US20130273317A1 - Optical member, method for manufacturing optical member, and optical film of optical member - Google Patents

Optical member, method for manufacturing optical member, and optical film of optical member Download PDF

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US20130273317A1
US20130273317A1 US13/860,988 US201313860988A US2013273317A1 US 20130273317 A1 US20130273317 A1 US 20130273317A1 US 201313860988 A US201313860988 A US 201313860988A US 2013273317 A1 US2013273317 A1 US 2013273317A1
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Prior art keywords
polymer
layer
optical member
refractive index
branched
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Tomonari Nakayama
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Canon Inc
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Canon Inc
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Assigned to CANON KABUSHIKI KAISHA reassignment CANON KABUSHIKI KAISHA ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: NAKAYAMA, TOMONARI
Publication of US20130273317A1 publication Critical patent/US20130273317A1/en
Priority to US15/433,941 priority Critical patent/US10459125B2/en
Abandoned legal-status Critical Current

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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
    • B05D1/38—Successively applying liquids or other fluent materials, e.g. without intermediate treatment with intermediate treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/42—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating of an organic material and at least one non-metal coating
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C09D161/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C09D161/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/06—Polyhydrazides; Polytriazoles; Polyamino-triazoles; Polyoxadiazoles
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/006—Anti-reflective 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
    • G02B1/11—Anti-reflection 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
    • G02B1/11—Anti-reflection coatings
    • G02B1/111—Anti-reflection coatings using layers comprising organic materials
    • 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
    • G02B1/113—Anti-reflection coatings using inorganic layer materials only
    • G02B1/115—Multilayers
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/425—Coatings comprising at least one inhomogeneous layer consisting of a porous layer
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/73—Anti-reflective coatings with specific characteristics
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/77—Coatings having a rough surface
    • 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.]
    • Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]

Definitions

  • the present invention relates to an antireflection optical member, a method for manufacturing the optical member, and an optical film of the optical member and more particularly to an optical member having high antireflection performance from a visible region to a near-infrared region and a method for manufacturing the optical member.
  • an antireflection structure having a fine periodic structure having a pitch less than or equal to a wavelength in a visible light region it is known that the formation of a fine periodic structure having an appropriate pitch and height results in high antireflection performance in a wide wavelength range.
  • a known method for forming a fine periodic structure includes the application of a film in which fine particles having a particle size less than or equal to the visible light wavelength are dispersed.
  • a method for forming a fine periodic structure by patterning with a micromachining apparatus such as an electron-beam lithography system, a laser interference exposure apparatus, a semiconductor exposure apparatus, or an etching apparatus, is known to enable the control of pitch and height and allows the formation of an antireflection fine periodic structure (Japanese Patent Laid-Open No. 50-70040).
  • boehmite which is an aluminum oxide hydroxide
  • an aluminum oxide film formed by a liquid phase method is subjected to steam treatment or hot-water immersion treatment to form a fine periodic structure of crystals, for example, made of boehmite on its surface layer, thereby forming an antireflection film (see K. Tadanaga, N. Katata, and T. Minami: “Super-Water-Repellent Al 2 O 3 Coating Films with High Transparency”, J. Am. Ceram. Soc., 80[4], 1040-42 (1997)).
  • a layer having an intermediate refractive index between the refractive indexes of the substrate and the fine periodic structure is formed between the substrate and the fine periodic structure to improve the antireflection effect.
  • a layer having an intermediate refractive index made of a transparent organic resin not only has an antireflection effect but also protects a glass substrate from damage caused by moisture or water vapor (see Japanese Patent Laid-Open No. 2008-233880).
  • An antireflection porous film containing fine particles in its surface layer and a film having a textured structure containing aluminum oxide crystals are convenient and have high productivity and excellent optical performance.
  • a large difference in refractive index between a substrate and these films results in an insufficient antireflection effect.
  • a layer having an intermediate refractive index disposed between the substrate and the porous film or the film having the textured structure can improve the antireflection effect.
  • the refractive index of the substrate varies greatly with the application of the substrate.
  • a thin-film material that allows for a refractive index and a thickness suitable for the refractive index of the substrate.
  • an optical member having a high-performance antireflection film that has high in-plane uniformity.
  • the present invention provides an antireflection optical member that has high in-plane uniformity and a method for manufacturing the optical member.
  • the present invention also provides an optical film for use in the optical member.
  • the present invention provides an optical member having the following structure and a method for manufacturing the optical member.
  • An optical member that can solve the problems described above has a laminated body configured to reduce light reflection disposed on a substrate, wherein a surface of the laminated body is a porous layer or a layer having a textured structure, and at least one layer of the laminated body is a polymer layer containing a linear polymer and a branched polymer having a refractive index of 1.7 or more.
  • a method for manufacturing an optical member that can solve the problems described above is a method for manufacturing an optical member including a laminated body configured to reduce light reflection disposed on a substrate. This method includes
  • optical film of an optical member that can solve the problems described above, wherein the optical member includes a laminated body on a substrate.
  • a surface of the laminated body includes a porous layer or a layer having a textured structure.
  • the optical film is used in at least one layer of the laminated body and includes a polymer layer containing a linear polymer and a branched polymer having a refractive index of 1.7 or more.
  • the present invention can provide an antireflection optical member that has high in-plane uniformity and a method for manufacturing the optical member.
  • the present invention can also provide an optical film for use in the optical member.
  • FIG. 1 is a schematic view of an optical member according to an embodiment of the present invention.
  • FIG. 2 is a schematic view of an optical member according to another embodiment of the present invention.
  • FIG. 3 is a graph of the refractive index distribution of an optical member according to another embodiment of the present invention.
  • FIG. 4 is a schematic view of an optical member according to another embodiment of the present invention.
  • FIG. 5 is a schematic view of an optical member according to another embodiment of the present invention.
  • FIG. 6 is a graph of the infrared transmission spectrum of a branched melamine polymer c used in Examples 1, 3, 4, 5, 7, and 8 and Comparative Examples 1 and 3.
  • FIG. 7 is a graph showing the relationship between the branched melamine polymer content of a mixed layer of a polyimide a and a branched melamine polymer and the refractive index of the mixed layer in Examples 1 and 2.
  • FIG. 8 is a graph of the infrared transmission spectrum of a branched melamine polymer d used in Examples 2 and 6 and Comparative Example 2.
  • FIG. 9 is a graph showing the relationship between the branched melamine polymer content of a mixed layer of a polyimide b or a polycarbonate and a branched melamine polymer c and the refractive index of the mixed layer in Examples 3 and 4.
  • FIG. 10 is a graph of the absolute reflectance of a surface of a glass B on which a polymer layer and a layer having a textured structure of aluminum oxide crystals are stacked in Examples 5 to 7.
  • FIG. 11 is a graph of the absolute reflectance of a surface of the glass B on which a polymer layer and a porous layer of silicon oxide are stacked in Example 8.
  • FIG. 12 is a graph of the absolute reflectance of a surface of the glass B on which a polymer layer and a layer having a textured structure of aluminum oxide crystals are stacked in Comparative Examples 1 and 2.
  • FIG. 13 is a graph of the absolute reflectance of a surface of the glass B on which a polymer layer and a porous layer of silicon oxide are stacked in Comparative Example 3.
  • FIG. 14 is a graph of the absolute reflectance of a surface of the glass B on which a polymer layer and a layer having a textured structure of aluminum oxide crystals are stacked in Comparative Example 4.
  • FIG. 15 is an enlarged electron micrograph of a surface of an optical member according to another embodiment of the present invention.
  • An optical member includes a laminated body configured to reduce light reflection disposed on a substrate.
  • a surface of the laminated body is a porous layer or a layer having a textured structure (projections), and at least one layer of the laminated body is a polymer layer containing a linear polymer and a branched polymer.
  • the optical member includes a laminated body on a substrate.
  • a surface of the laminated body includes a porous layer or a layer having a textured structure.
  • the optical film is used in at least one layer of the laminated body and includes a polymer layer containing a linear polymer and a branched polymer.
  • FIG. 1 is a schematic view of an optical member according to an embodiment of the present invention.
  • an optical member according to an embodiment of the present invention includes a substrate 1 , a polymer layer 2 disposed on the substrate 1 , and a low-refractive-index layer 3 disposed on the polymer layer 2 .
  • the low-refractive-index layer 3 is a porous layer or a layer having a textured structure.
  • the polymer layer 2 and the low-refractive-index layer 3 constitute a laminated body 9 .
  • An optical film of an optical member according to an embodiment of the present invention includes the polymer layer 2 .
  • the laminated body 9 composed of the polymer layer 2 and the low-refractive-index layer 3 can reduce light reflection on the surface of the substrate 1 .
  • the polymer layer 2 contains a linear polymer and a branched polymer. Components of the polymer layer 2 other than the linear polymer and the branched polymer complement the polymers and are compatible with, can be mixed with, or can be dispersed in the polymer layer 2 , provided that the components do not impair the characteristics of the polymers.
  • a large difference in refractive index between the substrate 1 and the low-refractive-index layer 3 which is a porous layer or a layer having a textured structure, results in strong reflection at their interface and a low antireflection effect.
  • the formation of the polymer layer 2 between the substrate 1 and the low-refractive-index layer 3 can produce a higher antireflection effect than the formation of the low-refractive-index layer 3 directly on the substrate 1 .
  • the polymer layer 2 may have a thickness of 10 nm or more and 100 nm or less depending on the refractive index of the substrate.
  • the polymer layer 2 having a thickness of less than 10 nm has little antireflection effect.
  • the polymer layer 2 having a thickness of more than 100 nm has a markedly reduced antireflection effect.
  • the branched polymer of the polymer layer 2 has a branched molecular chain in its molecule.
  • the branched polymer may be a multi-branched polymer, such as a dendrimer or a hyperbranched polymer.
  • the branched polymer may be a branched polycarbonate, a branched polyamide, a branched polyimide, or a branched melamine polymer.
  • a plurality of ⁇ conjugated systems, such as aromatic rings are generally introduced to increase refractive index, this significantly reduces solubility in the case of linear polymers.
  • a branched polymer rarely has intermolecular entanglement of molecular chains because of the excluded volume effect of branched molecular chains.
  • a branched polymer has a high degree of solubility in solvents, is easily compatible with another polymer, and is suitably used in combination with a linear polymer.
  • the branched polymer in the polymer layer 2 is effective in controlling the refractive index of the polymer layer 2 .
  • the branched polymer preferably has a refractive index of 1.7 or more, more preferably 1.7 or more and less than 2.0, at a wavelength of 550 nm.
  • the branched polymer having a refractive index of less than 1.7 at a wavelength of 550 nm is not significantly effective in controlling the refractive index of the polymer layer 2 .
  • the branched polymer having a refractive index of 2.0 or more has strong absorption in a visible light region and reduces transmittance through the polymer layer 2 .
  • the branched polymer in the polymer layer 2 may have a structure represented by the following general formula (1). This structure imparts a high refractive index and high heat resistance to the branched polymer.
  • R1 and R2 independently denote a divalent organic group having an aromatic ring or a heterocycle, and n is an integer of 3 or more.
  • the divalent organic group having an aromatic ring or a heterocycle include, but are not limited to, a phenylene group, a naphthylene group, and a biphenyl group.
  • the linear polymer in the polymer layer 2 has a molecular chain of repeated monomer units and has no branch point in the molecular chain. Entanglement of molecular chains of the linear polymer during film formation yields a dense and uniform film even in the case of a thin film having a thickness of submicron or less, such as the polymer layer 2 .
  • the branched polymer Although having excellent solubility and compatibility, the branched polymer rarely has the entanglement of molecular chains and rarely yields a dense and uniform film. Thus, the branched polymer can be combined with a linear polymer, which can yields a dense and uniform film even in the case of a thin film, to form a uniform thin film.
  • the linear polymer for use in the polymer layer 2 may be any linear polymer that can be combined with the branched polymer.
  • the linear polymer include, but are not limited to, acrylic polymers, melamine polymers, phenolic resins, polycarbonates, polyesters, polyarylates, polyethers, polyureas, polyurethanes, polyamides, polyamideimides, polyimides, polyketones, polysulfones, polyphenylenes, polyxylylenes, and polycycloolefins.
  • the linear polymer may have an aromatic ring and/or an imide ring in its main chain.
  • the aromatic ring and the imide ring may have a structure represented by the following chemical formula.
  • the aromatic ring and the imide ring have a planar structure.
  • Molecular chains of the linear polymer having such a structure in the main chain can be easily oriented in parallel with a substrate.
  • the linear polymer is more effective in a thin film like the polymer layer 2 in terms of the uniformity of film thickness and refractive index.
  • the linear polymer causes little variations in film thickness and refractive index.
  • linear polymer having an aromatic ring and/or an imide ring in its main chain examples include, but are not limited to, aromatic polyethers, such as polyetherketones and polyethersulfones, aromatic polyesters, such as poly(ethylene terephthalate), aromatic polycarbonates, aromatic polyurethanes, aromatic polyureas, aromatic polyamides, and thermoplastic polyimides.
  • aromatic polyethers, aromatic polysulfides, aromatic polycarbonates, and polyimides have excellent heat resistance.
  • the linear polymer may have a lower refractive index than the branched polymer, and a difference in refractive index between the linear polymer and the branched polymer may be 0.04 or more and 0.4 or less.
  • the branched polymer When the difference in refractive index between the linear polymer and the branched polymer is less than 0.04, the branched polymer is not significantly effective in controlling the refractive index of the polymer layer 2 . When the difference in refractive index between the linear polymer and the branched polymer is more than 0.4, this results in an excessively large refractive index difference and possibly impairs the in-plane uniformity of refractive index.
  • the branched polymer content is preferably 10% by weight or more and 90% by weight or less, more preferably 15% by weight or more and 85% by weight or less, of the total weight of the linear polymer and the branched polymer.
  • a branched polymer content of less than 10% by weight may result in an insufficient amount of branched polymer for controlling the refractive index.
  • a branched polymer content of more than 90% by weight may result in an uneven thickness of the polymer layer 2 because of an insufficient amount of linear polymer.
  • the linear polymer content is preferably 10% by weight or more and 90% by weight or less, more preferably 15% by weight or more and 85% by weight or less, of the total weight of the linear polymer and the branched polymer.
  • a method for manufacturing an optical member according to an embodiment of the present invention is a method for manufacturing an optical member including a laminated body configured to reduce light reflection disposed on a substrate. This method includes
  • the polymer layer 2 is formed as described below.
  • a polymer solution of a linear polymer and a branched polymer dissolved in a solvent is prepared in advance or immediately before use.
  • the polymer solution can be prepared by dissolving a linear polymer powder and a branched polymer powder in the solvent.
  • the polymer solution may also be prepared by mixing a linear polymer solution and a branched polymer solution or mixing reaction solutions after polymerization.
  • the polymers in the linear polymer solution and the branched polymer solution may be polymer precursors.
  • the linear polymer is a polyimide
  • the polymer in the solution may be a polyimide precursor, such as polyamic acid.
  • the solvent for use in the polymer solutions may be a solvent for dissolving both the linear polymer and the branched polymer.
  • the solvent include, but are not limited to, ketones, such as 2-butanone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; esters, such as ethyl acetate, n-butyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, ethyl lactate, and ⁇ -butyrolactone; ethers, such as tetrahydrofuran, dioxane, diisopropyl ether, dibutyl ether, cyclopentylmethyl ether, and diglyme; aromatic hydrocarbons, such as toluene, xylene, and ethylbenzene; chlorinated hydrocarbons, such as chloroform, methylene chloride, and tetrachloro
  • the polymer layer 2 is formed by applying the polymer solution of the linear polymer and the branched polymer to a substrate or a thin film disposed on the substrate.
  • the polymer solution can be applied by a known method, such as dipping, spin coating, spraying, printing, or flow coating, or a combination thereof.
  • the applied polymer solution is dried and/or baked at 23° C. or more and 250° C. or less at normal pressure or under reduced pressure.
  • the polymer solution is dried and/or baked for approximately five minutes to two hours principally in order to remove the solvent.
  • the polymer solution may be heated by light, radiation, or electromagnetic wave irradiation using a circulating hot-air oven, a muffle furnace, infrared rays, or a microwave.
  • the polymer layer 2 may contain component(s) other than the linear polymer and the branched polymer, provided that the component(s) does not impair the optical properties, transparency, heat resistance, and water-fastness of the polymer layer 2 .
  • the amount of component(s) other than the linear polymer and the branched polymer is less than 20 parts by weight per 100 parts by weight of the linear polymer and the branched polymer. Twenty parts by weight or more of the component(s) other than the linear polymer and the branched polymer may impair the transparency, strength, and thickness uniformity of the polymer layer 2 .
  • the component(s) other than the linear polymer and the branched polymer may be a silane coupling agent for improving adhesiveness or a phosphate.
  • a phenolic antioxidant may be added to the polymer layer 2 in order to reduce coloring during heat treatment.
  • a thermosetting resin, a photocurable resin, and/or a cross-linker, such as an epoxy resin, a melamine resin, and/or an acrylic resin, may be added to the polymer layer 2 in order to improve the solvent resistance of the polymer layer 2 .
  • a small amount of inorganic fine particles such as SiO 2 , TiO 2 , ZrO 2 , ZnO, MgO, and/or Al 2 O 3 , may be added to the polymer layer 2 in order to control the refractive index or increase the hardness of the polymer layer 2 .
  • the low-refractive-index layer 3 which is a porous layer or a layer having a textured structure, disposed on the polymer layer 2 may have a refractive index of 1.4 or less at a wavelength of 550 nm and may be composed of a metal oxide, a metal halide, or a fluoropolymer.
  • the porous layer may be a layer of fine particles or hollow particles made of silicon oxide or magnesium fluoride.
  • a dispersion liquid of fine particles dispersed in water or a solvent may be applied to the polymer layer 2 by spin coating. Voids between particles can reduce the density and consequently the refractive index of the resulting layer.
  • the porous layer preferably has a thickness of 30 nm or more and 300 nm or less, more preferably 50 nm or more and 200 nm or less.
  • the layer having a textured structure serving as the low-refractive-index layer 3 has an infinite number of projections on its surface.
  • the layer having a textured structure is an antireflection film that has a nano structure of a certain material and that has an apparent refractive index changing in the thickness direction of the film.
  • the apparent refractive index is lower than the intrinsic refractive index of the material.
  • the layer having a textured structure has a nano structure of a material containing a metal oxide or a metallic compound and has an apparent refractive index that changes in the thickness direction of the layer, the apparent refractive index being lower than the intrinsic refractive index of the material.
  • the layer having a textured structure has a fine structure having a smaller dimension than the operating wavelength of an optical component to which the antireflection film is applied.
  • the fine structure has a plurality of closed spaces isolated from the outside atmosphere or open spaces in communication with the outside atmosphere.
  • the antireflection film has a refractive index lower than the refractive index of the material (the intrinsic refractive index of the material) of the antireflection film and thereby has a reduced apparent refractive index.
  • the intrinsic refractive index of the material is the refractive index of a non-porous thin film or a bulk of the material
  • the apparent refractive index is a reduced refractive index of a film having the fine structure containing spaces.
  • the apparent refractive index changes as the occupancy of the spaces or a solid portion in the film changes in the thickness direction.
  • FIG. 2 is a schematic cross-sectional view of an antireflection film according to an embodiment of the present invention.
  • the antireflection film includes a solid portion (textured structure) 5 and a space 11 .
  • the apparent refractive index may be increased stepwise or continuously in the traveling direction of light (arrow A).
  • the apparent refractive index may be decreased stepwise or continuously in the traveling direction of light (arrow B).
  • the refractive index may be approximately 1 on the outermost surface of the antireflection film in contact with the outside atmosphere and may be increased and approach the intrinsic refractive index of the material of the antireflection film (for example, 1.4 to 3.0) in the thickness direction of the antireflection film.
  • the antireflection film may include at least two layers of a fine structure having different space or solid portion occupancies or may have distribution in space or solid portion occupancy.
  • the outermost surface of the antireflection film has a fine textured structure with the thickness (t) of each raised portion (projection) being smaller than the operating wavelength, more specifically, being in the order of nanometer.
  • FIG. 15 is an enlarged electron micrograph of a surface of an optical member according to another embodiment of the present invention.
  • the material of the solid portion may be a metallic compound, for example, a metal oxide, such as silicon oxide, zinc oxide, titanium oxide, magnesium oxide, zirconium oxide, or aluminum oxide, a metal fluoride, such as magnesium fluoride, a metal fluoride oxide, or a metal hydroxide.
  • a metallic compound for example, a metal oxide, such as silicon oxide, zinc oxide, titanium oxide, magnesium oxide, zirconium oxide, or aluminum oxide, a metal fluoride, such as magnesium fluoride, a metal fluoride oxide, or a metal hydroxide.
  • the material of the solid portion may contain at least one of these substances.
  • the material of the solid portion may contain more than one metallic elements, for example, a multi-element metallic compound of a binary system or a ternary system.
  • the material of the solid portion may contain phosphorus and/or boron.
  • the crystal structure of the solid portion is not particularly limited and may be amorphous, microcrystalline, polycrystalline, or monocrystalline. Alternatively, the solid portion may contain microcrystals, polycrystals, and/or single crystals in an amorphous material.
  • the antireflection film may be manufactured by applying surface treatment, such as heat treatment or hot water treatment, to a solid film formed by a gas phase method, such as vacuum evaporation, sputtering, or chemical vapor deposition (CVD), a sol-gel method, or a liquid phase method, such as coating or spraying, to form a fine textured structure on the solid film.
  • a gas phase method such as vacuum evaporation, sputtering, or chemical vapor deposition (CVD), a sol-gel method, or a liquid phase method, such as coating or spraying
  • an amorphous aluminum oxide film formed on a substrate by a sol-gel method can be immersed in hot water to grow plate crystals of an oxide of aluminum called boehmite, a hydroxide of aluminum, or a hydrate thereof, forming a petal-shaped fine textured structure.
  • the polymer layer 2 is disposed as an intermediate layer between the antireflection film having such a fine textured structure and the substrate.
  • the intermediate layer may be a plurality of layers, a plurality of polymer layers according to an embodiment of the present invention, or a layer other than the polymer layers according to the present invention.
  • the layer other than the polymer layers according to the present invention may be a solid film having an intermediate refractive index between the apparent refractive index of the antireflection film and the refractive index of the substrate. More specifically, an inorganic substance, such as a metallic compound described above as the material of the antireflection film, or an organic substance, such as resin exemplified by polyimide, may be used.
  • the textured structure is formed of aluminum oxide, silicon oxide, a transparent polymer, and other component(s). Because of voids in the textured structure, the low-refractive-index layer has a refractive index distribution in the thickness direction and a high antireflection effect.
  • FIG. 2 is a schematic view of an optical member according to another embodiment of the present invention.
  • the optical member includes a substrate 1 , a polymer layer 2 disposed on the substrate 1 , and a layer 4 having a textured structure 5 disposed on the polymer layer 2 .
  • the textured structure 5 may be formed of aluminum oxide crystals.
  • aluminum oxide crystals refers to crystals deposited and grown on a surface of a layer mainly composed of aluminum oxide by immersing the layer in hot water to peptize the surface of the layer.
  • the refractive index of the layer 4 having the textured structure may continuously increase from the top toward the substrate in a linear (a) or curved (b or c) manner.
  • the layer 4 having a refractive index that continuously increases from the top toward the substrate has a higher reflectance-reduction effect than a plurality of layers in which the refractive index increases layer by layer from the top.
  • the layer 4 having the textured structure is formed of crystals mainly composed of an oxide or hydroxide of aluminum or a hydrate thereof.
  • the crystals may be formed of boehmite.
  • An oxide of aluminum, a hydroxide of aluminum, and hydrates of these compounds are hereinafter collectively referred to as aluminum oxide.
  • An upper end of randomly arranged large and small crystals forms the textured structure 5 .
  • the layer 4 having the textured structure may be divided into the textured structure 5 and its lower layer.
  • the lower layer may be formed of aluminum oxide alone or aluminum oxide and 30% by mole or less ZrO 2 , SiO 2 , TiO 2 , ZnO, and/or MgO.
  • FIG. 4 illustrates a substrate 1 having a flat surface, such as a plate, a film, or a sheet. It is desirable that the average of the angles ⁇ 1 between slopes 6 in the textured structure 5 and the substrate surface be 45 degrees or more and 90 degrees or less, preferably 60 degrees or more and 90 degrees or less.
  • FIG. 5 illustrates a substrate 1 having a two-dimensionally or three-dimensionally curved surface. It is desirable that the average of the angles ⁇ 2 between slopes 7 in the textured structure 5 and a tangent line 8 of the substrate surface be 45 degrees or more and 90 degrees or less, preferably 60 degrees or more and 90 degrees or less. When the angle ⁇ 1 or ⁇ 2 is more than 90 degrees, its supplementary angle is used.
  • the thickness of the layer 4 having the textured structure is preferably 20 nm or more and 1000 nm or less, more preferably 50 nm or more and 1000 nm or less.
  • the textured structure 5 has effective antireflection performance, maintains mechanical strength, and has advantages in manufacturing costs.
  • the antireflection performance is further improved.
  • the surface density of the textured structure 5 is also important and can be represented by the average surface roughness Ra′ and the surface area ratio Sr, which is defined later.
  • the average surface roughness Ra′ can be determined by applying the measurement of center-line average roughness to the surface.
  • the average surface roughness Ra′ is 5 nm or more, preferably 10 nm or more, more preferably 15 nm or more and 100 nm or less.
  • the surface area ratio Sr is 1.1 or more, preferably 1.15 or more, more preferably 1.2 or more and 3.5 or less.
  • the surface density of the textured structure 5 can be determined with a scanning probe microscope (SPM).
  • SPM scanning probe microscope
  • the average surface roughness Ra′ which is determined by applying the measurement of center-line average roughness Ra to the surface, and the surface area ratio Sr of the layer 4 having the textured structure can be determined by SPM observation. More specifically, the average surface roughness Ra′ (nm) can be determined by three-dimensionally applying the measurement of center-line average roughness Ra defined by JIS B 0601 to a surface to be measured.
  • the average surface roughness Ra′ refers to “the average of the absolute values of deviations of specified planes from the reference plane” and is expressed by the following equation (1):
  • Ra ′ 1 S 0 ⁇ ⁇ Y B Y T ⁇ ⁇ X L X R ⁇ ⁇ F ⁇ ( X , Y ) - Z 0 ⁇ ⁇ ⁇ ⁇ X ⁇ ⁇ ⁇ Y Equation ⁇ ⁇ ( 1 )
  • Ra′ average surface roughness (nm);
  • F(X,Y) a height at a point of measurement (X,Y), wherein X denotes the x-coordinate, and Y denotes the y-coordinate;
  • X L to X R the range of the surface to be measured on the x-coordinate
  • Y B to Y T the range of the surface to be measured on the y-coordinate
  • Z 0 the average height of the surface to be measured.
  • the actual surface area of the surface to be measured is determined as described below.
  • the surface to be measured is divided into minute triangles defined by adjacent three data points (A, B, and C).
  • the area ⁇ S of each of the minute triangles is then determined using a vector product.
  • ⁇ S( ⁇ ABC) [s(s ⁇ AB)(s ⁇ BC)(s ⁇ AC)]0.5, wherein AB, BC, and AC denote the lengths of their respective sides. s ⁇ 0.5(AB+BC+AC)].
  • the surface area S is the sum total of ⁇ S's.
  • the surface density of the textured structure 5 is such that Ra′ is 5 nm or more and Sr is 1.1 or more, the textured structure 5 can exhibit antireflection.
  • Ra′ of 10 nm or more and Sr of 1.15 or more result in a higher antireflection effect.
  • the fine textured structure is actually useful.
  • Ra′ is 100 nm or more and Sr is 3.5 or more, however, scattering due to the textured structure 5 predominates over the antireflection effect, resulting in poor antireflection performance.
  • a method for forming the layer 4 having the textured structure in the present invention may include
  • the layer mainly composed of aluminum oxide can be formed on the polymer layer 2 by a known gas phase method, such as chemical vapor deposition (CVD) or physical vapor deposition (PVD), a known liquid phase method, such as a sol-gel method, or a known hydrothermal synthesis using an inorganic salt.
  • CVD chemical vapor deposition
  • PVD physical vapor deposition
  • a gel film formed by the application of a precursor sol of aluminum oxide can be treated with hot water to grow aluminum oxide crystals of a textured structure. This method can form a uniform antireflection layer on a large-area or nonplanar substrate.
  • the raw material of the gel film formed from the precursor sol of aluminum oxide contains an Al compound alone or an Al compound and at least one compound selected from Zr, Si, Ti, Zn, and Mg compounds.
  • Metal alkoxides and salt compounds such as chlorides and nitrates, may be used as the raw materials for Al 2 O 3 , ZrO 2 , SiO 2 , TiO 2 , ZnO, and MgO.
  • metal alkoxides may be used as ZrO 2 , SiO 2 , and TiO 2 raw materials because of their excellent film-forming properties.
  • Examples of the aluminum compound include, but are not limited to, aluminum ethoxide, aluminum isopropoxide, aluminum n-butoxide, aluminum sec-butoxide, aluminum tert-butoxide, and aluminum acetylacetonate, oligomers thereof, aluminum nitrate, aluminum chloride, aluminum acetate, aluminum phosphate, aluminum sulfate, and aluminum hydroxide.
  • zirconium alkoxide examples include, but are not limited to, zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetra-n-propoxide, zirconium tetraisopropoxide, zirconium tetra-n-butoxide, and zirconium tetra-t-butoxide.
  • the silicon alkoxide may be represented by the general formula Si(OR) 4 .
  • R's may be the same or different and may independently denote a lower alkyl group, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, or an isobutyl group.
  • titanium alkoxide examples include, but are not limited to, tetramethoxytitanium, tetraethoxytitanium, tetra-n-propoxytitanium, tetraisopropoxytitanium, tetra-n-butoxytitanium, and tetraisobutoxytitanium.
  • Examples of the zinc compound include, but are not limited to, zinc acetate, zinc chloride, zinc nitrate, zinc stearate, zinc oleate, and zinc salicylate, particularly zinc acetate and zinc chloride.
  • magnesium compound examples include, but are not limited to, magnesium alkoxides, such as dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, and dibutoxymagnesium, magnesium acetylacetonate, and magnesium chloride.
  • the organic solvent may be any organic solvent that does not induce the gelation of the raw materials described above, such as alkoxides.
  • the organic solvent include, but are not limited to, alcohols, such as methanol, ethanol, 2-propanol, butanol, pentanol, ethylene glycol, and ethylene glycol mono-n-propyl ether; aliphatic or alicyclic hydrocarbons, such as n-hexane, n-octane, cyclohexane, cyclopentane, and cyclooctane; aromatic hydrocarbons, such as toluene, xylene, and ethylbenzene; esters, such as ethyl formate, ethyl acetate, n-butyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and ethylene glycol monobutyl ether acetate; ketones,
  • alkoxide raw materials aluminum, zirconium, and titanium alkoxides have particularly high reactivity to water and are abruptly hydrolyzed by the action of moisture in the air or the addition of water, producing turbidity and precipitation in the solution.
  • Aluminum salt compounds, zinc salt compounds, and magnesium salt compounds are difficult to dissolve in organic solvents and provide low solution stability. To avoid these problems, a stabilizer may be added to stabilize the solution.
  • the stabilizer examples include, but are not limited to, ⁇ -diketone compounds, such as acetylacetone, dipivaloylmethane, trifluoroacetylacetone, hexafluoroacetylacetone, benzoylacetone, dibenzoylmethane, 3-methyl-2,4-pentanedione, and 3-ethyl-2,4-pentanedione; ⁇ -ketoester compounds, such as methyl acetoacetate, ethyl acetoacetate, allyl acetoacetate, benzyl acetoacetate, isopropyl acetoacetate, tert-butyl acetoacetate, isobutyl acetoacetate, 2-methoxyethyl acetoacetate, and 3-keto-methyl n-valerate; and alkanolamines, such as monoethanolamine, diethanolamine, and triethanolamine.
  • alkanolamines such as mono
  • the molar ratio of the stabilizer to an alkoxide or a salt compound can be approximately one.
  • a catalyst can be added to promote part of reactions to form a desired precursor. Examples of the catalyst include, but are not limited to, nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, and ammonia.
  • the precursor sol of aluminum oxide may be applied to the polymer layer 2 or a surface of the laminated body disposed on the polymer layer 2 .
  • the precursor sol can be applied by a known method, such as dipping, spin coating, spraying, printing, or flow coating, or a combination thereof.
  • a film of the precursor sol of aluminum oxide can be dried and/or baked at 60° C. or more and 250° C. or less, preferably 100° C. or more and 200° C. or less, to form an aluminum oxide layer.
  • a heat-treatment temperature higher than 250° C. may cause damage, such as deformation, to the substrate.
  • the heating time depends on the heating temperature and may be 10 minutes or more.
  • the layer mainly composed of aluminum oxide formed on the polymer layer 2 by the method described above may be brought into contact with hot water or water vapor, for example, immersed in hot water or exposed to water vapor, to precipitate aluminum oxide crystals, thereby forming the textured structure 5 on the surface.
  • an amorphous aluminum oxide layer may remain in a lower portion of the textured structure 5 in the layer 4 having the textured structure.
  • a surface of the layer mainly composed of aluminum oxide in contact with hot water or water vapor is peptized, and some components are eluted from the layer. Because of a difference in hot-water solubility between hydroxides, crystals mainly composed of aluminum oxide are precipitated and grown on the surface layer.
  • the temperature of hot water may be in the range of 40° C. to 100° C.
  • the hot-water treatment time may be in the range of approximately 5 minutes to 24 hours.
  • Crystallization in the layer mainly composed of aluminum oxide to which an oxide, such as TiO 2 , ZrO 2 , SiO 2 , ZnO, or MgO, is added as a different component utilizes a difference in hot-water solubility between the components.
  • an oxide such as TiO 2 , ZrO 2 , SiO 2 , ZnO, or MgO
  • the ratios of inorganic components can be altered to control the size of the textured structure in a wide range. This allows the textured structure of the crystals to be controlled in the wide range described above.
  • Use of ZnO as an accessory component allows eutectic crystallization with aluminum oxide. This allows the refractive index of the layer 4 having the textured structure to be controlled in a further wide range, thereby achieving excellent antireflection performance.
  • Examples of the material of the substrate 1 include, but are not limited to, glass, resin, glass mirrors, and resin mirrors.
  • Representative examples of the resin substrate include, but are not limited to, films and formed products made of thermoplastic resins, such as polyester, cellulose triacetate, cellulose acetate, poly(ethylene terephthalate), polypropylene, polystyrene, polycarbonate, polysulfone, polyacrylate, polymethacrylate, ABS resin, poly(phenylene oxide), polyurethane, polyethylene, polycycloolefin, and poly(vinyl chloride); and cross-linked films and cross-linked formed products made of various thermosetting resins, such as unsaturated polyester resin, phenolic resin, cross-linking polyurethane, cross-linking acrylic resin, and cross-linking saturated polyester resin.
  • thermoplastic resins such as polyester, cellulose triacetate, cellulose acetate, poly(ethylene terephthalate), polypropylene, polystyrene, polycarbonate, polys
  • a substrate for use in the present invention may be any substrate, such as a plate, a film, or a sheet, that can have a shape for each intended use and may have a two- or three-dimensionally curved surface.
  • the thickness of the substrate is generally, but is not limited to, 5 mm or less.
  • An optical member according to an embodiment of the present invention may further include another functional layer.
  • a hard coat layer may be disposed on the layer 4 having the textured structure to improve film hardness.
  • a water repellent layer for example, formed of a fluoroalkylsilane or an alkylsilane may be formed to prevent the adhesion of dirt.
  • An adhesive layer or a primer layer may be formed to improve the adhesion between the substrate and the layer mainly composed of aluminum oxide.
  • Optical members according to embodiments of the present invention can be used in various displays for use in word processors, computers, television sets, plasma display panels, and the like; polarizers for liquid crystal displays, and sunglass lenses, prescription glass lenses, viewing lens for cameras, prisms, fly-eye lenses, toric lenses, various optical filters, and sensors made of various optical lens materials and transparent plastics; imaging optical systems, optical systems for observation, such as binoculars, and projection optical systems for use in liquid crystal projectors; various optical lenses, such as scanning optical systems, for use in laser-beam printers; and covers for various measuring instruments and windowpanes for automobiles and trains.
  • a polymer was collected from the polymerization solution by reprecipitation in methanol and was washed with methanol several times. The polymer was dried at 100° C. under vacuum to yield 6.8 g (yield 93%) of polyimide a as a light yellow powder.
  • the imidization rate was 99.5% as determined by measuring the residual amount of carboxy group from a 1 H-NMR spectrum.
  • a polymer was collected from the polymerization solution by reprecipitation in methanol and was washed with methanol several times. The polymer was dried at 100° C. under vacuum to yield 6.1 g (yield 93%) of polyimide b as a light yellow powder.
  • the imidization rate was 99.1% as determined by measuring the residual amount of carboxy group from a 1 H-NMR spectrum.
  • An infrared transmission spectrum was measured from 650 to 4000 cm ⁇ 1 using an infrared spectrometer (Spectrum One, manufactured by PerkinElmer, Inc.) and an accompanying universal ATR.
  • Reflectance was measured with an absolute reflectometer (USPM-RU, manufactured by Olympus Corp.) at a wavelength in the range of 400 to 700 nm at an incident angle of 0 degrees.
  • a minimum value of less than 0.05% was rated good (circle), and a minimum value of 0.05% or more was rated poor (cross).
  • a mean value of less than 0.1% was rated good (circle), a mean value of 0.1% or more and less than 0.2% was rated fair (triangle), and a mean value of 0.2% or more was rated poor (cross).
  • the film thickness was measured with a spectroscopic ellipsometer (VASE, manufactured by J. A. Woollam Japan Co., Inc.) at a wavelength in the range of 380 to 800 nm.
  • VASE spectroscopic ellipsometer
  • the refractive index was measured with a spectroscopic ellipsometer (VASE, manufactured by J. A. Woollam Japan Co., Inc.) at a wavelength in the range of 380 to 800 nm.
  • the refractive index at a wavelength of 550 nm was employed.
  • a substrate surface treated with Pd/Pt was observed with a field emission scanning electron microscope (FE-SEM) (S-4800, manufactured by Hitachi High-Technologies Corp.) at an accelerating voltage of 2 kV.
  • FE-SEM field emission scanning electron microscope
  • a photo-curing paint of a branched melamine polymer (product name Hypertech UR101, manufactured by Nissan Chemical Industries, Ltd.) was diluted with a cyclopentanone/cyclohexanone mixed solvent to a concentration of 2.9% by weight to prepare a branched melamine polymer c solution.
  • FIG. 6 is a graph of the infrared transmission spectrum of the branched melamine polymer c.
  • the infrared transmission spectrum in FIG. 6 shows that the branched melamine polymer c contains a branched melamine polymer having a repeating structure represented by the following general formula (2) (wherein R3 and R4 independently denote a divalent organic group having an aromatic ring, such as a phenylene group).
  • the branched melamine polymer c solution was mixed with the polyimide a solution at room temperature to yield a mixed solution of the polyimide a and the branched melamine polymer c.
  • the following six polymer solutions were prepared: four mixed solutions having different branched melamine polymer c contents, the polyimide a solution, and the branched melamine polymer c solution.
  • the substrate was heated at 140° C. for 30 minutes to form a polymer layer having a thickness in the range of approximately 45 to 50 nm.
  • the polymer layer other than a polyimide a layer was irradiated with light from an ultra-high-pressure mercury lamp at an illuminance of 13 mW for 70 seconds to cure the polymer layer.
  • the following six polymer layers were formed: the polyimide a layer, mixed layers having a branched melamine polymer c content of 16%, 29%, 45%, or 60% by weight, and a branched melamine polymer c layer.
  • FIG. 7 is a graph showing the relationship between the branched melamine polymer content (% by weight) of a polymer layer and the refractive index of the polymer layer.
  • FIG. 7 shows that the refractive indexes of the mixed layers of the polyimide a and the branched melamine polymer c were plotted on a straight line between the refractive index of the polyimide a layer (1.680) and the refractive index of the branched melamine polymer c layer (1.813).
  • Table 1 summarizes the results of Examples 1 to 10 and Comparative Examples 1 to 3.
  • a heat-curing paint of a branched melamine polymer (product name Hypertech UR202, manufactured by Nissan Chemical Industries, Ltd.) was diluted with a cyclopentanone/cyclohexanone mixed solvent to a concentration of 2.9% by weight to yield a branched melamine polymer d solution.
  • FIG. 8 is a graph of the infrared transmission spectrum of the branched melamine polymer d.
  • the infrared transmission spectrum in FIG. 8 shows that the branched melamine polymer d contains a branched melamine polymer having a repeating structure represented by the following general formula (4) (wherein R5 and R6 denote a divalent organic group having an aromatic ring, such as a phenylene group).
  • the branched melamine polymer d solution was mixed with the polyimide a solution at room temperature to yield a blend solution of the polyimide a and the branched melamine polymer d.
  • the following five polymer solutions were prepared: three blend solutions having different branched melamine polymer d contents, the polyimide a solution, and the branched melamine polymer d solution.
  • Example 2 The same procedures as in Example 1 were performed except that the temperature of heating after spin coating was changed from 140° C. to 200° C. and photoirradiation was not performed.
  • the resulting polymer layers had a thickness in the range of approximately 45 to 50 nm and were the following five uniform layers: a polyimide a layer, three mixed layers having a branched melamine polymer d content of 37% by weight, 48% by weight, or 58% by weight, and a branched melamine polymer d layer.
  • FIG. 7 is a graph showing the relationship between the branched melamine polymer d content (% by weight) of a polymer layer and the refractive index of the polymer layer.
  • Example 2 The same procedures as in Example 1 were performed except that the linear polymer was a polyimide b having a repeating structure represented by the following general formula (5).
  • the resulting polymer layers had a thickness in the range of approximately 45 to 50 nm and were the following four uniform layers: a polyimide b layer, two mixed layers having a branched melamine polymer c content of 32% by weight or 63% by weight, and a branched melamine polymer c layer.
  • FIG. 9 is a graph showing the relationship between the branched melamine polymer content (% by weight) of a polymer layer and the refractive index of the polymer layer.
  • Example 2 The same procedures as in Example 1 were performed except that the linear polymer was a polycarbonate having a repeating structure represented by the following general formula (6).
  • the resulting polymer layers had a thickness in the range of approximately 45 to 50 nm and were the following five uniform layers: a polycarbonate layer, three mixed layers having a branched melamine polymer c content of 41% by weight, 68% by weight, or 81% by weight, and a branched melamine polymer c layer.
  • FIG. 9 is a graph showing the relationship between the branched melamine polymer content (% by weight) of a polymer layer and the refractive index of the polymer layer.
  • the polymer layer was spin-coated with a proper amount of precursor sol of aluminum oxide at 4000 rpm for 20 seconds and was baked in a circulating hot-air oven at 140° C. for 60 minutes. The polymer layer was coated with an amorphous aluminum oxide layer.
  • the polymer layer was then immersed in hot water at 80° C. for 20 minutes and was dried at 60° C. for 15 minutes.
  • the FE-SEM observation of the layer surface showed the presence of a fine textured structure of random complicated crystals mainly composed of aluminum oxide.
  • FIG. 10 is a graph of the absolute reflectance of a surface of the glass B on which the polymer layer and the layer having the textured structure of aluminum oxide crystals are stacked in Example 5.
  • the absolute reflectance had a minimum of 0.04% and a mean value of 0.08% at a wavelength in the range of 400 to 700 nm.
  • the glass substrate had an excellent antireflection surface layer.
  • the glass substrate had no clouding due to light scattering.
  • Table 1 and FIG. 10 show the results.
  • a mixed layer of the polyimide a and the branched melamine polymer d (having a branched melamine polymer d content of 58% by weight and a refractive index of 1.740) was formed as a polymer layer on a polished surface of the glass B in the same manner as in Example 2.
  • An amorphous aluminum oxide layer was formed on the polymer layer in the same manner as in Example 5, was subjected to hot water treatment, and was dried.
  • a surface of the resulting layer had a fine textured structure of random complicated crystals mainly composed of aluminum oxide.
  • FIG. 10 is a graph of the absolute reflectance of a surface of the glass B on which the polymer layer and the layer having the textured structure of aluminum oxide crystals are stacked in Example 6.
  • the absolute reflectance had a minimum of 0.03% and a mean value of 0.07% at a wavelength in the range of 400 to 700 nm.
  • the glass substrate had an excellent antireflection surface layer.
  • the glass substrate had no clouding due to light scattering.
  • a mixed layer of the polyimide b and the branched melamine polymer c (having a branched melamine polymer c content of 63% by weight and a refractive index of 1.738) was formed as a polymer layer on a polished surface of the glass B in the same manner as in Example 3.
  • An amorphous aluminum oxide layer was formed on the polymer layer in the same manner as in Example 5, was subjected to hot water treatment, and was dried.
  • a surface of the resulting layer had a fine textured structure of random complicated crystals mainly composed of aluminum oxide.
  • FIG. 10 is a graph of the absolute reflectance of a surface of the glass B on which the polymer layer and the layer having the textured structure of aluminum oxide crystals are stacked in Example 7.
  • the absolute reflectance of the glass substrate had a minimum of 0.03% and a mean value of 0.07% at a wavelength in the range of 400 to 700 nm.
  • the glass substrate had an excellent antireflection surface layer.
  • the glass substrate had no clouding due to light scattering.
  • the photo-curing paint of a branched melamine polymer used in Example 1 was diluted with a mixed solvent of cyclopentanone and cyclohexanone to a concentration of 4.0% by weight to yield a branched melamine polymer c solution.
  • the polyimide a was dissolved in a mixed solvent of cyclopentanone and cyclohexanone to yield a polyimide a solution having a concentration of 3.0% by weight.
  • the branched melamine polymer c solution was mixed with the polyimide a solution at room temperature to yield a blend solution of the polyimide a and the branched melamine polymer c.
  • a polished surface of the glass B was spin-coated with a proper amount of the polymer blend solution at 3500 rpm for 20 seconds.
  • the polymer blend solution was heated at 140° C. for 30 minutes to form a polymer layer having a thickness of approximately 75 nm.
  • the polymer layer was irradiated with light from an ultra-high-pressure mercury lamp at an illuminance of 13 mW for 70 seconds to cure the polymer layer, thereby forming a mixed layer of the polyimide a and the branched melamine polymer c (having a branched melamine polymer c content of 45% by weight and a refractive index of 1.741).
  • the polymer layer was spin-coated with a proper amount of sol of silicon oxide fine particles at 3000 rpm for 20 seconds and was baked in a circulating hot-air oven at 200° C. for 60 minutes to coat the polymer layer with a porous layer of silicon oxide having a thickness of 100 nm and a refractive index of 1.28.
  • FIG. 11 is a graph of the absolute reflectance of a surface of the glass B on which the polymer layer and the porous layer of silicon oxide are stacked in Example 8.
  • the absolute reflectance of the glass substrate had a minimum of 0.03% and a mean value of 0.17% at a wavelength in the range of 400 to 700 nm.
  • the glass substrate had an excellent antireflection surface layer.
  • the glass substrate had no clouding due to light scattering.
  • a polymer layer made of the branched melamine polymer c alone (having a refractive index 1.813) was formed as a polymer layer on a polished surface of the glass B in the same manner as in Example 1.
  • An amorphous aluminum oxide layer was formed on the polymer layer in the same manner as in Example 5, was subjected to hot water treatment, and was dried.
  • the FE-SEM observation of the layer surface showed the presence of a fine textured structure of random complicated crystals mainly composed of aluminum oxide.
  • FIG. 12 is a graph of the absolute reflectance of a surface of the glass B on which the polymer layer and the layer having the textured structure of aluminum oxide crystals are stacked in Comparative Example 1.
  • the absolute reflectance had a minimum of 0.07% and a mean value of 0.17% at a wavelength in the range of 400 to 700 nm. Although the antireflection performance was satisfactory, the minimum reflectance was more than 0.05% because of an uneven polymer layer surface.
  • a polymer layer made of the branched melamine polymer d alone (having a refractive index 1.782) was formed as a polymer layer on a polished surface of the glass B in the same manner as in Example 2.
  • An amorphous aluminum oxide layer was formed on the polymer layer in the same manner as in Example 5, was subjected to hot water treatment, and was dried.
  • the FE-SEM observation of the layer surface showed the presence of a fine textured structure of random complicated crystals mainly composed of aluminum oxide.
  • FIG. 12 is a graph of the absolute reflectance of a surface of the glass B on which the polymer layer and the layer having the textured structure of aluminum oxide crystals are stacked in Comparative Example 2.
  • the absolute reflectance had a minimum of 0.10% and a mean value of 0.18% at a wavelength in the range of 400 to 700 nm. Although the antireflection performance was satisfactory, the minimum reflectance was more than 0.05% because of an uneven polymer layer surface.
  • the photo-curing paint of a branched melamine polymer used in Example 1 was diluted with a mixed solvent of cyclopentanone and cyclohexanone to a concentration of 4.0% by weight to yield a branched melamine polymer c solution.
  • a polished surface of the glass B was spin-coated with a proper amount of the branched melamine polymer c solution at 3500 rpm for 20 seconds.
  • the branched melamine polymer c solution was heated at 140° C. for 30 minutes to form a polymer layer having a thickness of approximately 75 nm.
  • the polymer layer was irradiated with light from an ultra-high-pressure mercury lamp at an illuminance of 13 mW for 70 seconds to cure the polymer layer, thereby forming a polymer layer having a refractive index of 1.816.
  • a porous layer of silicon oxide having a thickness of 101 nm and a refractive index of 1.28 was formed on the polymer layer in the same manner as in Example 8.
  • FIG. 13 is a graph of the absolute reflectance of a surface of the glass B on which the polymer layer and the porous layer of silicon oxide are stacked in Comparative Example 3.
  • the absolute reflectance had a minimum of 0.06% and a mean value of 0.35% at a wavelength in the range of 400 to 700 nm.
  • the mean reflectance was more than 0.2%, indicating poor antireflection performance.
  • the minimum reflectance was more than 0.05% because of an uneven polymer layer surface.
  • a polymer layer made of the polyimide a alone (having a refractive index 1.680) was formed as a polymer layer on the glass B in the same manner as in Example 1.
  • An amorphous aluminum oxide layer was formed on the polymer layer in the same manner as in Example 5, was subjected to hot water treatment, and was dried.
  • the FE-SEM observation of the layer surface showed the presence of a fine textured structure of random complicated crystals mainly composed of aluminum oxide.
  • FIG. 14 is a graph of the absolute reflectance of a surface of the glass B on which the polymer layer and the layer having the textured structure of aluminum oxide crystals are stacked in Comparative Example 4.
  • the absolute reflectance had a minimum of 0.08% and a mean value of 0.22% at a wavelength in the range of 400 to 700 nm.
  • the refractive index of the polymer layer made of the polyimide a alone was too low to reduce the reflectance of the glass B, resulting in poor antireflection performance.
  • the minimum reflectance was more than 0.05%
  • the mean value reflectance was more than 0.2%.
  • An optical member according to an embodiment of the present invention can be applied to a transparent substrate having any refractive index and has an excellent antireflection effect for visible light.
  • Optical members according to embodiments of the present invention can be used in various displays for use in word processors, computers, television sets, plasma display panels, and the like; polarizers for liquid crystal displays, and sunglass lenses, prescription glass lenses, viewing lens for cameras, prisms, fly-eye lenses, toric lenses, various optical filters, and sensors made of various optical lens materials and transparent plastics; imaging optical systems, optical systems for observation, such as binoculars, and projection optical systems for use in liquid crystal projectors; various optical lenses, such as scanning optical systems, for use in laser-beam printers; and covers for various measuring instruments and windowpanes for automobiles and trains.

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CN103376480A (zh) 2013-10-30
US20170160437A1 (en) 2017-06-08
CN103376480B (zh) 2015-06-17
JP2013220573A (ja) 2013-10-28
US10459125B2 (en) 2019-10-29

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