US20120064303A1 - Optical device and method of manufacturing the same - Google Patents

Optical device and method of manufacturing the same Download PDF

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Publication number
US20120064303A1
US20120064303A1 US13/302,461 US201113302461A US2012064303A1 US 20120064303 A1 US20120064303 A1 US 20120064303A1 US 201113302461 A US201113302461 A US 201113302461A US 2012064303 A1 US2012064303 A1 US 2012064303A1
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United States
Prior art keywords
region
layer
optical device
recesses
protrusions
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Abandoned
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US13/302,461
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English (en)
Inventor
Kazuhiro Yashiki
Chikara Sawamura
Koji Umezaki
Akira Kubo
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Toppan Inc
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Toppan Printing Co Ltd
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Assigned to TOPPAN PRINTING CO., LTD. reassignment TOPPAN PRINTING CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KUBO, AKIRA, SAWAMURA, CHIKARA, UMEZAKI, KOJI, YASHIKI, KAZUHIRO
Publication of US20120064303A1 publication Critical patent/US20120064303A1/en
Priority to US13/838,476 priority Critical patent/US9272308B2/en
Abandoned legal-status Critical Current

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    • 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
    • B05D5/061—Special surface effect
    • B05D5/063—Reflective effect
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/20—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof characterised by a particular use or purpose
    • B42D25/29—Securities; Bank notes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/30—Identification or security features, e.g. for preventing forgery
    • B42D25/324—Reliefs
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/18—Diffraction gratings
    • G02B5/1842—Gratings for image generation
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/32—Holograms used as optical elements
    • B42D2033/18—
    • B42D2033/24—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/30—Identification or security features, e.g. for preventing forgery
    • B42D25/328—Diffraction gratings; Holograms
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24479—Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness
    • Y10T428/24612—Composite web or sheet

Definitions

  • the present invention relates to an optical technique that offers, for example, forgery prevention effect, decorative effect and/or aesthetic effect.
  • optical devices include a microstructure such as diffraction grating, hologram, lens array, etc.
  • the microstructures are hard to analyze. Further, in order to manufacture an optical device including the microstructure, an expensive manufacturing apparatus such as electron beam writer is necessary. For these reasons, the above optical devices achieve an excellent performance in forgery prevention.
  • the optical devices include a relief structure formation layer with a main surface having the microstructure and a reflective layer provided thereon.
  • the reflective layer may be formed in a pattern on a part of the main surface in order to further enhance the forgery prevention effect. For example, when the reflective layer is provided on the main surface to have contours corresponding to micro-characters, a pattern that emits diffracted light and has a shape corresponding to the micro-characters can be obtained.
  • photolithography can be used (for example, refer to Patent Document 1). This method allows forming a patterned reflective layer with high definition.
  • This method requires alignment of the relief structure formation layer with respect to a mask. Simultaneously achieving a high producibility and a high positional accuracy is, however, impossible or very difficult. For example, according to this method, a displacement of 100 ⁇ m or more may be produced between the target position and the contour of the reflective layer.
  • Patent Document 2 employed are the following methods in order to form a reflective layer with a high positional accuracy.
  • prepared first is a relief structure formation layer that includes a “first region” having a relief structure with a greater depth-to-width ratio and a “second region” as a flat region or a region having a relief structure with a smaller depth-to-width ratio.
  • a metal reflective layer is formed on the relief structure formation layer to have a uniform surface density.
  • the stacked body thus obtained is subjected to an etching treatment.
  • the portion of the metal reflective layer corresponding to the “first region” is lower in etching resistance than the portion corresponding to the “second region”. Therefore, the portion corresponding to the “first region” can be removed before the portion of the metal reflective layer corresponding to the “second region” is removed completely. That is, the metal reflective layer can be formed only on the “second region”.
  • the portion of the metal reflective layer corresponding to the “second region” is partially removed by the etching treatment. For this reason, there is a possibility that the portion of the metal reflective layer corresponding to the “second region” has an excessively small thickness and thus has an insufficient reflectance. Alternatively, there is a possibility that the thickness of the metal reflective layer greatly varies at the portion corresponding to the “second region”. That is, according to this method, it is difficult to stably form the metal reflective layer.
  • utilized is a difference between the transmittance of the portions of the above-described stacked body corresponding to the “first region” and the “second region”. Specifically, utilized is the fact that the stacked body has a higher transmittance at the portion corresponding to the “first region” than at the portion corresponding to the “second region”.
  • prepared first is a stacked body of a relief structure formation layer and a metal reflective layer.
  • a photosensitive layer is formed on the metal reflective layer.
  • the stacked body is entirely irradiated with light from the relief structure formation layer's side. This makes it possible to cause a photoreaction at a higher efficiency in the portion of the photosensitive layer corresponding to the “first region”.
  • either one of the regions of the photosensitive layer corresponding to the “first region” and the “second region” is removed by treating it with a suitable solvent, etc.
  • the metal reflective layer is subjected to an etching treatment using the partially removed photosensitive layer as a mask.
  • an etching treatment using the partially removed photosensitive layer as a mask.
  • this method requires an exposure process for the photosensitive layer. Therefore, this method is disadvantageous in cost and producibility.
  • An object of the present invention is to provide an optical technique that makes it possible to stably form a reflective layer with a high positional accuracy.
  • an optical device comprising a relief structure formation layer including first and second regions adjacent to each other, the first region including first and second sub-regions, the first sub-region being adjacent to the second region and extending along a boundary between the first and second regions, the second sub-region being adjacent to the second region with the first sub-region interposed therebetween, the second region being provided with recesses or protrusions and having a ratio of surface area to apparent area greater than that of the first region; a first layer made of a first material having a refractive index different from that of a material of the relief structure formation layer and covering at least the second sub-region, a portion of the first layer corresponding to the second sub-region having a surface profile corresponding to a surface profile of the second sub-region, a ratio of an amount of the first material at a position of the second region to an apparatus area of the second region being zero or smaller than a ratio of an amount of the first material at a position of the second sub-region to an apparatus
  • a method of manufacturing an optical device comprising forming a relief structure formation layer including first and second regions adjacent to each other, the second region being provided with recesses or protrusions and having a ratio of surface area to apparent area greater than that of the first region; vapor-depositing a first material having a refractive index different from that of a material of the relief structure formation layer entirely on the first and second regions to form a reflective material layer, the reflective material layer having a surface profile corresponding to surface profiles of the first and second regions, or the reflective material layer having a surface profile corresponding to the surface profile of the first region at a portion corresponding to the first region and being partially opened correspondingly to an arrangement of the recesses or protrusions at a portion corresponding to the second region; vapor-depositing a second material different from the first material on the reflective material layer to form a mask layer, the mask layer having a surface profile corresponding to the surface profiles of the first and second regions, or the mask layer
  • FIG. 1 is a plan view schematically showing an example of an optical device according to an embodiment of the present invention
  • FIG. 2 is a sectional view of the optical device taken along a line II-II shown in FIG. 1 ;
  • FIG. 3 is a sectional view schematically showing a method of manufacturing the optical device shown in FIGS. 1 and 2 ;
  • FIG. 4 is a sectional view schematically showing the method of manufacturing the optical device shown in FIGS. 1 and 2 ;
  • FIG. 5 is a sectional view schematically showing the method of manufacturing the optical device shown in FIGS. 1 and 2 ;
  • FIG. 6 is a sectional view schematically showing the method of manufacturing the optical device shown in FIGS. 1 and 2 ;
  • FIG. 7 is a plan view schematically showing an optical device according to a modified example.
  • FIG. 8 is a sectional view of the optical device taken along a line VIII-VIII shown in FIG. 7 ;
  • FIG. 9 is a plan view schematically showing an optical device according to another modified example.
  • FIG. 10 is a sectional view of the optical device taken along a line X-X shown in FIG. 9 ;
  • FIG. 11 is a plan view schematically showing an optical device according to another embodiment of the present invention.
  • FIG. 12 is a sectional view of the optical device taken along a line XII-XII shown in FIG. 11 ;
  • FIG. 13 is a sectional view schematically showing a method of manufacturing the optical device shown in FIGS. 11 and 12 ;
  • FIG. 14 is a sectional view schematically showing the method of manufacturing the optical device shown in FIGS. 11 and 12 ;
  • FIG. 15 is a sectional view schematically showing the method of manufacturing the optical device shown in FIGS. 11 and 12 ;
  • FIG. 16 is a sectional view schematically showing the method of manufacturing the optical device shown in FIGS. 11 and 12 ;
  • FIG. 17 is a sectional view schematically showing the method of manufacturing the optical device shown in FIGS. 11 and 12 ;
  • FIG. 18 is a graph showing an example of a relationship between presence or absence of the mask layer and the etching rate.
  • FIG. 1 is a plan view schematically showing an example of an optical device according to an embodiment of the present invention.
  • FIG. 2 is a sectional view of the optical device taken along a line II-II shown in FIG. 1 .
  • the X and Y directions are parallel with a main surface of the optical device 10 and perpendicular to each other, while the Z direction is perpendicular to the main surface of the optical device 10 .
  • the display portion DP 1 is the portion of the optical device 10 that corresponds to the first region R 1 described later
  • the display portion DP 2 is the portion of the optical device 10 that corresponds to the second region R 2 described later.
  • the optical device 10 shown in FIGS. 1 and 2 includes a relief structure formation layer 110 , a first layer 120 ′ and a second layer 130 ′.
  • the first layer 120 ′ partially covers the main surface of the relief structure formation layer 110 .
  • the second layer 130 ′ covers the first layer 120 ′.
  • FIGS. 1 and 2 A method of manufacturing the optical device 10 shown in FIGS. 1 and 2 will be described with reference to FIGS. 3 to 6 .
  • FIGS. 3 to 6 are sectional views schematically showing a method of manufacturing the optical device shown in FIGS. 1 and 2 .
  • prepared first is a relief structure formation layer 110 that has a main surface including a first region R 1 and a second region R 2 as shown in FIG. 3 .
  • the first region R 1 is flat or provided with a recessed structure and/or a protruding structure. Recesses and protrusions constitute the recessed structure and the protruding structure, respectively. In the case where the first region R 1 is provided with the recesses or protrusions, the recesses or protrusions may be arranged one-dimensionally or two-dimensionally. Also, in this case, the recesses or protrusions may be arranged regularly or randomly.
  • FIG. 3 shows the case where the first region R 1 is provided with grooves as the recesses that are arranged one-dimensionally and regularly. Typically, the grooves form a diffraction grating or hologram that emits a diffracted light when illuminated with a white light.
  • the cross sections of the grooves that are perpendicular to the lengthwise directions thereof have, for example, tapered shapes such as shapes of letters V and U or rectangular shapes.
  • FIG. 3 shows the case where the cross sections are V-shaped as an example.
  • the widths of the openings of the grooves provided to the first region R 1 are set within, for example, a range of 100 to 3,000 nm.
  • the depths of the grooves are set within, for example, a range of 20 to 1,500 nm.
  • the mean value of ratios of the depths to the widths of the openings of the grooves is set, for example, at 0.5 or less, and typically within a range of 0.05 to 0.3.
  • the second region R 2 is provided with a recessed structure and/or a protruding structure.
  • Recesses and protrusions constitute the recessed structure and the protruding structure, respectively.
  • the recesses or protrusions may be arranged one-dimensionally or two-dimensionally. Also, the recesses or protrusions may be arranged regularly or randomly.
  • FIG. 3 shows the case where the second region R 2 is provided with grooves as the recesses that are arranged one-dimensionally and regularly.
  • the cross sections of the grooves that are perpendicular to the lengthwise directions thereof have, for example, tapered shapes such as shapes of letters V and U or rectangular shapes.
  • FIG. 3 shows the case where the cross sections are V-shaped as an example.
  • the second region R 2 has a ratio of a surface area to an apparent area greater than that of the first region R 1 .
  • an “apparent area” of a region means an area of an orthogonal projection of the region on a plane parallel with the region, that is, an area of the region from which the recessed structure and the protruding structure are omitted.
  • a “surface area” of a region means an area of the region in consideration of the recessed structure and the protruding structure.
  • the recesses or protrusions on the second region R 2 typically have a mean value of ratios of the depths to the diameters or widths of the openings of the recesses or a mean value of ratios of the heights to the diameters or widths of the bottoms of the protrusions greater than that of the recesses or protrusions on the first region R 1 .
  • the groves on the second region R 2 have a ratio of the depth to the width of the opening of the groove greater than that of the grooves on the first region R 1 .
  • the widths of the grooves on the second region R 2 are set within, for example, a range of 100 to 3,000 nm.
  • the depths of the grooves are set within, for example, a range of 80 to 6,000 nm.
  • the mean value of the ratios of the depths to the widths of the openings of the grooves on the second region R 2 is set greater than the mean value of the ratios of the depths to the widths of the openings of the grooves on the first region R 1 .
  • the mean value of the ratios of the depths to the widths of the openings of the grooves on the second region R 2 is set within, for example, a range of 0.8 to 2.0, and typically a range of 0.8 to 1.2. When the value is excessively large, there is a possibility that the producibility of the relief structure formation layer 110 is degraded.
  • the relief structure formation layer 110 can be formed by, for example, pressing a stamping die provided with fine protrusions against a resin.
  • the protrusions have shapes that correspond to the shapes of the recesses on the region R 2 or the recesses on the regions R 1 and R 2 .
  • the relief structure formation layer 110 is formed by, for example, a method in which a substrate is coated with a thermoplastic resin and then a plate having the above-described protrusions thereon is pressed against the resin while applying heat thereto.
  • a thermoplastic resin for example, acrylic resin, epoxy resin, cellulosic resin, vinyl resin, mixtures thereof or copolymers thereof is used.
  • the relief structure formation layer 110 may be formed by a method in which a substrate is coated with a thermosetting resin, a plate having the above-described protrusions thereon is pressed against the resin while applying heat thereto, and then the plate is removed therefrom.
  • a thermosetting resin for example, urethane resin, melamine resin, epoxy resin, phenol resin, mixtures thereof or copolymers thereof is used.
  • the urethane resin can be obtained by, for example, adding polyisocyanate as a crosslinking agent to acrylic polyol or polyester polyol having a reactive hydroxyl group and causing crosslinking reaction thereof.
  • the relief structure formation layer may be formed by a method in which a substrate is coated with a radiation-curing resin, the rein is irradiated with radiation such as ultraviolet ray while pressing the late against the resin, and then the plate is removed therefrom.
  • the relief structure formation layer may be formed by a method in which the composition is injected between a substrate and the plate, this material is cured by a radiation exposure, and then the plate is removed therefrom.
  • the radiation-curing resin typically contains a polymerizable compound and an initiator.
  • the polymerizable compound for example, a compound capable of causing a photo-induced radical polymerization is used.
  • a compound capable of causing a photo-induced radical polymerization for example a monomer, oligomer or polymer having an ethylenic unsaturated bond or ethylenic unsaturated group is used.
  • a monomer such as 1,6-hexanediol, neopentyl glycol diacrylate, trimethylol propane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol pentaacrylate and dipentaerythritol hexaacrylate; an oligomer such as epoxy acrylate, urethane acrylate and polyester acrylate; or a polymer such as urethane-modified acrylic resin and epoxy-modified acrylic resin may be used.
  • a photo-induced radical polymerization initiator is used as the initiator.
  • the photo-induced radical polymerization initiator for example, benzoin-based compound such as benzoin, benzoin methyl ether and benzoin ethyl ether; anthraquinone-based compound such as anthraquinone and methyl anthraquinone; phenyl ketone-based compound such as acetophenone, diethoxy acetophenone, benzophenone, hydroxy acetophenone, 1-hydroxycyclohexyl phenyl ketone, ⁇ -aminoacetophenone and 2-methyl-1-(4-methyl thiophenyl)-2-morpholinopropane-1-one; benzyldimethyl ketal; thioxanthone; acylphosphine oxide; or Michler's ketone is used
  • a compound capable of causing photo-induced cationic polymerization may be used as the polymerizable compound.
  • the compound capable of causing photo-induced cationic polymerization for example, a monomer, oligomer or polymer having an epoxy group; a compound having an oxetane skeleton; or vinyl ether is used.
  • a photo-induced cationic polymerization initiator is uses as the initiator.
  • the photo-induced cationic polymerization initiator for example, aromatic diazonium salt, aromatic iodonium salt, aromatic sulfonium salt, aromatic sulfonium salt, aromatic phosphonium salt or a metal salt with mixed ligands is used.
  • a mixture of the compound capable of causing a photo-induced radical polymerization and the compound capable of causing a photo-induced cationic polymerization may be used as the polymerizable compound.
  • the initiator for example, a mixture of the photo-induced radical polymerization initiator and the photo-induced cationic polymerization initiator is used as the initiator.
  • an initiator that can function as both the photo-induced radical polymerization initiator and the photo-induced cationic polymerization initiator may be used.
  • aromatic iodonium salt or aromatic sulfonium salt is used.
  • a proportion of the initiator in the radiation-curing resin is set within, for example, a range of 0.1% to 15% by mass.
  • the radiation-curing resin may further contain sensitizing dye, dye, pigment, polymerization inhibitor, leveling agent, antifoaming agent, anti-sagging agent, adhesion promoter, coating surface-modifying agent, plasticizer, nitrogen-containing compound, crosslinking agent such as epoxy resin, release agent or a combination thereof.
  • the radiation-curing resin may further contain non-reactive resin in order to improve the moldability.
  • non-reactive resin for example, the above-described thermoplastic resin and/or thermosetting resin can be used.
  • the above-described plate used for forming the relief structure formation layer 110 is manufactured, for example, using an electron beam writer or nanoimprinting apparatus.
  • the above-described recesses or protrusions can be formed with a high degree of accuracy.
  • a reversal plate is manufactured first by transferring the relief structure of the original plate thereon, and replicated plates are manufactured by transferring the relief structure of the reversal plate thereon. Further, reversal plate is manufactured using the replicated plate as an original plate and replicated plates are manufactured by transferring the relief structure of the reversal plate thereon, if necessary. In actual manufacturing processes, the replicated plate thus obtained is used in normal cases.
  • the relief structure formation layer 110 typically includes a substrate and a resin layer formed thereon.
  • a film substrate is used typically.
  • a plastic film such as polyethylene terephthalate (PET) film, polyethylene naphthalate (PEN) film and polypropylene (PP) film is used.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PP polypropylene
  • paper, synthetic paper, multilayer plastic paper or resin-impregnated paper may be used as the substrate.
  • the substrate may be omitted.
  • the resin layer is formed by, for example, the above-described method.
  • the thickness of the resin layer is set within, for example, a range of 0.1 to 10 ⁇ m. When the thickness is excessively large, squeeze-out and/or wrinkling of the resin due to the pressure induced on the processing are prone to occur. When the thickness is excessively small, there is a possibility that formation of the recessed structure and/or protruding structure is difficult.
  • the thickness of the resin layer is set equal to or greater than the depth or height of the recesses or protrusions provided on the main surface thereof. The thickness is set at a value, for example, 1 to 10 times, typically a value 3 to 5 times the depth of height of the recesses or protrusions.
  • Formation of the relief structure formation layer 110 may be performed by the “press method” described in Japanese Patent No. 4194073, the “casting method” described in Japanese Utility Model No. 2524092, or the “photopolymer method” described in Japanese Patent Application Publication No. 2007-118563.
  • a first material having a refractive index different from that of the material of the relief structure formation layer 110 is vapor-deposited on the regions R 1 and R 2 .
  • a reflective layer 120 is formed on the main surface of the relief structure formation layer 110 that includes the regions R 1 and R 2 .
  • the first material for example, a material having a refractive index different from that of the material of the relief structure formation layer 110 by 0.2 or more is used. When this difference is small, there is a possibility that a reflection by the interface between the relief structure formation layer 110 and the first layer 120 ′ described later is less prone to occur.
  • the first material used typically is at least one metal material selected from the group consisting of Al, Sn, Cr, Ni, Cu, Au, Ag and alloys thereof.
  • the ceramic material or the organic polymer material listed below may be used as the first material with a relatively high transparency.
  • the parenthesized numerical value following the chemical formula or compound name indicates the refractive index of the corresponding material.
  • the ceramic material for example, Sb 2 O 3 (3.0), Fe 2 O 3 (2.7), TiO 2 (2.6), CdS (2.6), CeO 2 (2.3), ZnS (2.3), PbCl 2 (2.3), CdO (2.2), Sb 2 O 3 (5), WO 3 (5), SiO (5), Si 2 O 3 (2.5), In 2 O 3 (2.0), PbO (2.6), Ta 2 O 3 (2.4), ZnO (2.1), ZrO 2 (5), MgO (1), SiO 2 (1.45), Si 2 O 2 (10), MgF 2 (4), CeF 3 (1), CaF 2 (1.3-1.4), AlF 3 (1), Al 2 O 3 (1) or GaO (2) can be used.
  • organic polymer material for example, polyethylene (1.51), polypropylene (1.49), polytetrafluoroethylene (1.35), polymethylmethacrylate (1.49) or polystyrene (1.60) can be used.
  • the vapor deposition of the first material is performed using, for example, vacuum evaporation, sputtering, or chemical vapor deposition (CVD).
  • the vapor deposition is performed with uniform density in-plane directions parallel with the main surface of the relief structure formation layer 110 . Specifically, the vapor deposition is performed such that a ratio of the amount of the first material at the position of the first region R 1 to the apparent area of the first region R 1 and a ratio of the amount of the first material at the position of the second region R 2 to the apparent area of the second region R 2 are equal to each other.
  • the thickness in the case of supposing the main surface of the relief structure formation layer 110 is constituted entirely by a flat surface (hereinafter referred to as target thickness) is typically determined as follows. That is, the target thickness is determined such that the reflective material layer 120 satisfies the following conditions.
  • the portion of the reflective material layer 120 corresponding to the first region R 1 has a surface configuration that corresponds to the surface configuration of the first region R 1 .
  • this portion forms a continuous film having a surface configuration that corresponds to the grooves on the first region R 1 .
  • the portion of the reflective material layer 120 corresponding to the second region R 2 has a surface configuration that corresponds to the surface configuration of the second region R 2 or partially opens correspondingly to the arrangement of the recesses or protrusions on the second region R 2 .
  • FIG. 4 shows the former case as an example. That is, in the example shown in FIG. 4 , this portion forms a continuous film having a surface configuration that corresponds to the grooves on the second region R 2 .
  • the second region R 2 has a ratio of the surface area to the apparent area greater than that of the second region R 2 .
  • the portion of the reflective material layer 120 corresponding to the second region R 2 has a smaller mean thickness as compared with the portion of the reflective material layer 120 corresponding to the first region R 1 .
  • a “mean thickness” of a layer means a mean value of distances between points on a main surface of the layer and corresponding foots of perpendicular lines that extend from the points to the other main surface of the layer.
  • the reflective material layer 120 can be formed to have a surface configuration corresponding to the surface configuration of the first region R 1 at the portion corresponding to the first region R 1 and partially open correspondingly to the arrangement of the recesses and protrusions at the portion corresponding to the second region R 2 .
  • the target thickness of the reflective material layer 120 is typically set smaller than the depth or height of the recesses or protrusions on the second region R 2 .
  • the target thickness is typically set smaller than the depth or height thereof.
  • the target thickness of the reflective material layer 120 is set within, for example, a range of 5 to 500 nm, and typically a range of 30 to 300 nm.
  • the target thickness is excessively small, there is a possibility that a reflection by an interface between the relief structure formation layer 110 and the first layer 120 ′ described later is less prone to occur.
  • the target thickness is excessively large, there is a possibility that the reflective material layer 120 is difficult to form to satisfy the above-described conditions.
  • the mean thickness of the portion of the reflective material layer 120 corresponding to the first region R 1 is set within, for example a range of 5 to 500 nm, and typically a range of 30 to 300 nm.
  • the mean thickness is excessively small, there is a possibility that a reflection by an interface between the relief structure formation layer 110 and the first layer 120 ′ described later is less prone to occur.
  • the mean thickness is excessively large, there is a possibility that the producibility of the optical device 10 is degraded.
  • a second material different from the material of the reflective material layer 120 is vapor-deposited on the reflective material layer 120 as shown in FIG. 5 .
  • a mask layer 130 that faces the relief structure formation layer 110 with the reflective material layer 120 interposed therebetween.
  • an inorganic material is typically used as the second material.
  • the inorganic material include MgF 2 , Sn, Cr, ZnS, ZnO, Ni, Cu, Au, Ag, TiO 2 , MgO, SiO 2 and Al 2 O 3 .
  • the mask layer 130 and the second layer 130 ′ can deliver a higher performance in the conformability and abrasion resistance when the substrate is bent or an impact is applied thereto.
  • an organic material may be used as the second material.
  • the organic material for example, an organic material having a weight-average molecular weight of 1,500 or less is used. Examples of such an organic material include a polymerizable compound such as acrylate, urethaneacrylate and epoxyacrylate.
  • the organic material it is possible to use a substance obtained by mixing the polymerizable compound and an initiator together, vapor-depositing the radiation-curing resin thus obtained, and irradiating it with radiation to cause polymerization.
  • metal alkoxide may be used as the second material.
  • the second material it is possible to use a substance obtained by vapor-depositing the metal alkoxide and causing polymerization thereof. In this case, a dry treatment may be performed between the vapor deposition and the polymerization.
  • the vapor deposition of the second material is performed using, for example, vacuum evaporation, sputtering or CVD.
  • the vapor deposition is performed with uniform density in-plane directions parallel with the main surface of the relief structure formation layer 110 . Specifically, the vapor deposition is performed such that a ratio of the amount of the second material at the position of the first region R 1 to the apparent area of the first region R 1 and a ratio of the amount of the second material at the position of the second region R 2 to the apparent area of the second region R 2 are equal to each other.
  • the target thickness of the mask layer 130 is determined as follows. That is, the target thickness is determined such that the mask layer 130 satisfies the following conditions.
  • the portion of the mask layer 130 corresponding to the first region R 1 has a surface configuration that corresponds to the surface configuration of the first region R 1 .
  • this portion forms a continuous film having a surface configuration that corresponds to the grooves on the first region R 1 .
  • the portion of the mask layer 130 corresponding to the second region R 2 has a surface configuration that corresponds to the surface configuration of the second region R 2 or partially opens correspondingly to the arrangement of the recesses or protrusions on the second region R 2 .
  • FIG. 5 shows the latter case as an example. That is, in the example shown in FIG. 5 , this portion forms a discontinuous film on the reflective material layer 120 that partially opens correspondingly to the arrangement of the grooves on the second region R 2 .
  • the second region R 2 has a ratio of the surface area to the apparent area greater than that of the second region R 2 .
  • the portion of the mask layer 130 corresponding to the second region R 2 has a smaller mean thickness as compared with the portion of the mask layer 130 corresponding to the first region R 1 .
  • the mask layer 130 can be formed to have a surface configuration corresponding to the surface configuration of the first region R 1 at the portion corresponding to the first region R 1 and partially open correspondingly to the arrangement of the recesses and protrusions at the portion corresponding to the second region R 2 .
  • the target thickness of the mask layer 130 is typically set smaller than the depth or height of the recesses or protrusions on the second region R 2 .
  • the target thickness is typically set smaller than the depth or height thereof.
  • the target thickness of the mask layer 130 is typically set smaller than the target thickness of the reflective material layer 120 .
  • the target thickness of the mask layer 130 is set within, for example, a range of 0.3 to 200 nm, and typically a range of 3 to 80 nm.
  • the target thickness is excessively small, there is a possibility that the mean thickness of the portion of the mask layer 130 corresponding to the first region R 1 is excessively small, and thus the protection of the portion of the reflective material layer 120 corresponding to the first region R 1 by the mask layer 130 is insufficient.
  • the target thickness is excessively large, there is a possibility that the protection of the portion of the reflective material layer 120 corresponding to the second region R 2 by the mask layer 130 is excessive.
  • the mean thickness of the portion of the mask layer 130 corresponding to the first region R 1 is typically set smaller than the mean thickness of the portion of the reflective material layer 120 corresponding to the first region R 1 .
  • the mean thickness of the portion of the mask layer 130 corresponding to the first region R 1 is set within, for example a range of 0.3 to 200 nm, and typically a range of 3 to 80 nm.
  • the mean thickness is excessively small, there is a possibility that the mean thickness of the portion of the mask layer 130 corresponding to the first region R 1 is excessively small, and thus the mean thickness of the portion of the first layer 120 ′ described later corresponding to the first region R 1 is excessively small.
  • the target thickness is excessively large, there is a possibility that the protection of the portion of the reflective material layer 120 corresponding to the second region R 2 by the mask layer 130 is excessive.
  • the mask layer 130 is exposed to a reactive gas or liquid that can react with the material of the reflective material layer 120 . This allows the material of the reflective material layer 120 to cause the above-described reaction at least at a position of the second region R 2 .
  • an etching liquid capable of dissolving the material of the reflective material layer 120 is used as the reactive gas or liquid.
  • An alkaline solution such as sodium hydroxide solution, sodium carbonate solution and potassium hydroxide solution is typically used as the etching liquid.
  • an acidic solution such as hydrochloric acid, nitric acid, sulfuric acid and acetic acid may be used as the etching liquid.
  • the portion of the mask layer 130 corresponding to the first region R 1 forms a continuous film, while the portion corresponding to the second region R 2 forms a discontinuous film that opens partially.
  • the reactive gas or liquid can easily come in contact with the portion of the reflective material layer 120 that is not covered by the mask layer 130 as compared with the portion of the reflective material layer 120 that is covered by the mask layer 130 .
  • the former is easily etched than the latter.
  • the concentration and temperature of the etching liquid and the duration of etching, etc. only the portion of the reflective material layer 120 that corresponds to the second region R 2 can be removed as shown in FIG. 6 .
  • the first layer 120 ′ that covers only the first region R 1 of the regions R 1 and R 2 .
  • the optical device 10 shown in FIGS. 1 and 2 is thus obtained.
  • the optical device 10 obtained by the above-described method has the following characteristics.
  • the first layer 120 ′ is a reflective layer and typically made of the above-described first material.
  • the first layer 120 ′ covers only the first region R 1 of the regions R 1 and R 2 . That is, the first layer 120 ′ is provided only at a position corresponding to the first region R 1 .
  • a ratio of the amount of the first material at the position of the second region R 2 to the apparent area of the second region R 2 is zero.
  • the first layer 120 ′ has a surface configuration that corresponds to the surface configuration of the first region R 1 .
  • the first layer 120 ′ has a surface configuration that corresponds to the grooves on the first region R 1 .
  • the grooves on the first region R 1 typically form on the surface of the first layer 120 ′ a diffraction grating or hologram that emits a diffracted light when illuminated with a white light.
  • the display portion DP 1 of the optical device 10 can display a color corresponding to the diffracted light. Therefore, in this case, a higher forgery prevention effect and a higher decorative effect can be achieved.
  • An orthogonal projection of the contour of the first layer 120 ′ on the main surface of the relief structure formation layer 110 entirely overlaps the contour of the first region R 1 . That is, the first layer 120 ′ is patterned correspondingly to the shape of the first region R 1 . Thus, when the regions R 1 and R 2 are formed with a high positional accuracy, the first layer 120 ′ can be formed with a high positional accuracy.
  • the mean thickness of the portion of the first layer 120 ′ corresponding to the first region R 1 is typically equal to the mean thickness of the portion of the reflective material layer 120 corresponding to the first region R 1 . That is, the mean thickness falls within, for example, a range of 5 to 500 nm, and typically a range of 30 to 300 nm.
  • the maximum value of the shortest distances from the boundary between the regions R 1 and R 2 to the contour of the first layer 120 ′ is set, for example, less than 20 ⁇ m, preferably less than 10 ⁇ m, and more preferably less than 3 ⁇ m.
  • the second layer 130 ′ is, for example, a layer formed by vapor deposition.
  • the second layer 130 ′ covers the first layer 120 ′.
  • the second layer 130 ′ faces only the first region R 1 of the regions R 1 and R 2 with the first layer 120 ′ interposed therebetween. That is, the orthogonal projection of the contour of the first layer 120 ′ on the main surface of the relief structure formation layer 110 entirely overlaps an orthogonal projection of the contour of the second layer 130 ′ on the main surface.
  • a ratio of the amount of the second material at the position of the second region R 2 to the apparent area of the second region R 2 is zero.
  • the mean thickness of the portion of the second layer 130 ′ corresponding to the first region R 1 is equal to or smaller than the mean thickness of the portion of the mask layer 130 corresponding to the first region R 1 .
  • the mean thickness falls within, for example, a range of 0.3 to 200 nm, and typically a range of 3 to 80 nm.
  • the second layer 130 ′ plays, for example, a role of protecting the first layer 120 ′.
  • forgery of the optical device 10 is more difficult as compared with the case where the second layer 130 ′ is absent.
  • the second layer 130 ′ makes it possible to change the color of the portion of the optical device 10 where the first layer 120 ′ is provided without affecting the color of the other portion of the optical device 10 .
  • the second material it is possible to impart a blackish color to the portion of the optical device 10 where the first layer 120 ′ is provided.
  • Al is used as the first material and ZnS is used as the second material
  • the mean thickness of the first layer 120 ′ is small, these effects can be obtained when the optical device 10 is observed from the side of the relief structure formation layer 110 .
  • both the regions R 1 and R 2 are provided with grooves arranged regularly.
  • the structures of the regions R 1 and R 2 are not limited to this.
  • the first region R 1 may be flat.
  • the display portion D 1 is seen, for example, like a specular surface. Note that in this case, the ratio of the surface area to the apparent area of the first region R 1 is equal to 1.
  • the first region R 1 may be provided with recesses or protrusions arranged two-dimensionally.
  • the recesses or protrusions are typically tapered.
  • the recesses or protrusions have a shape of a circular cone, a pyramid, a circular truncated cone, a truncated pyramid, an elliptic paraboloid or a paraboloid of revolution.
  • the sidewalls of the recesses or protrusions may be smooth or stepwise.
  • the recesses or protrusions may have columnar shapes such as circular columns or prisms.
  • the recesses or protrusions arranged two-dimensionally may be arranged regularly or randomly.
  • the recesses or protrusions typically form on the surface of the first layer 120 ′ a diffraction grating or hologram that emits a diffracted light when illuminated with a white light.
  • the recesses or protrusions are arranged in a square lattice.
  • the recesses or protrusions may be arranged in a rectangular or triangle lattice.
  • the mean value of the diameters of the openings of the recesses or the mean value of the diameters of the bottoms of the protrusions is set within, for example, a range of 100 to 3,000 nm.
  • the mean value of the depths of the recesses or the mean value of the heights of the protrusions is set within, for example, a range of 20 to 1,500 nm.
  • the mean value of ratios of the depths to the diameters of the recesses or the mean value of the ratios of the heights to diameters of the bottoms of the protrusions is set, for example, at 0.5 or less, and typically within a range of 0.05 to 0.3.
  • the second region R 2 may be provided with recesses or protrusions arranged two-dimensionally.
  • the recesses or protrusions can employ, for example, the same structure as that described for the recesses or protrusions of the first region R 1 except that the mean value of the ratios of the depths to the diameters of the recesses or the mean vale of the ratios of the heights to the diameters of the bottoms of the protrusions is greater.
  • the mean value of the diameters of the openings of the recesses or the mean value of the diameters of the bottoms of the protrusions is set within, for example, a range of 100 to 3,000 nm.
  • the mean value of the depths of the recesses or the mean value of the heights of the protrusions is set within, for example, 80 to 6,000 nm.
  • the mean value of the ratios of the depths to the diameters of the recesses or the mean value of the ratios of the heights to the diameters of the bottom of the protrusions is set within, for example, a range of 0.8 to 2.0, and typically a range of 0.8 to 1.5.
  • the recesses or protrusions provided to the regions R 1 and R 2 may form a relief hologram, a diffraction grating, a sub-wavelength grating, micro-lenses, a polarizing element, a condensing element, a scattering element, a diffusing element or a combination thereof.
  • the reflective material layer 120 has a surface configuration that corresponds to the surface configurations of the regions R 1 and R 2
  • the portion of the mask layer 130 corresponding to the first region R 1 has a surface configuration that corresponds to the surface configuration of the first region R 1
  • the portion of the mask layer 130 corresponding to the second region R 2 partially opens correspondingly to the arrangement of the recesses or protrusions on the second region R 2 .
  • the structures of the layers are not limited to this.
  • both the reflective material layer 120 and the mask layer have surface configurations that correspond to the surface configurations of the regions R 1 and R 2 .
  • portions of the reflective material layer 120 and the mask layer 130 corresponding to the second region R 2 have mean thicknesses smaller than the mean thicknesses of the portions of these layers corresponding to the first region R 1 , respectively.
  • the portion of the mask layer 130 having a smaller mean thickness is prone to allow the reactive gas or liquid to permeate as compared with the portion having a larger mean thickness.
  • the mask layer 130 can be opened only above the second region R 2 .
  • the optical device 10 shown in FIGS. 1 and 2 can be manufactured.
  • both the reflective material layer 120 and the mask layer have surface configurations that correspond to the surface configurations of the first region R 1 at the portions corresponding to the first region R 1 and partially open correspondingly to the arrangement of the recesses or protrusions on the second region R 2 at the portion corresponding to the second region R 2 .
  • the optical device 10 shown in FIGS. 1 and 2 can be manufactured.
  • the portions of the reflective material layer 120 and the mask layer 130 corresponding to the second region R 2 are removed completely.
  • the removal may be performed such that parts of the portions remain.
  • the ratio of the amount of the second material at the position of the second region 2 to the apparent area of the second region R 2 may be made greater than zero and smaller than the ratio of the amount of the second material at the position of the first region R 1 to the apparent area of the first region R 1 .
  • each of the reflective material layer 120 and the first layer 120 ′ has a single-layer structure.
  • Each of the layers may have a multilayer structure.
  • the first layer 120 ′ of the optical device 10 may form a multilayer interference film.
  • the first layer 120 ′ includes, for example, a multilayer film in which a miller layer, a spacer layer and a half-mirror layer are stacked in this order from the side of the relief structure formation layer 110 .
  • the miller layer is a metal layer and typically includes an elemental metal or an alloy.
  • the metal included in the miller layer include aluminum, gold, copper and silver.
  • aluminum is in particular preferable.
  • the thickness of the miller layer is set, for example, at 300 nm or less, and typically within a range of 20 to 200 nm.
  • the spacer layer typically includes a dielectric material.
  • the refractive index of the dielectric material is 1.65 or less. Further, it is preferable that the dielectric material is transparent. Examples of the dielectric material include SiO 2 and MgF 2 .
  • the thickness of the spacer layer is set within, for example, a range of 5 to 500 nm.
  • the half-miller layer is a reflective layer having a light-transmitting property and typically includes an elemental metal, an alloy, a metallic oxide or a metallic sulfide.
  • the metal or alloy included in the half-miller layer include aluminum, nickel, Inocel (registered trademark), titanium oxide (TiO 2 ), zinc sulfide (ZnS), molybdenum sulfide (MoS 2 ) and ferric oxide (III) (Fe 2 O 3 ).
  • the thickness of the half-miller layer is set within, for example, a range of 5 to 80 nm.
  • the thickness is preferably set within a range of 30 to 80 nm.
  • the thickness is preferably set within a range of 5 to 45 nm.
  • each of the mask layer 130 and the second layer 130 ′ has a single-layer structure.
  • Each of the layers may have a multilayer structure.
  • the second layer 130 ′ of the optical device 10 may form a multilayer interference film.
  • the laminated structure of the first layer 120 ′ and the second layer 130 ′ may form a multilayer interference film.
  • the steps described with reference to FIGS. 4 and 6 may be repeated after forming the first layer 120 ′ and the second layer 130 ′.
  • the multilayer interference film can be formed stably with a high positional accuracy.
  • an etching liquid used as the reactive gas or liquid is not limited to this.
  • an etching gas that can vaporize the material of the reflective material layer 120 may be used as the reactive gas or liquid.
  • a gas or liquid that can react with the first material to change a portion of the reflective material layer 120 into a layer made of a material different from the first material may be used as the reactive gas or liquid.
  • the reactive gas or liquid it is possible to change the portion of the reflective material layer 120 corresponding to the second region R 2 into a layer made of a material different from the first material instead of removing this portion.
  • an oxidizer that can oxidize the first material can be used.
  • the oxidizer include oxygen, ozone, or halogen; halides such as chlorine dioxide, hypohalous acid, subhalogen acid, perhalogen acid, and salts thereof; inorganic peroxides such as hydrogen peroxide, persulfates, peroxocarbonates, peroxosulfates, and peroxophosphates; organic peroxides such as benzoyl peroxide, t-butylhydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, performic acid, peracetic acid, perbenzoic acid; metals or metal compounds such as cerium salts, salts of Mn (III), Mn (IV) and Mn (VI), silver salts, copper salts, chromium salts, cobalt salts, dichromates, chromates, permanganates, magnesium perphthalate, ferric chlor
  • the portion of the reflective material layer 120 ′ corresponding to at least the second region R 2 when the portion of the reflective material layer 120 ′ corresponding to at least the second region R 2 is reacted with the oxidizer, the portion can be changed into a layer made of Cu oxide.
  • the portion of the reflective material layer 120 ′ corresponding to at least the second region R 2 when the portion of the reflective material layer 120 ′ corresponding to at least the second region R 2 is reacted with the oxidizer, the portion can be changed into a layer made of Al oxide such as boehmite.
  • a reducer that can reduce the material of the reactive material layer 120 ′ may be used as the above-described reactive gas or liquid.
  • the reducer for example, hydrogen sulfide, sulfur dioxide, hydrogen fluoride, alcohols, carboxylic acids, hydrogen gas, hydrogen plasma, remote hydrogen plasma, diethylsilane, ethylsilane, dimethylsilane, phenylsilane, silane, disilane, aminosilane, boranes, diborane, alane, germane, hydrazine, ammonia, hydrazine, methylhydrazine, 1,1-dimethylhydrazine, 1,2-dimethyldhyrazine, t-butylhydrazine, benzylhydrazine, 2-hydrazinoethanol, 1-n-butyl-1-phenylhydrazine, phenylhydrazine, 1-naphthylhydrazine, 4-chlorophenylhydrazin
  • the second layer 130 ′ may be removed after forming the first layer 120 ′ by etching treatment, etc.
  • the removal of the second layer 130 ′ is effective, for example, in the case where ionization of the first material due to the difference between the ionization tendencies of the first and second materials is concerned.
  • FIG. 7 is a plan view schematically showing an optical device according to a modified example.
  • FIG. 8 is a sectional view of the optical device taken along a line VIII-VIII shown in FIG. 7 .
  • the optical device 10 shown in FIGS. 7 and 8 can be manufactured by the same method as that described with reference to FIGS. 3 to 6 except that the structures of the regions R 1 and R 2 included in the main surface of the relief structure formation layer 110 are changed.
  • the first region R 1 has a contour corresponding to micro-characters “TP”.
  • the first region R 1 includes a flat region FR constituted by a flat surface and an uneven region UR provided with recesses or protrusions.
  • the uneven region UR is bordered with the flat region FR.
  • the portion of the optical device 10 corresponding to the flat region FR is a display portion DPF, while the portion of the optical device 10 corresponding to the uneven region UR is a display portion DPU.
  • the width of the display portion DPF bordering the display portion DPU falls within, for example, a range of 10 to 2,000 ⁇ m, and typically a range of 50 to 1,000 ⁇ m.
  • the first layer 120 ′ need to be formed with an extremely high positional accuracy. Therefore, formation of such an optical device 10 using a conventional patterning method is impossible or very difficult.
  • the first layer 120 ′ can be formed with a high positional accuracy as described above. Therefore, when using this method, even a fine image such as the above-described micro-characters can be displayed with a high definition.
  • FIG. 9 is a plan view schematically showing an optical device according to another modified example.
  • FIG. 10 is a sectional view of the optical device taken along a line X-X shown in FIG. 9 .
  • the portion of the optical device corresponding to the first sub-region SR 1 which will be described later, is a display portion DSP 1
  • the portion of the optical device corresponding to the second sub-region SR 1 is a display portion DSP 2 .
  • the optical device 10 shown in FIGS. 9 and 10 has the same structure as that of the optical device shown in FIGS. 1 and 2 except for the followings.
  • the first region R 1 includes a first sub-region SR 1 and a second sub-region SR 2 .
  • the first sub-region SR 1 is adjacent to the second region R 2 and extends along the boundary between the regions R 1 and R 2 .
  • the second sub-region SR 2 is adjacent to the second region R 2 with the first sub-region SR 1 interposed therebetween.
  • the contour of the second sub-region SR 2 typically has a shape similar to the contour of the first region R 1 .
  • the first layer 120 ′ is provided only at the position corresponding to the second sub-region SR 2 . That is, only the second sub-region SR 2 of the regions R 1 and R 2 is covered with the first layer 120 ′. Further, the portion of the first layer 120 ′ corresponding to the second sub-region SR 2 has a surface configuration that corresponds to the surface configuration of the second sub-region SR 2 .
  • the mean thickness of the portion of the first layer 120 ′ corresponding to the second sub-region SR 2 falls within, for example, a range of 5 to 500 nm, and typically a range of 5 to 300 nm.
  • the mean thickness is excessively small, there is a possibility that the reflection by the interface between the relief structure formation layer 110 and the first layer 120 ′ is less prone to occur.
  • the mean thickness is excessively large, there is a possibility that the producibility of the optical device 10 is degraded.
  • the second layer 130 ′ faces the entire surface of the first region R 1 . That is, the second layer 130 ′ typically includes a first portion P 1 covering the first layer 120 ′ and a second portion P 2 outwardly protruding from the first portion P 1 .
  • a first orthogonal projection of the contour of the first layer 120 ′ on the main surface of the relief structure formation layer 110 has a shape similar to a second orthogonal projection of a contour of the vapor-deposited layer on the main surface and is surrounded by the second orthogonal projection.
  • the second material is colored
  • the difference between the colors can be perceived, for example, by the observation of the optical device 10 using a microscope.
  • the optical device 10 described with reference to FIGS. 9 and 10 can achieve a special optical effect.
  • the mean thickness of the portion of the second layer 130 ′ corresponding to the second sub-region SR 2 falls within, for example, a range of 0.3 to 200 nm, and typically a range of 3 to 80 nm.
  • the optical device 10 shown in FIGS. 9 and 10 is manufactured by, for example, the following method. That is, by adjusting the concentration and temperature of the etching liquid and the duration of the etching treatment, a side-etching is caused at a portion of the reflective material layer 120 corresponding to the first region R 1 after the steps described with reference to FIGS. 3 to 5 . This removes the portion of the reflective material layer 120 corresponding to the first sub-region SR 1 together with the portions of the reflective material layer 120 and the mask layer 130 corresponding to the second region R 2 . Thus, the optical device 10 shown in FIGS. 9 and 10 is obtained.
  • the above-described side-etching starts at the contour of the portion of the reflective material layer 120 corresponding to the first region R 1 and progresses toward the inside at a substantially constant rate.
  • the variations of the width of the portion removed by this side-etching i.e., the variations of the distance from the contour of the first sub-region SR 1 to the contour of the first region is relatively small.
  • the contour of the second sub-region SR 2 typically has a shape similar to the contour of the first region R 1 . Therefore, even in the case of employing such a method, the first layer 120 ′ can be formed with a high positional accuracy.
  • the portion of the reflective material layer 120 corresponding to the first region R 1 is covered with the mask layer 130 , no etching or almost no etching occurs at the main surface under the condition that the side-etching occurs at the side surface. Therefore, even in the case of employing such a method, the first layer 120 ′ can be formed stably.
  • the first orthogonal projection of the contour of the first layer 120 ′ on the relief structure formation layer 110 has a shape similar to the second orthogonal projection of the contour of the vapor-deposited layer on the main surface and is surrounded by the second orthogonal projection.
  • the structures of the first layer 120 ′ and the second layer 130 ′ are not limited to this.
  • a part of the first orthogonal projection overlaps a part of the second orthogonal projection, while the remainder of the first orthogonal projection has a shape similar to the remainder of the second projection and is surrounded by the second projection.
  • FIG. 11 is a plan view schematically showing an optical device according to another embodiment of the present invention.
  • FIG. 12 is a sectional view of the optical device taken along a line XII-XII shown in FIG. 11 .
  • FIGS. 13 to 17 are sectional views schematically showing a method of manufacturing the optical device shown in FIGS. 11 and 12 . Note that in FIG. 11 , the portion of the optical device 10 corresponding to the third region R 3 , which will be described later, is indicated as a display portion DP 3 .
  • FIGS. 11 and 12 A method of manufacturing the optical device 10 shown in FIGS. 11 and 12 will be described below with reference to FIGS. 13 to 17 .
  • a relief structure formation layer 110 having a main surface that includes a first region R 1 , a second region R 2 and a third region R 3 as shown in FIG. 13 .
  • the relief structure formation layer 110 has the same structure as that of the relies structure formation layer described with reference to FIG. 3 except that this relief structure formation layer 110 further includes the third region R 3 .
  • the third region R 3 is provided with recesses or protrusions.
  • the third region R 3 has a ratio of the specific surface area to the apparent area greater than that of the first region R 1 .
  • the third region R 3 has the same structure as that of the second region R 2 .
  • a first material is vapor-deposited on the regions R 1 to R 3 as shown in FIG. 14 .
  • Formation of the reflective material layer 120 is performed by the same method as that described with reference to FIG. 4 .
  • the portion of the reflective material layer 120 corresponding to the first region R 1 forms a continuous film having a surface configuration that corresponds to the grooves on the first region R 1 .
  • the portions of the reflective material layer 120 corresponding to the regions R 2 and R 3 form discontinuous films that partially open correspondingly to the arrangements of the groove on the regions R 2 and R 3 .
  • a cover layer 140 that faces only the third region R 3 of the regions R 2 and R 3 .
  • the cover layer 140 may further face at least a portion of the first region R 1 .
  • FIG. 16 shows the case where the cover layer 140 faces the entire third region R 3 and a part of the first region R 1 .
  • Formation of the cover layer 140 can be performed using a known pattern formation method.
  • the pattern formation method for example, flexographic printing, gravure printing, inkjet printing, offset printing or security intaglio printing is used.
  • the material of the cover layer 140 for example, the above-described thermoplastic resin, thermosetting resin or radiation-curing resin is used.
  • a high-temperature resin such as polycarbonate, polyamide and polyimide, a mixture thereof or a copolymer thereof may be used.
  • the resin may be dissolved in a solvent such as water or organic solvent and added with dye, pigment, leveling agent, antifoaming agent, anti-sagging agent, adhesion promoter, coating surface-modifying agent, plasticizer, nitrogen-containing compound, crosslinking agent such as epoxy resin or a combination thereof, if necessary.
  • a solvent such as water or organic solvent and added with dye, pigment, leveling agent, antifoaming agent, anti-sagging agent, adhesion promoter, coating surface-modifying agent, plasticizer, nitrogen-containing compound, crosslinking agent such as epoxy resin or a combination thereof, if necessary.
  • the mask layer 130 and the cover layer 140 are exposed to a reactive gas or liquid that can react with the material of the reflective material layer 120 .
  • a reactive gas or liquid that can react with the material of the reflective material layer 120 .
  • This allows the material of the reflective material layer 120 to cause the reaction with the material of the reflective material layer 120 at least at a position of the second region R 2 .
  • an etching liquid capable of dissolving the material of the reflective material layer 120 is used as an example of the reactive gas or liquid.
  • the portion of the mask layer 130 corresponding to the first region R 1 forms a continuous film, while the portion corresponding to the second region R 2 forms a discontinuous film that opens partially.
  • the portion of the mask layer 130 corresponding to the second region R 2 is easily etched than the portion corresponding to the first region R 1 .
  • the cover layer 140 is formed on the portion of the mask layer 130 corresponding to the third region R 3 .
  • the cover layer 140 is not formed on the portion of the mask layer 130 corresponding to the second region R 2 .
  • the portion of the mask layer 130 corresponding to the second region R 2 is easily etched than the portion corresponding to the third region R 3 .
  • the portion of the reflective material layer 120 that corresponds to the second region R 2 can be removed as shown in FIG. 17 . Note that when the portion of the reflective layer 120 corresponding to the second region R 2 is removed, the portion of the mask layer 130 corresponding to the second region R 2 is also removed.
  • the optical device 10 shown in FIGS. 11 and 12 is thus obtained.
  • the optical device 10 includes the relief structure formation layer 110 , the first layer 120 ′, the second layer 130 ′ and the cover layer 140 .
  • the first layer 120 ′ is also present on the region other than the first region R 1 , i.e., the third region R 3 . Therefore, for example, when the third region R 3 is provided with recesses or protrusions that offers an optical effect of hologram, diffraction grating, sub-wavelength grating, zero-order diffraction filter, polarized light separation filter, etc., an optical device 10 offering a further special visual effect can be obtained.
  • the optical device 10 may further include a protective film.
  • the optical device 10 may have antireflection treatment on the surface thereof.
  • at least one surface of the layers included in the optical device 10 may be subjected to corona treatment, flame treatment or plasma treatment.
  • the above-described techniques may be combined with a known process for partially forming a reflective layer.
  • the known process for example, used is a laser method in which a part of a reflective is removed using a laser to form a pattern.
  • this process it is possible to use a method in which forming a patterned mask on a reflective layer and removing the portion of the mask not covered by the mask.
  • this process it is possible to use a method in which a patterned mask is formed on a main surface of a layer or substrate, forming a reflective layer on the entire main surface, and then the portion of the reflective layer on the mask is removed together with the mask.
  • formation of the mask is performed, for example, using printing method or photoresist method.
  • the optical device 10 may be uses as a part of an adhesive label.
  • the adhesive label includes the optical device 10 and an adhesive layer provided on the back surface of the optical device 10 .
  • the optical layer 10 may be used as a part of a transfer foil.
  • the transfer foil includes the optical device 10 and a support layer releasably supporting the optical device 10 .
  • the optical device 10 may be supported by an article.
  • the optical device 10 may be supported by a plastic card, etc.
  • the optical device 10 may be embedded in a paper.
  • the optical device 10 may be broken into flakes and used as a component of pigment.
  • the optical device 10 may be used for purposes other than forgery prevention.
  • the optical device can be used as a toy, educational material, or decoration.
  • a laminated body of the relief structure formation layer 110 , the reflective material layer 120 and the mask layer 130 was manufactured by the following method.
  • a composition containing 50.0 parts by mass of urethane (meta)acrylate, 30.0 parts by mass of methyl ethyl ketone, 20.0 parts by mass of ethyl acetate and 1.5 parts by mass of photoinitiator was prepared as the material of an ultraviolet-curing resin.
  • the urethane (meta)acrylate used was a multi-functional substance having a molecular weight of 6,000.
  • the photoinitiator “Irgacure 184” manufactured by CIBA SPECIALTY CORP. was used.
  • the above-described composition was applied to a transparent PET film with a thickness of 23 ⁇ m by gravure printing such that the coated film thus obtained had a thickness of 1 ⁇ m in a dried state.
  • an original plate provided with protrusions was fixed on a cylindrical surface of a printing cylinder, and the coated film was irradiated with ultraviolet ray from the PET film's side while pressing the original plate against the coated film so as to cure the ultraviolet-curing resin.
  • the pressing was performed under the conditions that the pressure was 2 kgf/cm 2 , the temperature was 80° C., and the speed was 10 m/minute.
  • the ultraviolet irradiation was performed using a high-pressure mercury-vapor lamp at an intensity of 300 mJ/cm 2 .
  • the relief structure 110 having a main surface including the regions R 1 and R 2 .
  • the relief structure formation layer 110 had grooves arranged regularly on the entire first region R 1 .
  • the cross sections of the grooves were V-shaped.
  • the pitch of the grooves was 1,000 nm.
  • the relief structure formation layer 110 further had recesses arranged in a square lattice on the entire second region R 2 .
  • the recesses were pyramidal.
  • the minimum center-to-center distance of the recesses was 333 nm.
  • the reflective material layer 120 was formed.
  • the target thickness of the reflective material layer 120 was set at 50 nm.
  • MgF 2 as the second material was deposited on the main surface of the reflective material layer 120 opposite to the relief structure formation layer 110 by vacuum evaporation.
  • the mask layer 130 was formed.
  • the target thickness of MgF 2 was set at 20 nm.
  • laminated body LB 1 As above, the laminated body including the relief structure formation layer 110 , the reflective material layer 120 and the mask layer 130 was obtained.
  • laminated body LB 1 the laminated body thus manufactured is referred to as a “laminated body LB 1 ”.
  • a laminated body of the relief structure formation layer 110 and the reflective material layer 120 was manufactured by the method as that described for the laminated body LB 1 except that formation of the mask layer 130 was omitted.
  • the laminated body is referred to as a “laminated body LB 2 ”.
  • the laminated bodies LB 1 and LB 2 were subjected to an etching treatment using aqueous sodium hydroxide.
  • the temperature of the aqueous sodium hydroxide was changed, and the following evaluation was performed in each case. That is, measured were the time T 1 for the transmittance of the portion of the laminated body corresponding to the first region R 1 to reach 20% and the time T 2 for the transmittance of the portion of the laminated body corresponding to the second region R 2 to reach 80%.
  • FIG. 18 shows the results. Note that the concentration of the aqueous sodium hydroxide was 0.1 mol/L, and the temperatures of the solution were 60° C., 50° C., 40° C., 30° C. and 25° C. in decreasing order of temperature.
  • FIG. 18 is a graph showing an example of a relationship between presence or absence of the mask layer and the etching rate.
  • the greater the value of T 1 is, the smaller the etching rate at the portion of the reflective material layer 120 corresponding to the second region RG 2 .
  • the ratio T 1 /T 2 was almost equal to 1 in the case where the temperature of the aqueous sodium hydroxide was high. That is, in this temperature range, the etching selectivity was low. In the case where the temperature of the aqueous sodium hydroxide was low, when the temperature was lowered, the ratio T 1 /T 2 gradually increased. That is, in this temperature range, the etching selectivity was improved by lowering the temperature of the aqueous sodium hydroxide. Therefore, in the case of using the laminated body LB 2 , it is necessary to set the temperature of the aqueous sodium hydroxide low in order to manufacture the optical devices with a high stability. In this case, however, the time for the etching treatment should be prolonged inadmissibly. Therefore, in this case, it is impossible or very difficult to simultaneously achieve the producibility and stability in the manufacture of the optical devices.
  • the ratio T 1 /T 2 was high regardless of the temperature of the aqueous sodium hydroxide. That is, the laminated body LB 1 achieved a high etching selectivity regardless of the temperature of the aqueous sodium hydroxide. Therefore, in the case of using the laminated body LB 1 , the optical devices can be stably manufactured with a short etching time. That is, in this case, it is possible to simultaneously achieve the producibility and stability in the manufacture of the optical devices.
  • optical devices OD 1 to OD 9 were manufactured as follows.
  • the above-described laminated body LB 1 was subjected to an etching treatment. Specifically, the laminated body LB 1 was exposed to 0.1 mol/L aqueous sodium hydroxide at 60° C. for 7 seconds. Thus, the portions of the reflective material layer 120 and the mask layer 130 corresponding to the second region R 2 were removed.
  • optical device OD 1 As above, the optical device 10 was manufactured. Hereinafter, the optical device 10 is referred to as an “optical device OD 1 ”.
  • the optical device OD 1 had a laminated structure including the relief structure formation layer 110 , the first layer 120 ′ covering only the entire first region R 1 of the regions R 1 and R 2 , and the second layer 130 ′ covering the entire first layer 120 ′.
  • the mean thickness of the first layer 120 ′ was 50 nm.
  • the mean diameter of the second layer 130 ′ was 20 nm.
  • optical device OD 2 An optical device was manufactured by the same method as that for the optical device OD 1 except that the minimum center-to-center distance of the recesses on the second region R 2 was set at 200 nm, and the width of the opening and the depth of each recess were set at 200 nm and 160 nm, respectively.
  • the optical device is referred to as an “optical device OD 2 ”.
  • the mean thickness of the first layer 120 ′ was 50 nm.
  • the mean diameter of the second layer 130 ′ was 20 nm.
  • optical device OD 3 An optical device was manufactured by the same method as that for the optical device OD 1 except that the pitch of the grooves on the first region R 1 was set at 300 nm, the width of the opening and the depth of each groove were set at 300 nm and 100 nm, respectively, the minimum center-to-center distance of the recesses on the second region R 2 was set at 375 nm, and the width of the opening and the depth of each recess were set at 375 nm and 300 nm, respectively.
  • the optical device is referred to as an “optical device OD 3 ”.
  • the mean thickness of the first layer 120 ′ was 50 nm.
  • the mean diameter of the second layer 130 ′ was 20 nm.
  • optical device OD 4 An optical device was manufactured by the same method as that for the optical device OD 3 except that the minimum center-to-center distance of the recesses on the second region R 2 was set at 300 nm, and the width of the opening and the depth of each recess were set at 300 nm and 300 nm, respectively.
  • the optical device is referred to as an “optical device OD 4 ”.
  • the mean thickness of the first layer 120 ′ was 50 nm.
  • the mean diameter of the second layer 130 ′ was 20 nm.
  • the relief structure formation layer 110 whose main surface included the third region R 3 in addition to the regions R 1 and R 2 was formed by the same method as that described for the laminated body LB 1 .
  • the regions R 1 and R 2 of the relief structure formation layer 110 the same structures as those of the laminated body LB 1 were employed.
  • the third region R 3 the same structure as that in the second region R 2 was employed.
  • the reflective material layer 120 and the mask layer 130 were formed by the same method as that described for the laminated body LB 1 .
  • the cover layer 140 was formed to face only the entire third region R 3 and a part of the first region R 1 of the regions R 1 to R 3 .
  • optical device OD 5 the optical device thus obtained is referred to as an “optical device OD 5 ”.
  • the mean thickness of the first layer 120 ′ was 50 nm.
  • the mean diameter of the second layer 130 ′ was 20 nm.
  • optical device OD 6 An optical device was manufactured by the same method as that described for the optical device OD 1 except that the laminated body LB 2 was used instead of the laminated body LB 1 and was exposed to 0.1 mol/L aqueous sodium hydroxide at 30° C. for 60 seconds instead of exposing it to 0.1 mol/L aqueous sodium hydroxide at 60° C. for 7 seconds.
  • the optical device is referred to as an “optical device OD 6 ”.
  • optical device OD 7 An optical device was manufactured by the same method as that described for the optical device OD 6 except that the target thickness of the reflective material layer 120 was set at 20 nm.
  • the optical device is referred to as an “optical device OD 7 ”.
  • optical device OD 8 An optical device was manufactured by the same method as that described for the optical device OD 6 except that the target thickness of the reflective material layer 120 was set at 80 nm.
  • the optical device is referred to as an “optical device OD 8 ”.
  • an optical device was manufactured by the same method as that described for the optical device OD 1 except that the mask layer 130 was formed as follows.
  • the mask layer 130 was formed using gravure printing instead of forming it on the entire reflective material layer 120 by vapor deposition.
  • prepared first was a composition containing 50.0 parts by mass of vinyl chloride-vinyl acetate copolymer resin, 30.0 parts by mass of methyl ethyl ketone, and 20.0 parts by mass of ethyl acetate.
  • the composition was gravure-printed on the pattern formed by the portion of the reflective material layer 120 corresponding to the first region R 1 . This printing was performed such that the mask layer 130 had a mean thickness of 1.0 ⁇ m.
  • the optical device OD 9 the optical device OD 9 ”.
  • the selectivity for removal of the reflective material layer 120 was evaluated on each of the optical devices OD 1 to OD 9 .
  • the transmittances for visible light were measured at portions corresponding to the regions R 1 and R 2 .
  • the optical devices were evaluated as “OK” in the case where the transmittance for visible light at the portion corresponding to the first region R 1 was 20% or less and the transmittance for visible light at the portion corresponding to the second region R 2 was 90% or more.
  • the other optical devices were evaluated as “NG”. The results are summarized in TABLE 1 below.
  • Target thickness Selectivity Posi- of Target for tional Aspect Aspect reflective thickness removal of accuracy ratio in ratio in material of mask reflective of Optical 1st 2nd layer layer material reflective device region region (nm) (nm) layer layer OD1 0.1 1.0 50 20 OK OK OD2 0.1 0.8 50 20 OK OK OD3 0.33 0.8 50 20 OK OK OK OD4 0.33 1.0 50 20 OK OK OK OD5 0.1 1.0 50 20 OK OK OD6 0.1 1.0 50 0 NG OK OD7 0.1 1.0 20 0 NG OK OD8 0.1 1.0 80 0 NG OK OD9 0.1 1.0 50 1,000 OK NG
  • the “aspect ratio” means a mean value of the ratios of the depths to the widths of the openings of the grooves.
  • the selectivity for removal of the reflective material layer 120 was insufficient. That is, in the optical devices OD 6 to OD 8 , the transmittance for visible light at the portion corresponding to the first region R 1 was greater than 20% or the transmittance for visible light at the portion corresponding to the second region R 2 was less than 90%. On the other hand, in the optical devices OD 1 to OD 5 and OD 9 , the selectivity for removal of the reflective material layer 120 was high.
  • the positional accuracy of the reflective layer 120 was evaluated on each of the optical devices OD 1 to OD 9 .
  • the maximum value of the shortest distances from the boundary between the regions R 1 and R 2 to the contour of the first layer 120 ′ was measured.
  • the optical devices were evaluated as “OK” in the case where this value was less than 20 ⁇ m, while the optical devices were evaluated as “NG” in the case where this value was 20 ⁇ m or more.
  • the results are summarized in TABLE 1.
  • the positional accuracy of the reflective layer 120 was insufficient. That is, in the optical device OD 9 , the maximum value of the shortest distances from the boundary between the regions R 1 and R 2 to the contour of the first layer 120 ′ was 20 ⁇ m or more. On the other hand, in the optical devices OD 1 to OD 8 , the positional accuracy of the reflective layer 120 was high.
  • the optical devices OD 1 to OD 5 were excellent in both the selectivity for removal of the reflective material layer 120 and the positional accuracy of the first layer 120 ′.

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EP2444826B1 (de) 2019-05-22
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JPWO2010147185A1 (ja) 2012-12-06
US20130209676A1 (en) 2013-08-15
JP5545289B2 (ja) 2014-07-09
CN102460236B (zh) 2014-10-22
CN102460236A (zh) 2012-05-16
RU2531847C2 (ru) 2014-10-27
JP5051311B2 (ja) 2012-10-17
EP2444826A4 (de) 2012-10-03
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US9272308B2 (en) 2016-03-01
RU2011151400A (ru) 2013-07-27

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