WO2017164046A1 - Procédé de fabrication d'un film optique et moule - Google Patents

Procédé de fabrication d'un film optique et moule Download PDF

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WO2017164046A1
WO2017164046A1 PCT/JP2017/010552 JP2017010552W WO2017164046A1 WO 2017164046 A1 WO2017164046 A1 WO 2017164046A1 JP 2017010552 W JP2017010552 W JP 2017010552W WO 2017164046 A1 WO2017164046 A1 WO 2017164046A1
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Prior art keywords
mold
layer resin
atoms
upper layer
resin
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PCT/JP2017/010552
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English (en)
Japanese (ja)
Inventor
健一郎 中松
厚志 新納
林　秀和
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シャープ株式会社
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Priority to JP2018507270A priority Critical patent/JP6600078B2/ja
Priority to CN201780014466.9A priority patent/CN108780162B/zh
Publication of WO2017164046A1 publication Critical patent/WO2017164046A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/42—Moulds or cores; Details thereof or accessories therefor characterised by the shape of the moulding surface, e.g. ribs or grooves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
    • 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
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/06—Embossing
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/118—Anti-reflection coatings having sub-optical wavelength surface structures designed to provide an enhanced transmittance, e.g. moth-eye structures
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films

Definitions

  • the present invention relates to an optical film manufacturing method and a mold. More specifically, the present invention relates to a method for producing an optical film having a nanometer-sized concavo-convex structure and a mold preferably used in the method for producing an optical film.
  • an optical film having a nanometer-sized uneven structure has excellent antireflection properties. According to such a concavo-convex structure, since the refractive index continuously changes from the air layer to the base film, the reflected light can be dramatically reduced.
  • Nano Science Co., Ltd. “Knowledge of XPS analysis”, “Chemical state of carbon (C1s binding energy shift (chemical shift))”, [online], 2014, [searched on February 17, 2016], Internet (URL: http://www.nanoscience.co.jp/knowledge/XPS/knowledge02.html)
  • A. M.M. Ferraria et al. “XPS studies on direct fluorinated HDPE: problems and solutions (XPS studies of fluorinated HDPE: problems and solutions)”, Polymer 44, 2003, pp. 7241-7249 Thermo Fisher Scientific Inc.
  • a mold for forming a concavo-convex structure is usually used. And in order to improve mold release property, the surface treatment by a mold release agent, ie, the mold release process, was sometimes performed with respect to the metal mold
  • the resulting optical film has insufficient water repellency and oil repellency, that is, antifouling property. I understood that. For this reason, there is a problem that dirt such as fingerprints and oil attached to the surface of the optical film is likely to spread, and it is difficult to wipe off dirt that has entered between the convex portions.
  • the frictional resistance of the surface of the optical film is increased (sliding property is lowered), and there is a problem that the abrasion resistance is lowered.
  • This invention is made
  • the inventors of the present invention have studied various methods for producing an optical film having excellent antifouling properties and abrasion resistance. As a result, a lower layer resin and an upper layer resin are applied, and the two layers are laminated. We focused on the method of pressing the mold and forming a resin layer having a nanometer-sized uneven structure on the surface and then curing the resin layer. And it discovered that the density
  • a mold having a release agent containing fluorine atoms applied to the surface thereof is used, and the contact angle of hexadecane and the concentration of fluorine atoms on the surface of the mold applied with the release agent are set within a predetermined range.
  • the concentration of fluorine atoms on the surface of the optical film is remarkably increased, and as a result, the antifouling property and abrasion resistance are remarkably increased.
  • the inventors have conceived that the above problems can be solved brilliantly and have reached the present invention.
  • one embodiment of the present invention is a method for producing an optical film having a concavo-convex structure on the surface where a plurality of convex portions are provided at a pitch equal to or less than the wavelength of visible light, and a step of applying a lower layer resin and an upper layer resin (1 ) And the applied lower layer resin and the upper layer resin are laminated, a mold is pressed against the lower layer resin and the upper layer resin from the upper layer resin side to form a resin layer having the uneven structure on the surface.
  • the mold agent includes carbon atoms, oxygen atoms, and fluorine atoms as constituent atoms, and the mold includes aluminum atoms and oxygen atoms as constituent atoms, and the mold in which the release agent is applied.
  • Hexadeca on the surface was added dropwise, theta / measured by 2 methods, the contact angle immediately after hexadecane dropwise theta A (Unit: °), the contact angle after hexadecane dropwise 4 minutes theta B (unit: °) and by defining, theta A And ⁇ B is 85 ° or more, and the difference between ⁇ A and ⁇ B is 3.5 ° or less, the X-ray beam diameter is 100 ⁇ m, the analysis area is 1000 ⁇ m ⁇ 500 ⁇ m, and the photoelectron extraction angle is 45 °.
  • the number of carbon atoms, the number of aluminum atoms, the number of oxygen atoms, and the number of fluorine atoms on the surface of the mold coated with the release agent, as measured by X-ray photoelectron spectroscopy under conditions The ratio of the number of fluorine atoms to the total number may be a method for producing an optical film that is 30 atom% or more.
  • Another aspect of the present invention is a mold in which a plurality of recesses are provided on the surface with a pitch equal to or smaller than the wavelength of visible light, and a mold release agent is disposed on the surface of the mold.
  • the mold includes carbon atoms, oxygen atoms, and fluorine atoms as constituent atoms, the mold includes aluminum atoms and oxygen atoms as constituent atoms, and the mold in which the release agent is disposed.
  • ⁇ A and ⁇ B are 85 ° or more, and the difference between ⁇ A and ⁇ B is 3.5 ° or less, the X-ray beam diameter is 100 ⁇ m, the analysis area is 1000 ⁇ m ⁇ 500 ⁇ m, and the photoelectron extraction angle By X-ray photoelectron spectroscopy at 45 °
  • the ratio of the number of fluorine atoms to the total number of carbon atoms, aluminum atoms, oxygen atoms, and fluorine atoms measured on the surface of the mold on which the release agent is disposed is The mold may be 30 atom% or more.
  • the manufacturing method of the optical film excellent in antifouling property and abrasion resistance can be provided.
  • die used when manufacturing the optical film excellent in antifouling property and abrasion resistance can be provided.
  • FIG. 3 is a schematic cross-sectional view for explaining the manufacturing process of the optical film of Embodiment 1 (steps a to d).
  • 1 is a schematic cross-sectional view showing a mold according to Embodiment 1.
  • FIG. FIG. 6 is a schematic cross-sectional view for explaining the manufacturing process of the optical film of Embodiment 2 (steps a to e).
  • FIG. 10 is a schematic cross-sectional view for explaining the manufacturing process of the optical film of Embodiment 3 (steps a to d).
  • FIG. 10 is a schematic cross-sectional view for explaining the manufacturing process of the optical film of Embodiment 4 (steps a to e).
  • FIG. 1 is a schematic cross-sectional view for explaining a manufacturing process of the optical film of Embodiment 1 (steps a to d).
  • the coating method of the lower layer resin 5a and the upper layer resin 5b is not particularly limited, and examples thereof include a method of coating by a spray method, a gravure method, a slot die method, or the like. From the viewpoint of easily adjusting the film thickness and reducing the apparatus cost, a method of applying by a spray method is preferable. Among these, application using a swirl nozzle, electrostatic nozzle, or ultrasonic nozzle is particularly preferable.
  • the resin layer 8 is preferably cured by irradiation with active energy rays.
  • active energy rays refer to ultraviolet rays, visible rays, infrared rays, plasma, and the like.
  • the resin layer 8 is preferably cured by ultraviolet rays.
  • the active energy ray may be irradiated from the base film 2 side or from the resin layer 8 side.
  • count of irradiation of the active energy ray with respect to the resin layer 8 is not specifically limited, One time may be sufficient and multiple times may be sufficient.
  • the steps (a) to (d) can be performed continuously and efficiently.
  • the material for the base film 2 examples include triacetyl cellulose (TAC), polyethylene terephthalate (PET), polymethyl methacrylate (PMMA), cycloolefin polymer (COP), and polycarbonate (PC). You may choose according to it. According to such a material, the base film 2 having high hardness and excellent transparency and weather resistance can be obtained.
  • the base film 2 may be subjected to an easy adhesion treatment. For example, a triacetyl cellulose film (TAC film) subjected to the easy adhesion treatment or the like is used. Further, the base film 2 may be subjected to saponification treatment. For example, a triacetyl cellulose film (TAC film) subjected to saponification treatment or the like is used.
  • the thickness of the base film 2 is not particularly limited, it is preferably 10 ⁇ m or more and 120 ⁇ m or less, and more preferably 40 ⁇ m or more and 80 ⁇ m or less from the viewpoint of ensuring transparency and workability.
  • the upper layer resin 5b contains a fluorine-containing monomer.
  • the concentration of fluorine atoms on the surface of the polymer layer 3 opposite to the base film 2 is increased.
  • the surface energy of the polymer layer 3 is lowered, and the optical film 1 having excellent antifouling properties can be obtained.
  • the slipperiness of the surface on the opposite side to the base film 2 of the polymer layer 3 increases, and the optical film 1 excellent in abrasion resistance is obtained.
  • the fluorine-containing monomer has a reactive site and a site containing at least one selected from the group consisting of a fluoroalkyl group, a fluorooxyalkyl group, a fluoroalkenyl group, a fluoroalkanediyl group, and a fluorooxyalkanediyl group. It is preferable to have.
  • the reactive site refers to a site that reacts with other components by external energy such as light and heat.
  • Examples of such reactive sites include alkoxysilyl groups, silyl ether groups, hydrolyzed silanol groups, carboxyl groups, hydroxyl groups, epoxy groups, vinyl groups, allyl groups, acryloyl groups, methacryloyl groups, and the like. It is done.
  • the reactive site is preferably an alkoxysilyl group, a silyl ether group, a silanol group, an epoxy group, a vinyl group, an allyl group, an acryloyl group, or a methacryloyl group from the viewpoint of reactivity and handling properties, and a vinyl group or an allyl group.
  • An acryloyl group or a methacryloyl group is more preferable, and an acryloyl group or a methacryloyl group is particularly preferable.
  • a fluoroalkyl group, a fluorooxyalkyl group, a fluoroalkenyl group, a fluoroalkanediyl group, and a fluorooxyalkanediyl group are respectively an alkyl group, an oxyalkyl group, an alkenyl group, an alkanediyl group, and an oxyalkanediyl group. It is a substituent in which at least part of the hydrogen atoms it has are substituted with fluorine atoms.
  • a fluoroalkyl group, a fluorooxyalkyl group, a fluoroalkenyl group, a fluoroalkanediyl group, and a fluorooxyalkanediyl group are all substituents mainly composed of fluorine atoms and carbon atoms, and are branched in the structure. May be present, and a plurality of these substituents may be linked.
  • R f1 is a moiety containing at least one selected from the group consisting of a fluoroalkyl group, a fluorooxyalkyl group, a fluoroalkenyl group, a fluoroalkanediyl group, and a fluorooxyalkanediyl group.
  • R 2 represents an alkanediyl group, an alkanetriyl group, or an ester structure, urethane structure, ether structure, or triazine structure derived therefrom.
  • D 1 represents a reactive site.
  • fluorine-containing monomer represented by the general formula (A) examples include 2,2,2-trifluoroethyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate, and 2-perfluorobutyl.
  • the fluoropolyether moiety is a moiety composed of a fluoroalkyl group, an oxyfluoroalkyl group, an oxyfluoroalkyldiyl group, etc., and has a structure represented by the following general formula (B) or (C).
  • n1 is an integer of 1 to 3
  • n2 to n5 are 1 or 2
  • k, m, p, and s are integers of 0 or more.
  • a preferable combination of n1 to n5 is a combination in which n1 is 2 or 3, and n2 to n5 is 1 or 2, and a more preferable combination is n1 is 3, n2 and n4 are 2, and n3 and n5 are 1 or 2. 2 is a combination.
  • the number of carbon atoms contained in the fluoropolyether moiety is preferably 4 or more and 12 or less, more preferably 4 or more and 10 or less, and still more preferably 6 or more and 8 or less.
  • the number of carbon atoms is less than 4, there is a concern that the surface energy is reduced.
  • the number of carbon atoms is more than 12, there is a concern that the solubility in a solvent is lowered.
  • the fluorine-containing monomer may have a plurality of fluoropolyether sites per molecule.
  • fluorine-containing compounds containing a fluorine-containing monomer as a constituent component include, for example, a fluorine-based additive (product name: OPTOOL (registered trademark) DAC-HP) manufactured by Daikin Industries, Ltd., and fluorine manufactured by Daikin Industries, Ltd. Additive (Product name: Optool DSX), Fluorine additive manufactured by Daikin Industries, Ltd.
  • the upper resin 5b may contain one type of fluorine-containing monomer or may contain a plurality of types of fluorine-containing monomers.
  • the fluorine-containing monomer may also be contained in the lower layer resin 5a.
  • the concentration of the fluorine-containing monomer in the upper resin 5b is preferably higher than the concentration of the fluorine-containing monomer in the lower resin 5a.
  • the lower layer resin 5a preferably does not contain a fluorine-containing monomer.
  • the concentration of the fluorine-containing monomer in the upper layer resin 5b is preferably higher than 0% by weight and 10% by weight or less. When the concentration of the fluorine-containing monomer in the upper layer resin 5b is higher than 10% by weight, there is a concern about the occurrence of bleed-out and an increase in cost due to too much fluorine-containing monomer.
  • Each of the lower layer resin 5a and the upper layer resin 5b may appropriately include a polyfunctional acrylate, a monofunctional acrylate, a polymerization initiator, and the like.
  • polyfunctional acrylates include urethane acrylate, ethoxylated pentaerythritol tetraacrylate, pentaerythritol triacrylate, 1,9-nonanediol diacrylate, dipentaerythritol hexaacrylate, tripentaerythritol acrylate, and mono and dipentaerythritol acrylate.
  • Known urethane acrylates include, for example, polyfunctional acrylates (product name: UA-306H) manufactured by Kyoeisha Chemical Co., Ltd., polyfunctional acrylates (product name: U-10PA) manufactured by Shin-Nakamura Chemical Co., Ltd., and Shin-Nakamura. Examples thereof include polyfunctional acrylate (product name: UA-7100) manufactured by Chemical Industry Co., Ltd. Examples of known ethoxylated pentaerythritol tetraacrylates include polyfunctional acrylates (product name: ATM-35E) manufactured by Shin-Nakamura Chemical Co., Ltd.
  • Known pentaerythritol triacrylates include, for example, polyfunctional acrylates (product name: A-TMM-3LM-N) manufactured by Shin-Nakamura Chemical Co., Ltd., and polyfunctional acrylates (product name: Shin-Nakamura Chemical Co., Ltd.). : A-TMM-3L), polyfunctional acrylate (product name: PET-3) manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and the like.
  • Known examples of 1,9-nonanediol diacrylate include, for example, polyfunctional acrylate (product name: A-NOD-N) manufactured by Shin-Nakamura Chemical Co., Ltd.
  • dipentaerythritol hexaacrylate examples include, for example, polyfunctional acrylate manufactured by Kyoeisha Chemical Co., Ltd. (product name: Light Acrylate DPE-6A), and polyfunctional acrylate manufactured by Shin-Nakamura Chemical Co., Ltd. (product name: A- DPH) and the like.
  • Examples of the mixture of tripentaerythritol acrylate, mono- and dipentaerythritol acrylate, and polypentaerythritol acrylate examples include polyfunctional acrylate (product name: Biscote # 802) manufactured by Osaka Organic Chemical Industry Co., Ltd.
  • Examples of the ethoxylated polyglycerin polyacrylate include polyfunctional acrylate (product name: NK ECONOMER (registered trademark) A-PG5027E) manufactured by Shin-Nakamura Chemical Co., Ltd.
  • Known examples of trimethylolpropane triacrylate include, for example, polyfunctional acrylate (product name: light acrylate TMP-A) manufactured by Kyoeisha Chemical Co., Ltd.
  • Known examples of the alkoxylated dipentaerythritol polyacrylate include, for example, a polyfunctional acrylate manufactured by Nippon Kayaku Co., Ltd.
  • polyethylene glycol 200 diacrylate examples include polyfunctional acrylate (product name: PE-200) manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.
  • polyethylene glycol 300 diacrylate examples include polyfunctional acrylate (product name: PE-300) manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
  • polyethylene glycol 400 diacrylate examples include polyfunctional acrylate (product name: A-400) manufactured by Shin-Nakamura Chemical Co., Ltd.
  • Examples of known polyethylene glycol 600 diacrylate include polyfunctional acrylate (product name: A-600) manufactured by Shin-Nakamura Chemical Co., Ltd.
  • polyfunctional acrylate product name: A-600
  • EBECRYL trademark of Daicel Ornex, etc.
  • Examples of known ethoxylated glycerin triacrylate include polyfunctional acrylate (product name: A-GLY-9E) manufactured by Shin-Nakamura Chemical Co., Ltd.
  • 1,6-hexanediol diacrylate examples include, for example, polyfunctional acrylate (product name: A-HD-N) manufactured by Shin-Nakamura Chemical Co., Ltd.
  • Known examples of tripropylene glycol diacrylate include polyfunctional acrylate (product name: APG-200) manufactured by Shin-Nakamura Chemical Co., Ltd.
  • Known examples of ethoxylated (4 mol adduct) bisphenol A diacrylate include, for example, polyfunctional acrylate (product name: A-BPE-4) manufactured by Shin-Nakamura Chemical Co., Ltd.
  • dipropylene glycol diacrylate examples include polyfunctional acrylate (product name: APG-100) manufactured by Shin-Nakamura Chemical Co., Ltd.
  • APG-100 polyfunctional acrylate
  • Each of the lower layer resin 5a and the upper layer resin 5b may include one type of polyfunctional acrylate, or may include a plurality of types of polyfunctional acrylates.
  • Examples of monofunctional acrylates containing an alkyl group include lauryl acrylate and stearyl acrylate.
  • Examples of known lauryl acrylate include monofunctional acrylate (product name: LA) manufactured by Shin-Nakamura Chemical Co., Ltd.
  • Known examples of stearyl acrylate include a monofunctional acrylate (product name: Blemmer (registered trademark) SA) manufactured by NOF Corporation.
  • monofunctional acrylates those containing an ethylene oxide group or a propylene oxide group include, for example, polyethylene glycol monoacrylate and polypropylene glycol monoacrylate.
  • polyethylene glycol monoacrylates include monofunctional acrylates (product name: AM-90G) manufactured by Shin-Nakamura Chemical Co., Ltd.
  • polypropylene glycol monoacrylate include a monofunctional acrylate (product name: Blemmer AP-400) manufactured by NOF Corporation.
  • Examples of monofunctional acrylates containing hydroxyl groups include 2-hydroxyethyl methacrylate, 4-hydroxybutyl acrylate, and the like.
  • 2-hydroxyethyl methacrylate include a monofunctional acrylate (product name: 2HEMA) manufactured by Nippon Shokubai Co., Ltd.
  • 2-hydroxyethyl methacrylate include a monofunctional acrylate (product name: 2HEMA) manufactured by Nippon Shokubai Co., Ltd.
  • Examples of 4-hydroxybutyl acrylate include monofunctional acrylate (product name: 4HBA) manufactured by Nippon Kasei Co., Ltd.
  • Examples of monofunctional acrylates containing amide groups include, for example, N-acryloylmorpholine, N, N-dimethylacrylamide, N, N-diethylacrylamide, and N-vinyl. Examples include -2-pyrrolidone, N, N-dimethylmethacrylamide, N-methoxy-N-methyl-3-phenyl-acrylamide and the like.
  • Known examples of N-acryloylmorpholine include monofunctional amide monomers (product name: ACMO (registered trademark)) manufactured by KJ Chemicals.
  • N, N-dimethylacrylamide examples include monofunctional amide monomers (product name: DMAA (registered trademark)) manufactured by KJ Chemicals.
  • DMAA registered trademark
  • N, N-diethylacrylamide examples include monofunctional amide monomers (product name: DEAA (registered trademark)) manufactured by KJ Chemicals.
  • Known examples of N-vinyl-2-pyrrolidone include a monofunctional amide monomer (product name: N-vinylpyrrolidone) manufactured by Nippon Shokubai Co., Ltd.
  • Known examples of N, N-dimethylmethacrylamide include monofunctional amide monomers (product code: D0745) manufactured by Tokyo Chemical Industry Co., Ltd.
  • Known examples of N-methoxy-N-methyl-3-phenyl-acrylamide include monofunctional amide monomers manufactured by Sigma-Aldrich.
  • the adhesion between the base film 2 and the polymer layer 3 can be enhanced by the hydrogen bonding force of the amide group.
  • the base film 2 contains highly polar triacetyl cellulose, more specifically, even when triacetyl cellulose is present on at least the surface of the base film 2 on the polymer layer 3 side, The adhesion between the material film 2 and the polymer layer 3 can be enhanced.
  • the monofunctional amide monomer preferably contains at least one of N, N-dimethylacrylamide and N, N-diethylacrylamide.
  • N, N-dimethylacrylamide and N, N-diethylacrylamide have a high molecular weight among monofunctional amide monomers and a low glass transition temperature. Therefore, even if the content is small, the base film 2 and the polymer Adhesiveness with the layer 3 can be preferably increased.
  • Each of the lower layer resin 5a and the upper layer resin 5b may include one type of monofunctional acrylate, or may include a plurality of types of monofunctional acrylates.
  • the polymerization initiator examples include a photopolymerization initiator.
  • the photopolymerization initiator is active with respect to active energy rays, and is added to initiate a polymerization reaction for polymerizing the monomer.
  • a radical polymerization initiator, an anionic polymerization initiator, a cationic polymerization initiator and the like can be used.
  • photopolymerization initiators examples include acetophenones such as p-tert-butyltrichloroacetophenone, 2,2′-diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one; Ketones such as benzophenone, 4,4′-bisdimethylaminobenzophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone; benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc.
  • acetophenones such as p-tert-butyltrichloroacetophenone, 2,2′-diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one
  • Ketones such as benzophenone, 4,4′-bisdimethylaminobenzophenone, 2-
  • Benzoin ethers such as benzyl dimethyl ketal and hydroxycyclohexyl phenyl ketone; 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide; Scan (2,4,6-trimethylbenzoyl) - acylphosphine oxides such as triphenylphosphine oxide; 1-hydroxy - cyclohexyl - phenyl - phenones such as ketones, and the like.
  • 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide examples include, for example, a photopolymerization initiator (product name: IRGACURE (registered trademark) TPO) manufactured by BASF.
  • Known examples of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide include, for example, a photopolymerization initiator (product name: IRGACURE 819) manufactured by BASF.
  • Examples of known 1-hydroxy-cyclohexyl-phenyl-ketone examples include a photopolymerization initiator (product name: IRGACURE 184) manufactured by BASF.
  • At least one of the lower layer resin 5a and the upper layer resin 5b does not contain a solvent. That is, at least one of the lower layer resin 5a and the upper layer resin 5b is preferably solventless.
  • at least one of the lower layer resin 5a and the upper layer resin 5b is a solventless system, it is possible to reduce the cost associated with the use of the solvent and the environmental load (odor during use, etc.). Furthermore, an apparatus for drying and removing the solvent is unnecessary, and the apparatus cost can be reduced.
  • the fluorine-containing monomer is excessively mixed, and there is a concern that the fluorine atoms are less likely to be oriented on the surface of the polymer layer 3 opposite to the base film 2.
  • the thickness Da of the lower layer resin 5a is not particularly limited, but is preferably 5 ⁇ m or more and 10 ⁇ m or less. When the thickness Da of the lower layer resin 5a is less than 5 ⁇ m, the applicability of the lower layer resin 5a may be deteriorated (defects such as spots and lens defects occur). When the thickness Da of the lower layer resin 5a is larger than 10 ⁇ m, the obtained optical film 1 may be easily curled.
  • the thickness Da of the lower layer resin 5a in the present embodiment indicates the distance from the surface on the base film 2 side to the surface on the opposite side to the base film 2 as shown in FIG.
  • the viscosity of the lower layer resin 5a is preferably higher than 10 cp and lower than 10,000 cp at 25 ° C.
  • the viscosity at 25 ° C. of the lower layer resin 5a is higher than 10 cp, the fluorine-containing monomer in the upper layer resin 5b is less likely to be mixed into the lower layer resin 5a in a state where the lower layer resin 5a and the upper layer resin 5b are laminated.
  • the concentration of fluorine atoms on the surface of the resin 5b (polymer layer 3) opposite to the base film 2 tends to increase.
  • the viscosity of the lower layer resin 5a at 25 ° C. is less than 10,000 cp, the coating property of the lower layer resin 5a is improved, and the thickness of the lower layer resin 5a can be easily controlled.
  • the thickness Db of the upper layer resin 5b is not particularly limited, but is preferably 0.5 ⁇ m or more and 2 ⁇ m or less. As shown in FIG. 1A, the thickness Db of the upper layer resin 5b in the present embodiment is on the side opposite to the mold 6 (release agent 7) from the position corresponding to the bottom point of the recess of the mold 6. Refers to the distance to the surface.
  • the viscosity of the upper layer resin 5b is preferably higher than 0.1 cp and lower than 100 cp at 25 ° C.
  • the viscosity of the upper resin 5b at 25 ° C. is higher than 0.1 cp, the applicability of the upper resin 5b is enhanced, and the thickness of the upper resin 5b can be easily controlled.
  • the viscosity of the upper resin 5b at 25 ° C. is less than 100 cp, the fluidity of the fluorine-containing monomer in the upper resin 5b is preferably ensured.
  • the fluorine-containing monomer in the upper layer resin 5b is not easily mixed into the lower layer resin 5a, and the base film 2 of the upper layer resin 5b (polymer layer 3). It becomes easy to increase the concentration of fluorine atoms on the opposite surface.
  • the mold 6 has a plurality of recesses provided on the surface at a pitch Q (distance between the bottom points of adjacent recesses) Q that is equal to or less than the wavelength of visible light. Therefore, according to the mold 6, a moth-eye structure can be formed on the surface of the resin layer 8.
  • the mold 6 contains aluminum atoms and oxygen atoms as constituent atoms.
  • the mold 6 for example, one produced by the following method can be used. First, aluminum as a material for the mold 6 is formed on the support substrate by sputtering. Next, a female mold (mold 6) having a moth-eye structure can be produced by alternately repeating anodic oxidation and etching on the formed aluminum layer. At this time, the concavo-convex structure of the mold 6 can be changed by adjusting the time for performing anodic oxidation and the time for performing etching.
  • the material of the support substrate is not particularly limited.
  • glass metal material such as stainless steel and nickel; polypropylene, polymethylpentene, cyclic olefin polymer (typically, norbornene resin, etc., Nippon Zeon Co., Ltd.)
  • Polyolefin resins such as polymers (product name: ZEONOR (registered trademark)) and polymers manufactured by JSR (product name: ARTON (registered trademark)); polycarbonate resins; polyethylene terephthalate, polyethylene naphthalate, triacetyl Examples thereof include resin materials such as cellulose.
  • An aluminum substrate may be used instead of the aluminum film formed on the support substrate.
  • the shape of the mold 6 is not particularly limited, and examples thereof include a flat plate shape and a roll shape.
  • the pitch Q between adjacent concave portions is not particularly limited as long as it is equal to or less than the wavelength of visible light (780 nm), but from the viewpoint of realizing a preferable pitch P between adjacent convex portions 4 of the optical film 1 described later, 100 nm or more, It is preferably 400 nm or less, and more preferably 100 nm or more and 200 nm or less.
  • the pitch between adjacent concave portions of the mold is defined as all the pitches in a 1 ⁇ m square region of a planar photograph taken with a scanning electron microscope (product name: S-4700) manufactured by Hitachi High-Technologies Corporation. The average value of the distance between adjacent recessed parts is indicated.
  • a mold release agent 7 is applied to the surface of the mold 6. Therefore, the mold 6 can be easily peeled from the polymer layer 3 in the step (d). Furthermore, the surface energy of the mold 6 can be lowered. Therefore, in the step (b), when the mold 6 is pressed from the upper resin 5b side to the lower resin 5a, fluorine atoms are efficiently oriented on the surface of the upper resin 5b opposite to the base film 2. Can do. Furthermore, before hardening the resin layer 8, it can prevent that a fluorine atom leaves
  • the release agent 7 contains carbon atoms, oxygen atoms, and fluorine atoms as constituent atoms. Since the release agent 7 contains a fluorine atom, the interaction with the fluorine-containing monomer in the upper layer resin 5b is strengthened, and the fluorine atom in the upper layer resin 5b is more efficient on the surface opposite to the base film 2. Can be oriented.
  • Examples of the release agent 7 include those containing a fluorine-containing compound.
  • Known fluorine-containing compounds include, for example, a fluorine-based additive (product name: OPTOOL (registered trademark) DAC-HP) manufactured by Daikin Industries, Ltd. and a fluorine-based additive (product name: OPTOOL) manufactured by Daikin Industries, Ltd.
  • DSX a fluorine-based additive
  • OPTOOL AES4 a fluorine-based additive manufactured by Daikin Industries, Ltd.
  • a fluorine-based additive manufactured by Asahi Glass product name: Afluid
  • DIC a fluorine-based additive manufactured by DIC
  • a fluoric additive manufactured by DIC product name: Mega-Fac RS-75
  • a fluoric additive manufactured by Yushi Co., Ltd. product name: C10GACRY
  • Fluorine-based additives product name: C8HGOL
  • “OPTOOL DSX” manufactured by Daikin Industries, Ltd. is a blend of the following materials.
  • subjected to each material shows the mixture ratio of each material.
  • -Fluorine-containing compound 15 wt% or more, 25 wt% or less
  • -Perfluorohexane 75 wt% or more, 85 wt% or less
  • Hexadecane is dropped on the surface of the mold 6 to which the release agent 7 is applied, and the contact angle immediately after the hexadecane drop measured by the ⁇ / 2 method is ⁇ A (unit: °), contact after 4 minutes of hexadecane drop.
  • ⁇ A and ⁇ B are 85 ° or more, and the difference between ⁇ A and ⁇ B is 3.5 ° or less.
  • ⁇ A and ⁇ B are preferably 90 ° or more, and the difference between ⁇ A and ⁇ B is preferably 3 ° or less.
  • ⁇ A and ⁇ B are preferably as large as possible, but a preferable upper limit value of ⁇ A and ⁇ B is 150 °.
  • the surface of the mold to which the release agent is applied (arranged) is substantially the surface of the release agent applied (arranged) on the mold (the surface opposite to the mold). including.
  • the first measurement point the center portion of the sample is selected, and as the second and third measurement points, 25 mm away from the first measurement point in the longitudinal direction of the sample, and Two points that are point-symmetric with respect to the first measurement point are selected.
  • a release agent 7 is applied, which is measured by X-ray photoelectron spectroscopy (XPS) under conditions of an X-ray beam diameter of 100 ⁇ m, an analysis area of 1000 ⁇ m ⁇ 500 ⁇ m, and a photoelectron extraction angle of 45 °.
  • XPS X-ray photoelectron spectroscopy
  • the fluorine content on the surface of the mold 6 to which the release agent 7 is applied is preferably 43 atom% or more, and more preferably 49 atom% or more.
  • a preferable upper limit of the fluorine content on the surface of the mold 6 to which the release agent 7 is applied is 55 atom%, and a more preferable upper limit is 50 atom%.
  • the fluorine content on the surface of the mold 6 to which the release agent 7 is applied is higher than 55 atom%, the resulting polymer layer 3 may become cloudy.
  • the fluorine content was measured using an X-ray photoelectron spectroscopic analyzer (product name: PHI Quantera SXM) manufactured by ULVAC-PHI, and the apparatus specifications were as follows.
  • X-ray source Monochromatic AlK ⁇ ray (1486.6 eV)
  • Spectroscope Electrostatic concentric hemispherical analyzer
  • Amplifier Multi-channel type
  • the polymer layer 3 The density
  • the mold release effect by the mold release agent 7 is insufficient, at least one of the contact angle of hexadecane and the fluorine content on the surface of the mold 6 coated with the mold release agent 7 is It will be outside the above range.
  • the release effect by the release agent 7 is gradually reduced. Therefore, if the step (b) is continued as it is, there is a concern that the material (aluminum) of the mold 6 will be peeled off and the uneven structure cannot be formed.
  • die 6 might peel similarly.
  • the release agent 7 can be supplied to the surface of the mold 6 in the manufacturing process of the optical film 1 (for example, the release agent every predetermined time). 7) is preferably provided.
  • the thickness Dc of the release agent 7 is not particularly limited, but is preferably 1 nm or more and 5 nm or less. When the thickness Dc of the mold release agent 7 is less than 1 nm, the mold release agent 7 and the surface (hydroxyl group) of the mold 6 are efficiently bonded and do not adhere to each other. Further, the fluorine-containing monomer in the mold release agent 7 There is a concern that the chain formed by cross-linking of the (fluorine-based monomolecular monomers) does not become long (the cross-linking strength does not increase), and as a result, the release effect by the release agent 7 is reduced.
  • the thickness Dc of the release agent 7 indicates the distance from the surface on the mold 6 side to the surface on the opposite side to the mold 6 as shown in FIG.
  • the thickness D of the polymer layer 3 is not particularly limited, but it is preferably thin from the viewpoint of orienting fluorine atoms on the surface of the polymer layer 3 opposite to the base film 2 at a high concentration. Specifically, it is preferably 5 ⁇ m or more and 10 ⁇ m or less. When the thickness D of the polymer layer 3 is less than 5 ⁇ m, there is a concern that defects such as spots and lens defects may occur when the polymer layer 3 is formed. When the thickness D of the polymer layer 3 is larger than 10 ⁇ m, the obtained optical film 1 may be easily curled.
  • the thickness D of the polymer layer 3 in the present embodiment indicates the distance from the surface on the base film 2 side to the apex of the convex portion 4 as shown in FIG.
  • the shape of the convex portion 4 is not particularly limited, and for example, it is narrower toward the tip, such as a shape (bell shape) constituted by a columnar lower portion and a hemispherical upper portion, a cone shape (cone shape, conical shape), or the like.
  • the convex portion 4 may have a shape having a branch protrusion.
  • the branch protrusion indicates a convex portion corresponding to a portion having an irregular interval, which has been formed in the process of anodizing and etching for producing a mold for forming a moth-eye structure.
  • the bottom of the gap between adjacent convex portions 4 has an inclined shape, but it may have a horizontal shape without being inclined.
  • the pitch P between the adjacent convex portions 4 is not particularly limited as long as it is equal to or less than the wavelength of visible light (780 nm). However, from the viewpoint of sufficiently preventing optical phenomena such as moire and rainbow unevenness, it is 100 nm or more and 400 nm or less. It is preferable that it is 100 nm or more and 200 nm or less.
  • the pitch between adjacent convex portions of the optical film is defined as a branch in a 1 ⁇ m square region of a planar photograph taken with a scanning electron microscope (product name: S-4700) manufactured by Hitachi High-Technologies Corporation. The average value of the distance between all adjacent convex parts excluding the protrusions.
  • the pitch between adjacent convex portions is osmium oxide VIII (thickness, manufactured by Wako Pure Chemical Industries, Ltd.) on the uneven structure of the polymer layer using an osmium coater (product name: Neoc-ST) manufactured by Meiwa Forsys. : 5 nm) applied.
  • the height of the convex part 4 is not specifically limited, From the viewpoint of making it compatible with the preferable aspect ratio of the convex part 4 mentioned later, it is preferable that it is 50 nm or more and 600 nm or less, and it is more preferable that it is 100 nm or more and 300 nm or less.
  • the height of the convex portion is 10 pieces arranged continuously except for branch protrusions in a cross-sectional photograph taken with a scanning electron microscope (product name: S-4700) manufactured by Hitachi High-Technologies Corporation. The average value of the height of a convex part is shown.
  • the convex portion having a defect or a deformed portion (such as a portion deformed when preparing a sample) is excluded.
  • the sample one sampled in an area where there is no specific defect of the optical film is used.
  • the optical film is a roll produced continuously, the one sampled near the center is used.
  • the height of the convex portion was determined by using an osmium coater (product name: Neoc-ST) manufactured by Meiwa Forsys Co., Ltd., and osmium oxide VIII (thickness: 5 nm) manufactured by Wako Pure Chemical Industries, Ltd. on the concavo-convex structure of the polymer layer. ) Is applied.
  • the aspect ratio of the convex part 4 is not specifically limited, It is preferable that it is 0.8 or more and 1.5 or less. When the aspect ratio of the convex portion 4 is 1.5 or less, the workability of the moth-eye structure is sufficiently increased, sticking occurs, or the transfer condition when forming the moth-eye structure is deteriorated (the mold is clogged). Or concerns about it) When the aspect ratio of the convex portion 4 is 0.8 or more, optical phenomena such as moire and rainbow unevenness can be sufficiently prevented, and good reflection characteristics can be realized.
  • the aspect ratio of a convex part refers to the ratio (height / pitch) of the pitch between adjacent convex parts and the height of a convex part measured by the method as mentioned above.
  • the arrangement of the protrusions 4 is not particularly limited, and may be arranged randomly or regularly. From the viewpoint of sufficiently preventing the occurrence of moiré, it is preferably arranged randomly.
  • the optical film 1 excellent in antifouling property and abrasion resistance can be manufactured.
  • FIG. 2 is a schematic cross-sectional view illustrating the mold according to the first embodiment.
  • the mold 6 has a plurality of recesses provided on the surface at a pitch Q (distance between the bottom points of adjacent recesses) Q that is equal to or less than the wavelength of visible light. Therefore, according to the mold 6, a moth-eye structure can be formed on the surface of the object (for example, a resin layer).
  • the mold 6 contains aluminum atoms and oxygen atoms as constituent atoms.
  • a mold release agent 7 is disposed on the surface of the mold 6.
  • the release agent 7 contains carbon atoms, oxygen atoms, and fluorine atoms as constituent atoms. Thereby, the mold 6 having releasability and low surface energy is obtained.
  • Hexadecane is dropped on the surface of the mold 6 on which the mold release agent 7 is disposed, and the contact angle immediately after the hexadecane dropping measured by the ⁇ / 2 method is ⁇ A (unit: °), contact after 4 minutes of hexadecane dropping. If the angle is defined as ⁇ B (unit: °), ⁇ A and ⁇ B are 85 ° or more, and the difference between ⁇ A and ⁇ B is 3.5 ° or less.
  • Carbon on the surface of the mold 6 on which the release agent 7 is disposed measured by X-ray photoelectron spectroscopy under conditions of an X-ray beam diameter of 100 ⁇ m, an analysis area of 1000 ⁇ m ⁇ 500 ⁇ m, and a photoelectron extraction angle of 45 °
  • the ratio of the number of fluorine atoms to the total number of atoms, aluminum atoms, oxygen atoms, and fluorine atoms is 30 atom% or more.
  • die of Embodiment 1 is preferably used when manufacturing the optical film excellent in antifouling property and abrasion resistance.
  • die of Embodiment 1 As an example of the metal mold
  • FIG. 3 is a schematic cross-sectional view for explaining the manufacturing process of the optical film of Embodiment 2 (steps a to e). Since the manufacturing method of the optical film of Embodiment 2 is the same as the manufacturing method of the optical film of Embodiment 1 except that the lower layer resin and the upper layer resin are sequentially applied onto the base film, the overlapping points will be described. Omitted where appropriate. In addition, since the metal mold
  • FIG. 4 is a schematic cross-sectional view for explaining the manufacturing process of the optical film of Embodiment 3 (steps a to d). Since the manufacturing method of the optical film of Embodiment 3 is the same as the manufacturing method of the optical film of Embodiment 1 except that the lower layer resin and the upper layer resin are simultaneously coated on the base film, the overlapping points will be described. Omitted where appropriate. In addition, since the metal mold
  • the manufacturing method of the optical film of Embodiment 3 since the lower layer resin 5a and the upper layer resin 5b are applied simultaneously, the number of steps can be reduced as compared with the manufacturing method of the optical film of Embodiment 2.
  • FIG. 5 is a schematic cross-sectional view for explaining the manufacturing process of the optical film of Embodiment 4 (steps a to e). Since the manufacturing method of the optical film of Embodiment 4 is the same as the manufacturing method of the optical film of Embodiment 1 except that the upper layer resin and the lower layer resin are sequentially applied onto the mold, the explanation of overlapping points is appropriately given. Omitted. In addition, since the metal mold
  • the size of the mold M-1 was 5 cm ⁇ 10 cm.
  • Anodization was performed using oxalic acid (concentration: 0.03% by weight) under conditions of a liquid temperature of 5 ° C. and an applied voltage of 80V. The time for one anodic oxidation was 25 seconds.
  • Etching was performed using phosphoric acid (concentration: 1 mol / l) at a liquid temperature of 30 ° C. The time for performing one etching was set to 25 minutes.
  • the surface specification of the mold M-1 was as follows. ⁇ Pitch Q between adjacent recesses: 200 nm -Depth of recess: 400nm
  • a release treatment was performed by applying a release agent to the surface of the mold M-1.
  • a release agent a solution in which “OPTOOL DSX” manufactured by Daikin Industries, Ltd. was diluted with perfluorohexane to a solid content concentration of 0.1% by weight was used.
  • the thickness Dc of the release agent was 2 to 3 nm.
  • Mold M-2 to M-6 Resin is continuously transferred using a mold similar to the mold M-1, and the mold M-2, the mold M-3, the mold M-4, and the mold M are arranged in the order of short usage period. -5 and mold M-6 (mold with the longest use period) were prepared.
  • C1s peak, Al2p peak, O1s peak, and F1s peak were detected in each mold.
  • the release agent applied to the surface of each mold contained carbon atoms, oxygen atoms, and fluorine atoms as constituent atoms, and the F1s peak was derived from the release agent.
  • Each die contained aluminum atoms and oxygen atoms as constituent atoms, and the Al2p peak was derived from the die.
  • fluorine atoms relative to the total number of carbon atoms, aluminum atoms, oxygen atoms, and fluorine atoms on the surface of each mold coated with a release agent The ratio of the number (fluorine content) was calculated.
  • the fluorine content on the surface of the mold coated with the mold release agent obtained by measurement by X-ray photoelectron spectroscopy, is the fluorine content in the region within 6 nm in the depth direction from the outermost surface of the mold release agent. Point to.
  • the contact angle immediately after dropping of hexadecane on the surface and the contact angle after 4 minutes of dropping of hexadecane were 85 ° or more, and both The difference was 3.5 ° or less. Further, all of the molds M-1 to M-3 had a fluorine content of 30 atom% or more on the surface.
  • the mold M-4 had a contact angle with respect to the surface immediately after dropping of hexadecane and a contact angle after 4 minutes of dropping of hexadecane of less than 85 °. Further, the mold M-4 had a fluorine content of less than 30 atom% on the surface.
  • the mold M-5 had a contact angle of 85 ° or more immediately after the hexadecane was dropped on the surface, the contact angle after 4 minutes of hexadecane was less than 85 °. It was larger than 3.5 °. Further, the mold M-5 had a fluorine content of less than 30 atom% on the surface.
  • the mold M-6 had a contact angle immediately after dropping hexadecane on the surface and a contact angle after 4 minutes of dropping of hexadecane of less than 85 °, and the difference between them was 3.5 °. It was bigger than. Further, the mold M-6 had a fluorine content of less than 30 atom% on the surface.
  • Example 1 The optical film of Example 1 was produced by the optical film manufacturing method of Embodiment 4.
  • the upper layer resin 5b was applied onto the mold 6 (on the surface of the mold 6 coated with the release agent 7) by dropping it with a dropper.
  • the above upper layer resin UR-1 was used as the upper layer resin 5b.
  • the thickness Db of the upper layer resin 5b was 1 ⁇ m.
  • the mold M-2 described above was used as the mold 6 with the release agent 7 applied on the surface.
  • the lower layer resin 5a As the lower layer resin 5a, the lower layer resin LR-1 described above was used.
  • the thickness Da of the lower layer resin 5a was 8 ⁇ m.
  • a polyethylene terephthalate film with an easy-adhesion layer (product name: Cosmo Shine (registered trademark) A4300) manufactured by Toyobo Co., Ltd. was used.
  • the thickness of the base film 2 was 60 ⁇ m.
  • Examples 2 to 5 and Comparative Examples 1 to 5 An optical film of each example was produced in the same manner as in Example 1 except that the materials and members were changed as shown in Tables 3 to 8.
  • the description of each material and each member in Tables 3 to 8 is as follows. ⁇ Lower layer resin> ⁇ "LR-1”: Lower layer resin LR-1 ⁇ Upper layer resin> "UR-1" to "UR-3”: Upper resin UR-1 to UR-3 ⁇ Mold> ⁇ "M-1" to "M-6”: Molds M-1 to M-6
  • Anti-fouling property As antifouling property, (i) contact angle (water and hexadecane) and (ii) fluorine content on the surface of the optical film of each example were evaluated.
  • C1s peak, N1s peak, O1s peak, and F1s peak were detected in the optical film of each example. That is, it was found that the polymer layer of the optical film in each example contained carbon atoms, nitrogen atoms, oxygen atoms, and fluorine atoms as constituent atoms.
  • the ratio of the number of fluorine atoms to the total number of carbon atoms, nitrogen atoms, oxygen atoms, and fluorine atoms on the surface of the polymer layer was calculated.
  • the fluorine content on the surface of the polymer layer obtained by measurement by X-ray photoelectron spectroscopy refers to the fluorine content in a region within 6 nm in the depth direction from the outermost surface of the polymer layer.
  • Friction resistance The surface of the optical film of each example (the surface opposite to the base film of the polymer layer) was applied to steel wool (product name: # 0000) manufactured by Nippon Steel Wool Co., Ltd. with a load of 400 g. The state was rubbed once, and the dynamic friction resistance value at that time was measured. When rubbing with steel wool, a surface property measuring machine (product name: 14FW) manufactured by Shinto Kagaku Co., Ltd. was used as a testing machine, and the stroke width was 20 mm and the speed was 0.5 mm / s.
  • Examples 1 to 5 had a higher fluorine content on the surface of the optical film (the surface of the polymer layer) than Comparative Examples 1 to 5.
  • the contact angles of water and hexadecane with respect to the surface of the optical film were larger than those of Comparative Examples 1 to 5.
  • the contact angle of water with respect to the surface of the optical film is larger than 140 ° in Example 1.
  • it could not be dropped it was 101.3 ° in Comparative Example 1. Therefore, Example 1 was superior in water repellency to Comparative Example 1.
  • Example 1 was more excellent in oil repellency than Comparative Example 1. From the above, Examples 1 to 5 were superior in antifouling properties to Comparative Examples 1 to 5.
  • Examples 1 to 5 had lower friction resistance and better steel wool resistance than Comparative Examples 1 to 5. Therefore, Examples 1 to 5 were superior to Comparative Examples 1 to 5 in abrasion resistance.
  • Examples 1 to 5 were superior to Comparative Examples 1 to 5 in antifouling properties and abrasion resistance. That is, the contact angle immediately after dropping of hexadecane on the surface and the contact angle after 4 minutes of dropping of hexadecane are 85 ° or more, the difference between them is 3.5 ° or less, and the fluorine content on the surface is 30 atom%. It was found that an optical film excellent in antifouling property and abrasion resistance can be obtained by using the above molds (molds M-1 to M-3).
  • each number other than fluorine atoms with respect to the total number of carbon atoms, nitrogen atoms, oxygen atoms, and fluorine atoms on the surface of the polymer layer.
  • the ratio of the number of atoms was calculated.
  • Table 9 shows the calculation results.
  • Table 9 also shows the above-described fluorine content (ratio of the number of fluorine atoms).
  • FIG. 6 is a graph showing the narrow spectra of the optical films of Examples 1 to 3 and Comparative Examples 1 and 2, wherein (a) shows the C1s peak, (b) shows the N1s peak, c) shows the O1s peak, and (d) shows the F1s peak.
  • C / s on the vertical axis in FIG. 6 is an abbreviation for “counts / second”. The same applies to other drawings.
  • the measurement conditions for the narrow spectrum were as follows. ⁇ X-ray beam diameter: 100 ⁇ m (12.5 W, 15 kV) ⁇ Analysis area: 1000 ⁇ m ⁇ 500 ⁇ m -Photoelectron extraction angle: 45 ° ⁇ Pass energy: 112eV
  • each of the C1s peak and O1s peak of the obtained narrow spectrum was separated into a plurality of peaks, and a binding species corresponding to each peak was identified from each peak position and shape.
  • FIG. 7 is a graph showing the analysis result of the C1s peak of Example 1 in FIG.
  • FIG. 8 is a graph showing the analysis result of the C1s peak of Example 2 in FIG.
  • FIG. 9 is a graph showing the analysis result of the C1s peak of Example 3 in FIG.
  • FIG. 10 is a graph showing the analysis result of the C1s peak of Comparative Example 1 in FIG.
  • FIG. 11 is a graph showing the analysis result of the C1s peak of Comparative Example 2 in FIG. 7 to 11, the peak Cs corresponds to the C1s peak in each example in FIG.
  • the peaks C1 to C7 are spectra obtained by curve fitting with peaks derived from each bond type with respect to the peak Cs (C1s peak). Note that the obtained spectrum was subjected to charge correction so that the position of the peak C1 was 284.6 eV.
  • Table 10 shows the positions of the peaks C1 to C7 and the identified binding species. In identifying each binding species, the information described in Non-Patent Document 1 and Table 1 of Non-Patent Document 2 were used.
  • the peak C7 is identified as “CF 3 bond and OCF 2 bond”.
  • the peak derived from the CF 3 bond and the OCF 2 bond are shown. Since it is located at almost the same position as the peak derived from it, it was difficult to separate the two peaks.
  • FIG. 12 is a graph showing the analysis result of the O1s peak of Example 1 in FIG.
  • FIG. 13 is a graph showing the analysis result of the O1s peak of Example 2 in FIG.
  • FIG. 14 is a graph showing the analysis result of the O1s peak of Example 3 in FIG.
  • FIG. 15 is a graph showing the analysis result of the O1s peak of Comparative Example 1 in FIG.
  • FIG. 16 is a graph showing the analysis result of the O1s peak of Comparative Example 2 in FIG. 12 to 16, the peak Os corresponds to the O1s peak in each example in FIG. 6C.
  • peaks O1 to O3 are spectra obtained by curve fitting with peaks derived from each bond type with respect to peak Os (O1s peak).
  • Table 11 shows the positions of the peaks O1 to O3 and the identified binding species. In identifying each binding species, the information described in Non-Patent Document 3 and FIG. 2 of Non-Patent Document 4 were used.
  • each of the C1s peak and the O1s peak of the narrow spectrum on the surface of the optical film could be separated into peaks derived from each binding species.
  • One aspect of the present invention is a method for producing an optical film having a concavo-convex structure provided on the surface with a plurality of convex portions provided at a pitch equal to or less than the wavelength of visible light, the step of applying a lower layer resin and an upper layer resin (1);
  • a mold is pressed against the lower layer resin and the upper layer resin from the upper layer resin side to form a resin layer having the concavo-convex structure on the surface ( 2) and the step (3) of curing the resin layer
  • the upper layer resin contains a fluorine-containing monomer
  • a mold release agent is applied to the surface of the mold, and the mold release agent Includes carbon atoms, oxygen atoms, and fluorine atoms as constituent atoms
  • the mold includes aluminum atoms and oxygen atoms as constituent atoms, on the surface of the mold on which the release agent is applied.
  • Hexadecane is dropped measured by theta / 2 method, the contact angle immediately after hexadecane dropwise theta A (Unit: °), the contact angle after hexadecane dropwise 4 minutes theta B (unit: °) Defining a, theta A and theta B is 85 ° or more, and the difference between ⁇ A and ⁇ B is 3.5 ° or less, an X-ray beam diameter of 100 ⁇ m, an analysis area of 1000 ⁇ m ⁇ 500 ⁇ m, and a photoelectron extraction angle of 45 °.
  • the ratio of the number of atoms may be a method for producing an optical film that is 30 atom% or more.
  • “Applying the lower layer resin and the upper layer resin” in the step (1) is not limited to the case where the lower layer resin and the upper layer resin are applied on the same member, but the lower layer resin and the upper layer resin are different. This includes the case where it is applied onto a member. As a case where the lower layer resin and the upper layer resin are applied on different members, for example, the lower layer resin may be applied onto a base film and the upper layer resin may be applied onto the mold.
  • step (2) “pressing a mold from the upper layer resin side to the lower layer resin and the upper layer resin in a state where the applied lower layer resin and the upper layer resin are laminated” means the lower layer This includes not only the case where the mold is pressed after the resin and the upper layer resin are laminated, but also the case where the mold is pressed while the lower layer resin and the upper layer resin are laminated.
  • the lower layer resin and the upper layer resin are laminated (hereinafter also referred to as a lamination step), and the mold is attached to the lower layer resin and the upper layer resin from the upper layer resin side. It includes a method of performing pressing (hereinafter also referred to as pressing step) at the same timing or at different timings.
  • the following method (i) is preferable.
  • the lower layer resin is coated on a base film, the upper layer resin is coated on the mold, and then the mold coated with the upper layer resin is moved from the upper layer resin side to the base material.
  • the upper layer resin is laminated on the lower layer resin (the laminating step) while pressing against the lower layer resin applied on the film (the pressing step). That is, the step (1) is performed by applying the lower layer resin on a base film and applying the upper layer resin on the mold, and the step (2) is performed by applying the upper layer resin.
  • the mold may be pressed from the upper layer resin side against the lower layer resin coated on the base film. In this case, the concavo-convex structure can be formed while laminating the upper layer resin on the lower layer resin.
  • the number of steps can be reduced as compared with the case where the lower layer resin and the upper layer resin are sequentially applied onto the base film (method (ii) described later). Further, according to this method, the antifouling property can be preferably increased, and in particular, the loss of the constituent material of the upper layer resin can be minimized.
  • the lower layer resin and the upper layer resin are sequentially applied onto the base film (the lamination step), and then the mold is pressed against the lower layer resin and the upper layer resin from the upper layer resin side (the pressing step). ). That is, the said process (1) may be performed by apply
  • the lower layer resin and the upper layer resin can be efficiently applied by providing an apparatus of a general application method (for example, gravure method, slot die method, etc.).
  • the lower layer resin and the upper layer resin are simultaneously coated on the base film (the upper layer resin is formed on the side opposite to the base film of the lower layer resin) (the layering step), and then The mold is pressed against the lower layer resin and the upper layer resin from the upper layer resin side (the pressing step). That is, the said process (1) may be performed by apply
  • the upper layer resin and the lower layer resin are sequentially applied onto the mold (the laminating step), and then the mold on which the upper layer resin and the lower layer resin are applied is pressed against the base film ( Pressing step above). That is, the step (1) may be performed by sequentially applying the upper layer resin and the lower layer resin onto the mold. In this case, for example, if a flexible mold is used as the mold, the uneven structure can be easily formed regardless of the shape of the base film.
  • the step (1) may be performed by simultaneously applying the upper layer resin and the lower layer resin on the mold.
  • the uneven structure can be easily formed regardless of the shape of the base film.
  • Optical film 2 Base film 3: Polymer layer 4: Convex part 5a: Lower layer resin 5b: Upper layer resin 6: Mold 7: Release agent 8: Resin layer P, Q: Pitch D: Polymer layer Thickness Da: Lower layer resin thickness Db: Upper layer resin thickness Dc: Release agent thickness C1, C2, C3, C4, C5, C6, C7, Cs, O1, O2, O3, Os: peak

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Laminated Bodies (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)

Abstract

La présente invention concerne un procédé de fabrication d'un film optique présentant d'excellentes propriétés antisalissures et antifrottement. Ledit procédé de fabrication d'un film optique comprend une étape (1) consistant à appliquer une résine de couche inférieure et une résine de couche supérieure, une étape (2) consistant, lorsque la résine de couche inférieure et la résine de couche supérieure appliquées sont stratifiées, à presser un moule sur la résine de couche inférieure et la résine de couche supérieure à partir du côté résine de couche supérieure pour former une couche de résine comprenant une structure irrégulière sur une surface de celle-ci, et une étape (3) consistant à durcir la couche de résine. La résine de couche supérieure comprend un monomère contenant du fluor et une surface du moule a été revêtue d'un agent de démoulage. Dans la surface du moule revêtu de l'agent de démoulage, l'angle de contact de l'hexadécane mesuré par le procédé θ/2, et le rapport du nombre d'atomes de fluor par rapport au total du nombre d'atomes de carbone, du nombre d'atomes d'aluminium, du nombre d'atomes d'oxygène et du nombre d'atomes de fluor mesurés par spectroscopie photoélectronique aux rayons X se situe dans une plage prédéfinie.
PCT/JP2017/010552 2016-03-23 2017-03-16 Procédé de fabrication d'un film optique et moule WO2017164046A1 (fr)

Priority Applications (2)

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JP2018507270A JP6600078B2 (ja) 2016-03-23 2017-03-16 光学フィルムの製造方法
CN201780014466.9A CN108780162B (zh) 2016-03-23 2017-03-16 光学薄膜的制造方法以及模具

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JP2016-058990 2016-03-23

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Publication number Priority date Publication date Assignee Title
JP2019064056A (ja) * 2017-09-29 2019-04-25 シャープ株式会社 防汚性フィルムの製造方法
JP2020030313A (ja) * 2018-08-22 2020-02-27 シャープ株式会社 防汚性フィルムの製造方法
JPWO2020184727A1 (fr) * 2019-03-13 2020-09-17

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WO2011078265A1 (fr) * 2009-12-24 2011-06-30 三菱レイヨン株式会社 Procédé d'évaluation des performances d'un agent organique de démoulage, processus de production d'un moule et processus de production d'un film transparent présentant une structure finement rugosifiée à sa surface
WO2013187506A1 (fr) * 2012-06-15 2013-12-19 三菱レイヨン株式会社 Stratifié
WO2013191089A1 (fr) * 2012-06-22 2013-12-27 シャープ株式会社 Procédé de fabrication d'un film antireflet

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KR20160015160A (ko) * 2014-07-30 2016-02-12 스미또모 가가꾸 가부시키가이샤 방현 필름

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WO2011078265A1 (fr) * 2009-12-24 2011-06-30 三菱レイヨン株式会社 Procédé d'évaluation des performances d'un agent organique de démoulage, processus de production d'un moule et processus de production d'un film transparent présentant une structure finement rugosifiée à sa surface
WO2013187506A1 (fr) * 2012-06-15 2013-12-19 三菱レイヨン株式会社 Stratifié
WO2013191089A1 (fr) * 2012-06-22 2013-12-27 シャープ株式会社 Procédé de fabrication d'un film antireflet

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019064056A (ja) * 2017-09-29 2019-04-25 シャープ株式会社 防汚性フィルムの製造方法
JP2020030313A (ja) * 2018-08-22 2020-02-27 シャープ株式会社 防汚性フィルムの製造方法
JPWO2020184727A1 (fr) * 2019-03-13 2020-09-17
CN113574422A (zh) * 2019-03-13 2021-10-29 松下知识产权经营株式会社 光学元件及其制造方法
JP7349687B2 (ja) 2019-03-13 2023-09-25 パナソニックＩｐマネジメント株式会社 光学素子
CN113574422B (zh) * 2019-03-13 2023-10-13 松下知识产权经营株式会社 光学元件及其制造方法

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CN108780162B (zh) 2019-09-03
CN108780162A (zh) 2018-11-09

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