is applied in the film thickness direction (roll radial direction).
  • the present inventors have obtained the following findings regarding the optical film with an antifouling layer produced as described above.
  • the antifouling layer material is easily transferred from the antifouling layer to the back surface of the transparent substrate film. This problem is particularly likely to occur when the antifouling layer is formed by a dry coating method. In addition, the above problem is more likely to occur as the antifouling layer formed is thicker.
  • the present invention provides a method for producing an optical film with an antifouling layer, which is suitable for producing an optical film with an antifouling layer by a roll-to-roll method while suppressing adhesion of an antifouling layer material to the back surface of a transparent substrate film. and an optical film with an antifouling layer.
  • the present invention [1] includes an antifouling layer forming step of forming an antifouling layer on one side in the thickness direction of the transparent base film while transporting the transparent base film by a roll-to-roll method, It includes a method for producing an optical film with an antifouling layer, wherein the surface free energy of the other side in the thickness direction of the transparent substrate film is 45 mN/m or less.
  • the present invention [2] includes the method for producing an optical film with an antifouling layer according to [1] above, wherein the surface free energy is 20 mN/m or more.
  • the present invention [3] includes the method for producing an optical film with an antifouling layer according to [1] or [2] above, wherein in the antifouling layer forming step, the antifouling layer is formed by a dry coating method.
  • the present invention [4] includes the method for producing an optical film with an antifouling layer according to any one of [1] to [3] above, wherein the antifouling layer has a thickness of 6 nm or more.
  • the present invention [5] comprises a transparent base film and an antifouling layer disposed on one side in the thickness direction of the transparent base film, wherein the other side in the thickness direction of the transparent base film has a free surface.
  • An optical film with an antifouling layer having an energy of 45 mN/m or less is included.
  • the present invention [6] includes the optical film with an antifouling layer according to [5] above, wherein the surface free energy is 20 mN/m or more.
  • the present invention [7] includes the optical film with an antifouling layer according to [5] or [6] above, wherein the antifouling layer is a dry coating film.
  • the present invention [8] includes the optical film with an antifouling layer according to any one of [5] to [7] above, wherein the antifouling layer has a thickness of 6 nm or more.
  • the surface free energy of the other side (back side) in the thickness direction of the transparent substrate film is 45 mN/m or less. Therefore, this production method is suitable for producing an optical film with an antifouling layer by a roll-to-roll method while suppressing adhesion of the antifouling layer material to the back surface of the transparent base film.
  • the optical film with an antifouling layer of the present invention comprises a transparent substrate film having a back surface with a surface free energy of 45 mN/m or less. Such an optical film with an antifouling layer is suitable for roll-to-roll production while suppressing adhesion of the antifouling layer material to the back surface of the transparent base film.
  • FIG. 1A shows a step of preparing a transparent substrate film
  • FIG. 1B shows a step of forming a hard coat layer
  • FIG. 1C shows an example of a transfer suppression treatment step.
  • 2A shows the step of forming the adhesion layer
  • FIG. 2B shows the step of forming the antireflection layer
  • FIG. 2C shows the step of forming the antifouling layer.
  • FIG. 1A is a preparation step (FIG. 1A), a hard coat layer forming step (FIG. 1B), a transfer suppression treatment step (FIG. 1C), and an adhesion layer forming step ( 2A), an antireflection layer forming step (FIG. 2B), and an antifouling layer forming step (FIG. 2C).
  • a preparation step FIG. 1A
  • a hard coat layer forming step FIG. 1B
  • FIG. 1C is a transfer suppression treatment step
  • FIG. 1C an adhesion layer forming step
  • 2A an antireflection layer forming step
  • FIG. 2C antifouling layer forming step
  • a resin film 11 is prepared as shown in FIG. 1A.
  • the resin film 11 has a long shape so that this manufacturing method can be carried out by a roll-to-roll system. Also, the resin film 11 has a first surface 11a and a second surface 11b opposite to the first surface 11a.
  • the resin film 11 is a flexible transparent resin film.
  • materials for the resin film 11 include polyester resin, polyolefin resin, polystyrene resin, acrylic resin, polycarbonate resin, polyethersulfone resin, polysulfone resin, polyamide resin, polyimide resin, cellulose resin, norbornene resin, polyarylate resin, and A polyvinyl alcohol resin is mentioned.
  • Polyester resins include, for example, polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate.
  • Polyolefin resins include, for example, polyethylene, polypropylene, and cycloolefin polymers (COP).
  • Cellulose resins include, for example, triacetyl cellulose (TAC).
  • the material for the resin film 11 one selected from the group consisting of polyester resin, polyolefin resin, and cellulose resin is used from the viewpoint of transparency and strength, and more preferably the group consisting of PET, COP, and TAC. A more selected one is used.
  • the first surface 11a of the resin film 11 (the surface on which the hard coat layer 12 described below is laminated) may be subjected to a surface modification treatment.
  • Surface modification treatments include, for example, corona treatment, plasma treatment, ozone treatment, primer treatment, glow treatment, and coupling agent treatment.
  • the thickness of the resin film 11 is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, and even more preferably 20 ⁇ m or more.
  • the thickness of the resin film 11 is preferably 300 ⁇ m or less, more preferably 200 ⁇ m or less, from the viewpoint of handleability.
  • the total light transmittance (JIS K 7375-2008) of the resin film 11 is preferably 80% or higher, more preferably 90% or higher, still more preferably 95% or higher. Such a configuration is preferable for ensuring the transparency required for the optical film F when the manufactured optical film (optical film F described later) is provided on the surface of a display such as a touch panel display.
  • the total light transmittance of the resin film 11 is, for example, 100% or less.
  • a hard coat layer 12 is formed on the resin film 11 as shown in FIG. 1B.
  • the transparent substrate film 10 including the resin film 11 and the hard coat layer 12 is obtained.
  • the hard coat layer 12 forms one surface (surface 10a) in the thickness direction D of the transparent base film 10 .
  • the hard coat layer 12 is a layer for making it difficult for scratches to form on the exposed surface of the optical film F (the upper surface in the figure for the optical film F shown in FIG. 2C).
  • a hard-coat layer formation process is implemented by a roll-to-roll system in this embodiment.
  • the hard coat layer 12 can be formed, for example, by applying a curable resin composition (varnish) on the first surface 11a of the resin film 11 to form a coating film, and then drying and curing the coating film.
  • a curable resin composition contains a curable resin and a solvent.
  • the hard coat layer 12 is a cured product of a curable resin composition (specifically, a curable resin).
  • curable resins examples include polyester resins, acrylic resins, urethane resins, acrylic urethane resins, amide resins, silicone resins, epoxy resins, and melamine resins. These curable resins may be used alone, or two or more of them may be used in combination. From the viewpoint of ensuring high hardness of the hard coat layer 12, acrylic urethane resin is preferably used as the curable resin.
  • curable resins include ultraviolet curable resins and thermosetting resins.
  • the coating film is cured by ultraviolet irradiation.
  • the curable resin composition contains a thermosetting resin, the coating film is cured by heating.
  • an ultraviolet curable resin is preferably used from the viewpoint of improving the production efficiency of the optical film F because it can be cured without heating to a high temperature.
  • the UV-curable resin includes at least one selected from the group consisting of UV-curable monomers, UV-curable oligomers, and UV-curable polymers. Specific examples of the composition containing an ultraviolet curable resin include the composition for forming a hard coat layer described in JP-A-2016-179686.
  • Solvents contained in the curable resin composition include, for example, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, benzene, toluene, xylene, methanol, ethanol, isopropanol, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether. Acetate, dichloromethane, and chloroform are included.
  • the curable resin composition may contain fine particles.
  • the addition of fine particles to the curable resin composition is useful for adjusting the hardness, adjusting the surface roughness, adjusting the refractive index, and imparting antiglare properties of the hard coat layer 12 .
  • Microparticles include, for example, metal oxide particles, glass particles, and organic particles.
  • Materials for metal oxide particles include, for example, silica, alumina, titania, zirconia, calcium oxide, tin oxide, indium oxide, cadmium oxide, and antimony oxide.
  • Materials for the organic particles include, for example, polymethylmethacrylate, polystyrene, polyurethane, acrylic-styrene copolymers, benzoguanamine, melamine, and polycarbonate.
  • the thickness of the hard coat layer 12 is preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more, and even more preferably 5 ⁇ m, from the viewpoint of ensuring the hardness of the surface 23a of the antifouling layer 23 described later by ensuring the hardness of the hard coat layer 12. That's it. From the viewpoint of ensuring the flexibility of the optical film F, the thickness of the hard coat layer 12 is preferably 50 ⁇ m or less, more preferably 40 ⁇ m or less, still more preferably 35 ⁇ m or less, and particularly preferably 30 ⁇ m or less.
  • a surface 12a (the surface on which the adhesion layer 21 described later is laminated) as one surface in the thickness direction D of the hard coat layer 12 is subjected to a surface modification treatment as necessary.
  • Surface modification treatments include, for example, plasma treatment, corona treatment, ozone treatment, primer treatment, glow treatment, and coupling agent treatment.
  • the surface 12a is preferably plasma-treated.
  • argon gas for example, is used as an inert gas.
  • the discharge power in the plasma treatment is, for example, 10 W or more and, for example, 10000 W or less.
  • the second surface 11b of the resin film 11, which is the other surface (back surface 10b) in the thickness direction D of the transparent substrate film 10, is subjected to transfer suppression treatment.
  • the transfer suppressing treatment include attaching a lubricant to the back surface 10b and forming a resin layer (transfer suppressing layer) containing the lubricant.
  • Lubricants include, for example, wax esters, natural waxes containing the wax esters, silicone-based lubricants, and fluorine-based lubricants.
  • Wax esters are, for example, esters of higher fatty acids and higher alcohols.
  • Wax esters include, for example, myricyl cerotate, myricyl palmitate, cetyl palmitate, and stearyl stearate.
  • Natural waxes containing wax esters include, for example, vegetable waxes and animal waxes. Vegetable waxes include, for example, carnauba wax (containing myricyl cerotinate as a main component) and palm wax.
  • Animal waxes include, for example, beeswax and spermaceti.
  • silicone-based lubricants include dimethylpolysiloxane and modified products thereof, carboxyl-modified silicone, ⁇ -methylstyrene-modified silicone, ⁇ -olefin-modified silicone, polyether-modified silicone, epoxy-modified silicone, amino-modified silicone, amide-modified silicone, and alcohol-modified silicones;
  • the transparent substrate film 10 includes a resin film 11, a hard coat layer 12 on the first surface 11a, and a transfer suppressing layer 13 on the second surface 11b.
  • the transfer suppressing layer 13 forms the other surface (back surface 10b) in the thickness direction D of the transparent substrate film 10 .
  • the transfer suppressing layer 13 can be formed, for example, by applying a curable resin composition (varnish) on the second surface 11b of the resin film 11 to form a coating film, and then drying and curing the coating film.
  • the curable resin composition for forming the transfer suppressing layer 13 contains, for example, a curable resin, the lubricant described above, and a solvent, and if necessary, further contains other components such as an antistatic agent. .
  • the transfer suppressing layer 13 is a cured product of such a curable resin composition.
  • the curable resin and solvent include, for example, the curable resins and solvents described above for the hard coat layer 12 .
  • the content of the lubricant in the transfer suppressing layer 13 is preferably 5% by mass or more, more preferably 8% by mass. Above, more preferably 10% by mass or more, preferably 50% by mass or less, more preferably 45% by mass or less, and even more preferably 40% by mass or less.
  • the lubricant in the transfer suppressing layer 13 wax esters and natural waxes containing the wax esters are preferable because they are less likely to whiten even under hot and humid conditions. It is important for films that require optical transparency that components in the transfer inhibiting layer 13 are resistant to whitening.
  • the transfer suppressing layer 13 preferably contains an antistatic agent. Containing an antistatic agent in the transfer suppressing layer 13 is preferable for imparting antistatic properties to the optical film F and suppressing adhesion of foreign matter to the optical film F.
  • Antistatic agents include, for example, organic antistatic agents and inorganic antistatic agents.
  • Organic antistatic agents include, for example, cationic antistatic agents (having cationic functional groups such as quaternary ammonium salts, pyridinium salts, primary amino groups, secondary amino groups, and tertiary amino groups), and anionic antistatic agents.
  • Antistatic agents having anionic functional groups such as sulfonates, sulfates, phosphonates, and phosphates), zwitterionic antistatic agents (alkylbetaine and its derivatives, imidazoline and its derivatives, alanine and its derivatives, etc.), nonionic antistatic agents (aminoalcohol and its derivatives, glycerin and its derivatives, polyethylene glycol and its derivatives, etc.), and conductive polymers.
  • Conductive polymers include, for example, polythiophene, polyaniline, polypyrrole, polyethyleneimine, and allylamine.
  • inorganic antistatic agents include tin oxide, antimony oxide, indium oxide, cadmium oxide, titanium oxide, zinc oxide, indium, tin, antimony, gold, silver, copper, aluminum, nickel, chromium, titanium, iron, cobalt , copper iodide, indium-tin composite oxide (ITO), and antimony-tin composite oxide (ATO).
  • the content of the antistatic agent in the transfer suppressing layer 13 is preferably 0.03% by mass or more, more preferably 0.05% by mass or more, and still more preferably 0.1% by mass, from the viewpoint of ensuring good antistatic properties. % or more, preferably 10% by mass or less, more preferably 5% by mass or less.
  • the thickness of the transfer suppressing layer 13 is preferably 1 nm or more, more preferably 3 nm or more, and still more preferably 5 nm or more from the viewpoint of appropriately controlling the surface free energy of the back surface 10b of the transparent substrate film 10 within the range described later. be.
  • the thickness of the transfer suppressing layer 13 is preferably 1000 nm or less, more preferably 500 nm or less, and even more preferably 100 nm or less, from the viewpoints of ensuring good appearance of the optical film F and suppressing manufacturing costs.
  • the surface free energy of the back surface 10b of the transparent substrate film 10 is 45 mN/m or less, preferably 43 mN/m or less, more preferably 40 mN/m or less. Surface free energy is measured by the method described below with respect to the examples. The lower the surface free energy of the back surface 10b, the lower the affinity between the back surface 10b and an antifouling layer material such as an organic fluorine compound having a fluorinated alkyl group at its end.
  • the surface free energy of the back surface 10b of the transparent base film 10 is, for example, 15 mN/m or more from the viewpoint of properly transporting the transparent base film 10 (work film) in the roll-to-roll manufacturing process.
  • It is preferably 20 mN/m or more, more preferably 25 mN/m or more, and still more preferably 30 mN/m or more.
  • ⁇ d is the dispersive component of the surface free energy
  • ⁇ p is the polar component of the surface free energy
  • ⁇ h is the hydrogen bonding component of the surface free energy.
  • the method for obtaining the surface free energy is as described later with regard to Examples.
  • the adhesion layer 21 is a layer for ensuring adhesion of the inorganic oxide layer (antireflection layer 22 described later in this embodiment) to the organic layer (hard coat layer 12 in this embodiment).
  • materials for the adhesion layer 21 include metals such as silicon, nickel, chromium, aluminum, tin, gold, silver, platinum, zinc, titanium, tungsten, zirconium, and palladium, and alloys of two or more of these metals. , and oxides of these metals.
  • the adhesion layer 21 Indium tin oxide (ITO) or silicon oxide (SiOx) is preferably used as the material of .
  • ITO Indium tin oxide
  • SiOx silicon oxide
  • SiOx with less oxygen content than the stoichiometric composition is used, and more preferably SiOx with x of 1.2 or more and 1.9 or less is used.
  • the adhesion layer 21 is formed, for example, by depositing a material using a dry coating method. Dry coating methods include sputtering, vacuum deposition, and CVD, with sputtering being preferred.
  • a negative voltage is applied to the target placed on the cathode while gas is introduced into the sputtering chamber under vacuum conditions.
  • glow discharge is generated to ionize the gas atoms, and the gas ions collide with the target surface at high speed, ejecting the target material from the target surface and depositing the ejected target material on a predetermined surface.
  • Reactive sputtering is preferable as the sputtering method from the viewpoint of film formation rate.
  • a metal target is used as the target, and a mixed gas of an inert gas such as argon and oxygen (reactive gas) is used as the above gas.
  • Examples of power sources for carrying out the sputtering method include DC power sources, AC power sources, RF power sources, and MFAC power sources (AC power sources with a frequency band of several kHz to several MHz).
  • the discharge voltage in the sputtering method is, for example, 200 V or higher and, for example, 1000 V or lower.
  • the film forming pressure in the sputtering chamber where the sputtering method is performed is preferably 0.01 Pa or higher, more preferably 0.05 Pa or higher, and even more preferably 0.1 Pa or higher.
  • the film formation pressure is, for example, 2 Pa or less from the viewpoint of discharge stability.
  • the thickness of the adhesion layer 21 is preferably 1 nm or more and 10 nm or less from the viewpoint of ensuring both the adhesion between the hard coat layer 12 and the antireflection layer 22 and the transparency of the adhesion layer 21 .
  • the antireflection layer 22 is formed on one surface of the adhesion layer 21 in the thickness direction D.
  • the antireflection layer 22 is a layer for suppressing the reflection intensity of external light.
  • the antireflection layer 22 has high refractive index layers with a relatively high refractive index and low refractive index layers with a relatively low refractive index alternately in the thickness direction.
  • the net reflected light intensity is attenuated by interference between reflected light at multiple interfaces in multiple thin layers (high refractive index layer, low refractive index layer) included in the same layer.
  • the optical film thickness the product of the refractive index and the thickness
  • such antireflection layer 22 in the present embodiment includes a first high refractive index layer 22a, a first low refractive index layer 22b, a second high refractive index layer 22c, and a second low refractive index layer 22c. and a layer 22d in this order toward one side in the thickness direction D.
  • the first high refractive index layer 22a, the first low refractive index layer 22b, the second high refractive index layer 22c, and the second low refractive index layer 22d can each be formed by depositing materials using a dry coating method. Dry coating methods include sputtering, vacuum deposition, and CVD, with sputtering being preferred. As the sputtering method, reactive sputtering is preferable from the viewpoint of film formation speed.
  • the conditions of the sputtering method in this step are the same as those described above as the conditions of the sputtering method in the adhesion layer forming step.
  • Each of the first high refractive index layer 22a and the second high refractive index layer 22c is made of a high refractive index material having a refractive index of preferably 1.9 or more at a wavelength of 550 nm.
  • high refractive index materials include niobium oxide (Nb 2 O 5 ), titanium oxide, zirconium oxide, indium tin oxide (ITO), and Antimony tin oxide (ATO) is mentioned, preferably niobium oxide is used.
  • the optical film thickness (product of refractive index and thickness) of the first high refractive index layer 22a is, for example, 20 nm or more and, for example, 55 nm or less.
  • the optical film thickness of the second high refractive index layer 22c is, for example, 60 nm or more and is, for example, 330 nm or less.
  • Each of the first low refractive index layer 22b and the second low refractive index layer 22d is made of a low refractive index material having a refractive index of preferably 1.6 or less at a wavelength of 550 nm.
  • low refractive index materials include, for example, silicon dioxide (SiO 2 ) and magnesium fluoride, preferably silicon dioxide.
  • the optical film thickness of the first low refractive index layer 22b is, for example, 15 nm or more and, for example, 70 nm or less.
  • the optical film thickness of the second low refractive index layer 22d is, for example, 100 nm or more and is, for example, 160 nm or less.
  • the antifouling layer 23 is formed on one surface of the antireflection layer 22 in the thickness direction D by a roll-to-roll method.
  • the antifouling layer 23 is a layer having an antifouling function.
  • the antifouling function of the antifouling layer 23 includes a function of suppressing adhesion of contaminants such as oil from hands to the exposed surface (upper surface in the figure) of the optical film F, and a function of facilitating removal of adhering contaminants. .
  • the antifouling layer 23 is formed by depositing an antifouling layer material on the antireflection layer 22 by a dry coating method. That is, the antifouling layer 23 is a film (dry coating film) formed by a dry coating method. Dry coating methods include, for example, vacuum deposition, sputtering, and CVD.
  • the antifouling layer 23 is preferably a film (vacuum vapor deposition film) formed by a vacuum vapor deposition method.
  • the structure in which the antifouling layer 23 is a dry coating film (preferably a vacuum deposition film) is suitable for ensuring high bonding strength of the antifouling layer 23 to the base, and therefore suitable for ensuring the peeling resistance of the antifouling layer 23. .
  • the high antifouling property of the antifouling layer 23 helps to maintain the antifouling function of the antifouling layer 23 .
  • an organic fluorine compound having a fluorinated alkyl group at its terminal is preferably used as the material for the antifouling layer 23.
  • the organic fluorine compound is suitable for exhibiting excellent antifouling properties in the antifouling layer 23 by superimposing high hydrophobicity and high oleophobicity due to the terminal fluorinated alkyl group.
  • an alkoxysilane compound having a perfluoropolyether group represented by the following general formula (1) is preferably used.
  • R 1 represents a linear or branched fluorinated alkyl group (having, for example, 1 or more and 20 or less carbon atoms) in which one or more hydrogen atoms in the alkyl group are substituted with fluorine atoms. preferably represents a perfluoroalkyl group in which all hydrogen atoms in an alkyl group are substituted with fluorine atoms.
  • R 2 represents a structure containing at least one repeating structure of perfluoropolyether (PFPE) groups, preferably a structure containing two repeating structures of PFPE groups.
  • PFPE groups include repeating structures of linear PFPE groups and repeating structures of branched PFPE groups.
  • the repeating structure of the linear PFPE group for example, a structure represented by -(OC n F 2n ) p - (n represents an integer of 1 or more and 20 or less, p represents an integer of 1 or more and 50 or less The same applies below).
  • the repeating structure of the branched PFPE group for example, a structure represented by -(OC(CF 3 ) 2 ) p - and a structure represented by -(OCF 2 CF(CF 3 )CF 2 ) p - is mentioned.
  • the repeating structure of the PFPE group preferably includes a repeating structure of a linear PFPE group, more preferably -(OCF 2 ) p - and -(OC 2 F 4 ) p -.
  • R 3 represents an alkyl group having 1 to 4 carbon atoms, preferably a methyl group.
  • X represents an ether group, a carbonyl group, an amino group, or an amide group, preferably an ether group.
  • n represents an integer of 1 or more.
  • m represents an integer of preferably 20 or less, more preferably 10 or less, and even more preferably 5 or less.
  • alkoxysilane compounds having a perfluoropolyether group compounds represented by the following general formula (2) are preferably used.
  • q represents an integer of 1 or more and 50 or less
  • r represents an integer of 1 or more and 50 or less
  • alkoxysilane compound having a perfluoropolyether group may be used alone, or two or more of them may be used in combination.
  • the thickness of the antifouling layer 23 is preferably 6 nm or more, more preferably 7 nm or more, from the viewpoint of ensuring the antifouling property of the antifouling layer 23 .
  • the thickness of the antifouling layer 23 is preferably 25 nm or less, more preferably 20 nm or less, and even more preferably 18 nm or less from the viewpoint of suppressing peeling of the antifouling layer material.
  • a series of processes from the adhesion layer forming step to the antifouling layer forming step are carried out in one pass line while conveying the work film by a roll-to-roll method.
  • the work film is never exposed to the atmosphere.
  • the work film is wound up by a winding roller arranged at the end of the pass line.
  • the optical film F is manufactured as described above.
  • the optical film F includes a transparent substrate film 10, an adhesion layer 21, an antireflection layer 22, and an antifouling layer 23 in this order toward one side in the thickness direction D.
  • Optical film F is one embodiment of the optical film with an antifouling layer of the present invention.
  • the optical film F has a shape that spreads in a direction perpendicular to the thickness direction D (surface direction).
  • the optical film F is used with the transparent substrate film 10 side attached to an adherend via, for example, an adhesive.
  • the adherend include a transparent cover arranged on the image display side of a display such as a touch panel display.
  • the surface free energy of the back surface 10b of the transparent substrate film 10 is 45 mN/m or less, preferably 43 mN/m or less, more preferably 40 mN/m. It is below.
  • the configuration in which the surface free energy of the back surface 10b is as low as this is the antifouling layer-attached optical film F that is wound up on a take-up roller into a roll after the above-described antifouling layer forming step (FIG. 2C). It is suitable for suppressing the transfer of the antifouling layer material from the layer 23 to the back surface 10b of the transparent base film 10 .
  • Such transfer inhibition of the antifouling layer material helps achieve good antifouling properties in the antifouling layer 23 .
  • the transfer suppression of the antifouling layer material is good for the back surface 10b of the transparent base film 10 in the adhesive when the transparent base film 10 side of the optical film F is bonded to the adherend via the adhesive. Helps to develop stickiness.
  • the optical film with an antifouling layer in which the contact angle of the fluorine-based solvent on the back surface 10b of the transparent base film 10 is as low as described above, suppresses the adhesion of the antifouling layer material to the back surface 10b, and is rolled to roll. suitable for manufacturing.
  • the optical film F may be an optical film without the antireflection layer 22.
  • FIG. 3 shows an optical film F obtained by carrying out the antifouling layer forming step (FIG. 2C) after such a step.
  • the inorganic oxide underlayer 24 is formed by depositing a material using a dry coating method. Dry coating methods include sputtering, vacuum deposition, and CVD, with sputtering being preferred. Examples of the material of the inorganic oxide underlayer 24 include silicon dioxide (SiO 2 ) and magnesium fluoride, preferably silicon dioxide.
  • the thickness of the inorganic oxide underlayer 24 is preferably 50 nm or more, more preferably 65 nm or more, and still more preferably 80 nm or more, from the viewpoint of ensuring the peeling resistance of the antifouling layer 23 .
  • the thickness of the inorganic oxide underlayer 24 is, for example, 300 nm or less.
  • a hard coat layer was formed on one side of a long polyethylene terephthalate (PET) film (50 ⁇ m thick) as a transparent substrate film (hard coat layer forming step).
  • PET polyethylene terephthalate
  • a mixture of UV-curable monomers and oligomers (containing urethane acrylate as a main component) in a butyl acetate solution (trade name “Unidic 17-806”, solid content concentration 80% by mass, manufactured by DIC Corporation) ) 100 parts by mass (in terms of solid content), a photopolymerization initiator (trade name “IRGACURE906”, manufactured by BASF) 5 parts by mass, and a leveling agent (trade name “GRANDIC PC4100”, manufactured by DIC) 0.01 parts by mass were mixed to obtain a mixed liquid.
  • a mixed solvent of cyclopentanone (CPN) and propylene glycol monomethyl ether (PGM) (the mass ratio of CPN and PGM is 45:55) was added to adjust the solid content concentration of the mixed liquid to 36% by mass.
  • an ultraviolet curable resin composition (varnish) was prepared.
  • the resin composition was applied to one surface (first surface) of the PET film to form a coating film.
  • this coating film was dried by heating and then cured by UV irradiation. The heating temperature was 90° C. and the heating time was 60 seconds.
  • a high-pressure mercury lamp was used as a light source, ultraviolet rays with a wavelength of 365 nm were used, and the cumulative irradiation light amount was 300 mJ/cm 2 .
  • a series of processes from the formation of the coating film to the curing described above were carried out in one pass line in a roll-to-roll system. As a result, a hard coat layer (HC) having a thickness of 5 ⁇ m was formed on the PET film.
  • HC hard coat layer
  • a transfer suppressing layer (first transfer suppressing layer) was formed on the second surface of the PET film as follows.
  • a binder aqueous dispersion containing a polyester resin as a binder (product name "Binalol MD-1480", aqueous dispersion of saturated copolyester resin, resin content 25% by mass, manufactured by Toyobo Co., Ltd.), carnauba as a slipping agent.
  • PEDT poly(3,4-ethylenedioxythiophene)
  • PSS polystyrene sulfonate
  • a conductive polymer aqueous solution (product name "Baytron P", manufactured by HC Stark) containing .8% by weight was prepared.
  • 100 parts by mass of solid content of the aqueous dispersion of binder, 30 parts by mass of solid content of the aqueous dispersion of lubricant, and 30 parts by mass of solid content of the above aqueous dispersion of conductive polymer are added.
  • 50 parts by mass of solid content and 20 parts by mass of melamine-based cross-linking agent were added and mixed by stirring for about 20 minutes. As a result, a coating liquid having a solid concentration of about 0.15% by mass was obtained.
  • the second surface of the PET film was subjected to corona treatment.
  • the coating liquid was applied to the second surface (corona-treated surface) with a bar coater to form a coating film, and then the coating film was dried by heating at 130° C. for 2 minutes. Thereby, a transfer suppressing layer having a thickness of 10 nm was formed on the second surface.
  • a long roll-shaped PET film having the HC layer formed on the first surface and the transfer suppressing layer formed on the second surface was obtained.
  • the roll-shaped HC layer-attached PET film is set as a work film on the delivery roller arranged at the starting end of the pass line, and the work film is delivered from the delivery roller.
  • the work film is never exposed to the atmosphere during the process.
  • the work film is wound up by a winding roller arranged at the end of the pass line.
  • the HC layer surface of the HC layer-attached PET film was plasma-treated under a vacuum atmosphere of 1.0 Pa in a plasma treatment apparatus (HC layer pretreatment step).
  • a plasma treatment apparatus HC layer pretreatment step
  • argon gas was used as an inert gas
  • the discharge power was 780W.
  • an adhesion layer and an antireflection layer were sequentially formed on the HC layer of the HC layer-attached PET film after the plasma treatment (sputter film formation step).
  • a 1.5 nm-thick indium tin oxide (ITO) layer as an adhesion layer and a first high refractive index layer were formed on the HC layer of the HC layer-attached PET film by a sputtering deposition apparatus.
  • An SiO 2 layer with a thickness of 85 nm as a refractive index layer was formed in succession.
  • an ITO target was used, argon gas was used as an inert gas, oxygen gas was used as a reactive gas in an amount of 10 parts by volume with respect to 100 parts by volume of argon gas, and the discharge voltage was set to 400 V.
  • the pressure in the film chamber was set to 0.2 Pa, and the ITO layer was formed by MFAC sputtering.
  • a Nb target is used, 100 parts by volume of argon gas and 5 parts by volume of oxygen gas are used, the discharge voltage is 415 V, the film formation pressure is 0.42 Pa, and the Nb target is formed by MFAC sputtering. 2 O 5 layers were deposited.
  • a Si target is used, 100 parts by volume of argon gas and 30 parts by volume of oxygen gas are used, the discharge voltage is 350 V, the film formation pressure is 0.3 Pa, and MFAC sputtering is performed to form SiO. Two layers were deposited.
  • a Nb target is used, 100 parts by volume of argon gas and 13 parts by volume of oxygen gas are used, the discharge voltage is 460 V, the film formation pressure is 0.5 Pa, and the Nb target is formed by MFAC sputtering. 2 O 5 layers were deposited.
  • a Si target is used, 100 parts by volume of argon gas and 30 parts by volume of oxygen gas are used, the discharge voltage is 340 V, the film formation pressure is 0.25 Pa, and MFAC sputtering is performed to form SiO. Two layers were deposited. As described above, antireflection layers (first high refractive index layer, first low refractive index layer, second high refractive index layer, second low refractive index layer) was laminated.
  • an antifouling layer was formed on the antireflection layer (antifouling layer forming step). Specifically, an antifouling layer having a thickness of 10 nm was formed on the antireflection layer by a vacuum deposition method using a vacuum deposition apparatus.
  • a vacuum deposition method an alkoxysilane compound containing a perfluoropolyether group was used as a deposition source.
  • This vapor deposition source is a solid content obtained by drying "KY1903-1" (perfluoropolyether group-containing alkoxysilane compound, solid content concentration 20% by mass) manufactured by Shin-Etsu Chemical Co., Ltd.
  • the heating temperature of the vapor deposition source in the vacuum vapor deposition method was set to 260.degree.
  • the optical film of Example 1 (a long roll-shaped optical film with an antifouling layer) was produced.
  • the optical film of Example 1 includes a transparent base film (a hard coat layer forms one side and the first transfer suppressing layer forms a rear side as the other side), an adhesion layer, an antireflection layer, and an antifouling layer. and in this order.
  • Example 2 In the transfer suppression treatment step, the optical film of Example 2 (a long roll-shaped An optical film with an antifouling layer) was produced.
  • the transfer suppression treatment step in this example while conveying the work film by a roll-to-roll method, first, on the second surface of the PET film with the above-mentioned HC layer, indium tin oxide having a thickness of 1.5 nm ( ITO) layer and a 10 nm-thick SiO2 layer thereon are sequentially formed by sputtering to form an adhesion layer, and then a 10-nm-thick second transfer inhibiting layer is formed on the adhesion layer by a vacuum evaporation method. formed.
  • ITO indium tin oxide having a thickness of 1.5 nm
  • SiO2 10 nm-thick SiO2
  • a perfluoropolyether group-containing alkoxysilane compound (solid content obtained by drying "KY1903-1" manufactured by Shin-Etsu Chemical Co., Ltd.) is used as the deposition source, and the heating temperature of the deposition source is set to The temperature was set at 260° C. (similar to the vacuum deposition method in the antifouling layer forming step in Example 1).
  • the optical film of Example 2 comprises a transparent substrate film (a hard coat layer forms one surface and a second transfer suppressing layer forms a rear surface as the other surface), a hard coat layer, an adhesion layer, and an antireflection layer. and an antifouling layer in this order.
  • Comparative Example 1 An optical film of Comparative Example 1 (a long roll-shaped optical film with an antifouling layer) was produced in the same manner as the optical film of Example 1, except that the transfer suppression treatment step was not performed.
  • ⁇ Thickness of antifouling layer> The thickness of the antifouling layer in each optical film of Examples 1 and 2 and Comparative Example 1 was measured.
  • a scanning fluorescent X-ray spectrometer (trade name “ZSX Primus II”, manufactured by Rigaku Corporation) was used for the measurement.
  • Table 1 shows the measured thickness T1 (nm) of the antifouling layer.
  • ⁇ Transfer of antifouling layer material> The degree of transfer of the antifouling layer material to the second surface (rear surface) of the transparent substrate film in each of the optical films of Examples 1 and 2 and Comparative Example 1 was examined. Specifically, the thickness of the antifouling layer material transferred to the back surface of the transparent substrate film was measured. A scanning fluorescent X-ray spectrometer (trade name “ZSX Primus II”, manufactured by Rigaku Corporation) was used for the measurement. Table 1 shows the measured thickness T2 (nm).
  • the surface free energy of the back surface (second surface) of the transparent substrate film in each of the optical films of Examples 1 and 2 and Comparative Example 1 was determined as follows. First, under conditions of 23° C. and a relative humidity of 55%, water (H 2 O), methylene iodide (CH 2 I 2 ) and 1-bromonaphthalene, the contact angle was measured using a contact angle meter for each droplet (approximately 1 ⁇ L). For this measurement, a contact angle meter (product name: "CA-X type contact angle meter", manufactured by Kyowa Interface Science Co., Ltd.) was used.
  • the optical film with an antifouling layer of the present invention can be applied to, for example, an antireflection film with an antifouling layer, a transparent conductive film with an antifouling layer, and an electromagnetic shielding film with an antifouling layer.
  • Optical film (optical film with antifouling layer) D thickness direction 10 transparent substrate film 11 resin film 10a front surface 10b back surface 12 hard coat layer 13 transfer suppressing layer 21 adhesion layer 22 antireflection layer 22a first high refractive index layer 22b first low refractive index layer 22c second high refractive index index layer 22d second low refractive index layer 23 antifouling layer 23a surface

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JP2010244016A (ja) * 2009-03-18 2010-10-28 Toppan Printing Co Ltd 防眩フィルム、偏光板、透過型液晶ディスプレイ
WO2012137662A1 (ja) * 2011-04-05 2012-10-11 東レ株式会社 ガスバリア性フィルム
JP2017123316A (ja) * 2016-01-08 2017-07-13 日本製紙株式会社 透明導電性フィルムの製造方法及びそれを用いたタッチパネル、ディスプレイ、太陽電池、照明
JP2017227898A (ja) * 2016-06-17 2017-12-28 日東電工株式会社 反射防止フィルムおよびその製造方法、ならびに反射防止層付き偏光板

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JP2010244016A (ja) * 2009-03-18 2010-10-28 Toppan Printing Co Ltd 防眩フィルム、偏光板、透過型液晶ディスプレイ
WO2012137662A1 (ja) * 2011-04-05 2012-10-11 東レ株式会社 ガスバリア性フィルム
JP2017123316A (ja) * 2016-01-08 2017-07-13 日本製紙株式会社 透明導電性フィルムの製造方法及びそれを用いたタッチパネル、ディスプレイ、太陽電池、照明
JP2017227898A (ja) * 2016-06-17 2017-12-28 日東電工株式会社 反射防止フィルムおよびその製造方法、ならびに反射防止層付き偏光板

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