WO2022014577A1 - 積層体 - Google Patents

積層体 Download PDF

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Publication number
WO2022014577A1
WO2022014577A1 PCT/JP2021/026255 JP2021026255W WO2022014577A1 WO 2022014577 A1 WO2022014577 A1 WO 2022014577A1 JP 2021026255 W JP2021026255 W JP 2021026255W WO 2022014577 A1 WO2022014577 A1 WO 2022014577A1
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WO
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Prior art keywords
layer
base material
antifouling
refractive index
thickness direction
Prior art date
Application number
PCT/JP2021/026255
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English (en)
French (fr)
Japanese (ja)
Inventor
幸大 宮本
智剛 梨木
Original Assignee
日東電工株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to JP2022536381A priority Critical patent/JP7186334B2/ja
Priority to KR1020227045623A priority patent/KR102520745B1/ko
Priority to CN202180049608.1A priority patent/CN115867436B/zh
Publication of WO2022014577A1 publication Critical patent/WO2022014577A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/083—Oxides of refractory metals or yttrium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/10—Glass or silica
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/12—Organic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3464—Sputtering using more than one target
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/56—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks
    • C23C14/562—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks for coating elongated substrates
    • 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
    • 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
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films

Definitions

  • the present invention relates to a laminated body, and more particularly to a laminated body provided with an antifouling layer.
  • an antireflection film including a film base material, an antireflection layer, and an antifouling layer in order has been proposed (see, for example, Patent Document 1).
  • the present invention is to provide a laminated body capable of suppressing deterioration of the antifouling property of the antifouling layer even after wiping off the dirt adhering to the antifouling layer.
  • a base material layer and an antifouling layer are provided in order toward one side in the thickness direction, and the antifouling layer contains an alkoxysilane compound having a perfluoropolyether group, and a micro-angle incident X is provided.
  • the position of the center of gravity of the peak derived from the periodic arrangement in the in-plane direction of the perfluoropolyether group of the antifouling layer measured by the in-plane diffraction measurement in the line diffraction method is 1.8 ⁇ -1 or less.
  • the present invention [2] includes the laminate according to the above [1], which comprises a primer layer on the other surface of the antifouling layer in the thickness direction.
  • the primer layer contains the laminate according to the above [2], which is a layer containing silicon dioxide.
  • the antifouling layer is the laminate according to the above [3], wherein the alkoxysilane compound having a perfluoropolyether group is formed in the primer layer via a siloxane bond.
  • the present invention [5] includes the laminate according to the above [1], further comprising an adhesion layer and an antireflection layer between the base material layer and the antifouling layer.
  • the present invention [6] includes the laminate according to the above [5], wherein the antireflection layer is composed of two or more layers having different refractive indexes from each other.
  • the present invention [7] includes the laminate according to the above [6], wherein the antireflection layer contains one selected from the group consisting of a metal, a metal oxide, and a metal nitride.
  • the present invention [8] includes the laminate according to the above [6] or [7], wherein one surface of the antireflection layer in the thickness direction is a layer containing silicon dioxide.
  • the antifouling layer in the laminate of the present invention contains an alkoxysilane compound having a perfluoropolyether group. Further, in the antifouling layer, the position of the center of gravity of the peak derived from the periodic arrangement in the in-plane direction of the perfluoropolyether group of the antifouling layer measured by the in-plane diffraction measurement in the micro-angle incident X-ray diffraction method is 1. It is 8 ⁇ -1 or less. Therefore, even after wiping off the dirt adhering to the antifouling layer, it is possible to suppress the deterioration of the antifouling property of the antifouling layer.
  • FIG. 1 shows a cross-sectional view of a first embodiment of the laminated body of the present invention.
  • 2A to 2C show one embodiment of the manufacturing method of the first embodiment of the laminated body of the present invention.
  • FIG. 2A shows a step of preparing a base material in the first step.
  • FIG. 2B shows a step of arranging a hard coat layer (functional layer) on a base material in the first step.
  • FIG. 2C shows a second step of arranging the antifouling layer on the base material layer.
  • 3A and 3B show explanatory views of an alkoxysilane compound having a perfluoropolyether group deposited on the substrate layer.
  • FIG. 3A shows an explanatory diagram of an alkoxysilane compound having a single perfluoropolyether group deposited on the substrate layer.
  • FIG. 3B shows an explanatory diagram of an alkoxysilane compound having a plurality of perfluoropolyether groups deposited on the substrate layer.
  • FIG. 4 shows a cross-sectional view of a second embodiment of the laminated body of the present invention.
  • 5A-5D show one embodiment of the manufacturing method of the 2nd Embodiment of the laminated body of this invention.
  • FIG. 5A shows a step of preparing a base material in the third step.
  • FIG. 5B shows a step of arranging a hard coat layer (functional layer) on a base material in the third step.
  • FIG. 5C shows a fourth step of sequentially arranging the adhesion layer and the optical functional layer (antireflection layer) on the base material layer.
  • FIG. 5D shows a fifth step of arranging the antifouling layer on the optical functional layer (antireflection layer).
  • FIG. 6 shows a cross-sectional view of a modified example of the first embodiment of the laminate of the present invention (a laminate having a primer layer between the base material layer and the antifouling layer).
  • FIG. 7 shows the result of the in-plane diffraction (inplane) measurement of Example 2.
  • FIG. 8 shows the result of fitting in the in-plane diffraction (inplane) measurement of Example 2.
  • the vertical direction of the paper surface is the vertical direction (thickness direction)
  • the upper side of the paper surface is the upper side (one side in the thickness direction)
  • the lower side of the paper surface is the lower side (the other side in the thickness direction).
  • the left-right direction and the depth direction of the paper surface are plane directions orthogonal to the vertical direction. Specifically, it conforms to the direction arrows in each figure.
  • the laminate 1 has a film shape (including a sheet shape) having a predetermined thickness.
  • the laminated body 1 extends in the plane direction orthogonal to the thickness direction.
  • the laminate 1 has a flat upper surface and a flat lower surface.
  • the laminated body 1 includes a base material layer 2 and an antifouling layer 3 in order toward one side in the thickness direction. More specifically, the laminate 1 includes a base material layer 2 and an antifouling layer 3 directly arranged on the upper surface (one side in the thickness direction) of the base material layer 2.
  • the total light transmittance (JIS K 7375-2008) of the laminated body 1 is, for example, 80% or more, preferably 85% or more.
  • the thickness of the laminated body 1 is, for example, 300 ⁇ m or less, preferably 200 ⁇ m or less, and for example, 10 ⁇ m or more, preferably 30 ⁇ m or more.
  • the base material layer 2 is a base material for ensuring the mechanical strength of the laminated body 1.
  • the base material layer 2 has a film shape.
  • the base material layer 2 is arranged on the entire lower surface of the antifouling layer 3 so as to come into contact with the lower surface of the antifouling layer 3.
  • the base material layer 2 includes a base material 4 and a functional layer 5. Specifically, the base material layer 2 includes the base material 4 and the functional layer 5 in order toward one side in the thickness direction.
  • the total light transmittance (JIS K 7375-2008) of the base material layer 2 is, for example, 80% or more, preferably 85% or more.
  • the base material 4 is a treated body to which antifouling property is imparted by the antifouling layer 3.
  • the base material 4 has a film shape.
  • the base material 4 preferably has flexibility.
  • the base material 4 is arranged on the entire lower surface of the functional layer 5 so as to be in contact with the lower surface of the functional layer 5.
  • Examples of the base material 4 include a polymer film.
  • Examples of the material of the polymer film include polyester resin, (meth) acrylic resin, olefin resin, polycarbonate resin, polyether sulfone resin, polyarylate resin, melamine resin, polyamide resin, polyimide resin, cellulose resin, and polystyrene resin.
  • Examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate.
  • Examples of the (meth) acrylic resin include polymethacrylate.
  • Examples of the olefin resin include polyethylene, polypropylene, and cycloolefin polymers.
  • Examples of the cellulose resin include triacetyl cellulose. As the material of the polymer film, cellulose resin is preferable, and triacetyl cellulose is more preferable.
  • the thickness of the base material 4 is, for example, 1 ⁇ m or more, preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, and for example, 200 ⁇ m or less, preferably 150 ⁇ m or less, more preferably 100 ⁇ m or less.
  • the thickness of the base material 4 can be measured using a dial gauge ("DG-205" manufactured by PEACOCK).
  • the functional layer 5 has a film shape.
  • the functional layer 5 is arranged on one side of the base material 4 in the thickness direction.
  • Examples of the functional layer 5 include a hard coat layer.
  • the base material layer 2 includes the base material 4 and the hard coat layer in order toward one side in the thickness direction.
  • the functional layer 5 is a hard coat layer
  • the hard coat layer is a protective layer for suppressing the occurrence of scratches on the base material 4.
  • the hardcourt layer is formed, for example, from a hardcourt composition.
  • the hardcourt composition contains a resin and, if necessary, particles. That is, the hardcourt layer contains a resin and, if necessary, particles.
  • thermoplastic resin examples include polyolefin resins.
  • the curable resin examples include an active energy ray-curable resin that is cured by irradiation with active energy rays (for example, ultraviolet rays and electron beams) and a thermosetting resin that is cured by heating.
  • active energy rays for example, ultraviolet rays and electron beams
  • thermosetting resin that is cured by heating.
  • the curable resin is preferably an active energy ray curable resin.
  • the active energy ray-curable resin examples include (meth) acrylic ultraviolet curable resin, urethane resin, melamine resin, alkyd resin, siloxane-based polymer, and organic silane condensate.
  • the active energy ray-curable resin is preferably a (meth) acrylic ultraviolet curable resin.
  • the resin can contain, for example, the reactive diluent described in JP-A-2008-88309. Specifically, the resin can include polyfunctional (meth) acrylates.
  • the resin can be used alone or in combination of two or more.
  • Examples of the particles include metal oxide fine particles and organic fine particles.
  • Examples of the material of the metal oxide fine particles include silica, alumina, titania, zirconia, calcium oxide, tin oxide, indium oxide, cadmium oxide, and antimony oxide.
  • Examples of the material of the organic fine particles include polymethylmethacrylate, silicone, polystyrene, polyurethane, acrylic-styrene copolymer, benzoguanamine, melamine, and polycarbonate.
  • Preferred examples of the organic fine particles include polymethylmethacrylate.
  • the purpose of including the particles in the hard coat layer is, for example, to impart antiglare property, improve adhesion, improve hardness, and adjust the refractive index.
  • Particles can be used alone or in combination of two or more.
  • a thixotropy-imparting agent for example, organic clay
  • a photopolymerization initiator for example, organic clay
  • a filler for example, a filler
  • a leveling agent for example, organic clay
  • the hard coat composition can be diluted with a known solvent.
  • a diluted solution of the hard coat composition is applied to one surface of the base material 4 in the thickness direction, and if necessary, heated and dried. After drying, the hardcourt composition is cured by, for example, irradiation with active energy rays or heating.
  • the thickness of the hard coat layer is 1 ⁇ m or more, 50 ⁇ m or less, preferably 30 ⁇ m or less.
  • the antifouling layer 3 is a layer for preventing the adhesion of stains such as dirt and fingerprints to one side of the base material layer 2 in the thickness direction.
  • the antifouling layer 3 has a film shape.
  • the antifouling layer 3 is arranged on the entire upper surface of the base material layer 2 so as to be in contact with the upper surface of the base material layer 2.
  • the antifouling layer 3 is formed of an alkoxysilane compound having a perfluoropolyether group.
  • the antifouling layer 3 contains an alkoxysilane compound having a perfluoropolyether group, preferably an alkoxysilane compound having a perfluoropolyether group.
  • alkoxysilane compound having a perfluoropolyether group examples include a compound represented by the following general formula (1).
  • R 1 is a linear or branched alkyl fluoride group in which one or more hydrogen atoms in the alkyl group are replaced with a fluorine atom (for example, the number of carbon atoms is 1 or more and 20 or less).
  • R 2 represents a structure containing at least one repeating structure of a perfluoropolyether (PFPE) group, and preferably represents a structure containing two repeating structures of a PFPE group.
  • the repeating structure of the PFPE group include a repeating structure of a linear PFPE group and a repeating structure of a branched PFPE group.
  • the repeating structure of the linear PFPE group for example, a structure represented by- (OC n F 2n) p- (n represents an integer of 1 or more and 20 or less, and p is an integer of 1 or more and 50 or less. Represented. The same shall apply hereinafter).
  • Examples of the repeating structure of the branched PFPE group include a structure represented by-(OC (CF 3 ) 2 ) p- and a structure represented by-(OCF 2 CF (CF 3 ) CF 2 ) p-. Can be mentioned.
  • the repeating structure of the PFPE group is preferably a repeating structure of a linear PFPE group, and more preferably- (OCF 2 ) p- and-(OC 2 F 4 ) p- .
  • R 3 represents an alkyl group having 1 or more and 4 or less carbon atoms, and preferably represents a methyl group.
  • X represents an ether group, a carbonyl group, an amino group, or an amide group, and preferably represents an ether group.
  • M represents an integer of 1 or more. Further, m represents an integer of preferably 20 or less, more preferably 10 or less, still more preferably 5 or less.
  • the compound represented by the following general formula (2) is preferably used.
  • q represents an integer of 1 or more and 50 or less
  • r represents an integer of 1 or more and 50 or less
  • alkoxysilane compound having a perfluoropolyether group a commercially available product can also be used. Specifically, Optool UD509 (alkoxysilane compound having a perfluoropolyether group represented by the above general formula (2), Daikin Industries, Ltd.) , Optool UD120 (manufactured by Daikin Industries, Ltd.), and KY1903-1 (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • Alkoxysilane compounds having a perfluoropolyether group can be used alone or in combination of two or more.
  • the antifouling layer 3 is formed by the method described later.
  • the thickness of the antifouling layer 3 is, for example, 1 nm or more, preferably 5 nm or more, and for example, 30 nm or less, preferably 20 nm or less, more preferably 15 nm or less, still more preferably 10 nm or less.
  • the thickness of the antifouling layer 3 can be measured by fluorescent X-rays (ZXS PrimusII manufactured by Rigaku).
  • the position of the center of gravity of the peak derived from the periodic arrangement in the in-plane direction of the perfluoropolyether group measured by the in-plane diffraction measurement in the micro-angle incident X-ray diffraction method described later in the antifouling layer 3 is 1.8 ⁇ . -1 or less, preferably, 1.7 ⁇ -1 or less, for example, 1.4 ⁇ -1 or higher, preferably, 1.5 ⁇ -1 or higher, more preferably, 1.6 ⁇ -1 or higher, more preferably, It is 1.65 ⁇ -1 or more, particularly preferably 1.67 ⁇ -1 or more, and most preferably 1.68 ⁇ -1 or more.
  • the position of the center of gravity is the type of alkoxysilane compound having a perfluoropolyether group, and the surface treatment method for the base material layer 2 in the second step described later (when the surface treatment method is plasma treatment, the gas used for plasma treatment).
  • the type) and the output power of the plasma treatment when the surface treatment method is plasma treatment can be adjusted to the above-mentioned predetermined value or less.
  • the half-value full width of the peak derived from the periodic arrangement in the in-plane direction of the perfluoropolyether group measured by the in-plane diffraction measurement in the micro-angle incident X-ray diffraction method described later is, for example, 0.1 ⁇ -1 or more. Further, for example, it is 1.0 ⁇ -1 or less.
  • the full width at half maximum of the peak indicating the lamellar multilayer structure as measured by in-plane diffraction measurement in grazing incidence X-ray diffraction method to be described later, for example, 0.0 ⁇ -1 or more, and is, for example, 1.0 ⁇ -1 or less Is.
  • peak A1 (detailed in Examples described later) is observed between the wave numbers of 0.2 to 1.0 ⁇ -1.
  • the perfluoropolyether group of the peak showing the lamella laminated structure measured by the in-plane diffraction measurement in the micro-angle incident X-ray diffraction method described later and the perfluoropolyether group measured by the in-plane diffraction measurement in the micro-angle incident X-ray diffraction method described later.
  • Intensity ratio to peak derived from periodic arrangement in the in-plane direction peak showing lamella laminated structure measured by in-plane diffraction measurement in micro-angle incident X-ray diffraction method described later / surface in micro-angle incident X-ray diffraction method described later
  • the peak derived from the periodic arrangement in the in-plane direction of the perfluoropolyether group measured by the internal diffraction measurement is, for example, 0 or more, and for example, 1.0 or less.
  • in-plane diffraction (inplane) measurement full width at half maximum, position of center of gravity, and integrated strength
  • the water contact angle of the antifouling layer 3 is, for example, 100 ° or more, preferably 105 ° or more, and for example, 120 ° or less.
  • the antifouling property of the antifouling layer 5 can be improved.
  • the manufacturing method of the method for manufacturing the laminated body 1 includes a first step of preparing the base material layer 2 and a second step of arranging the antifouling layer 3 on the base material layer 2. Further, in this manufacturing method, each layer is arranged in order by, for example, a roll-to-roll method.
  • a diluted solution of the hardcoat composition is applied to one surface of the substrate 4 in the thickness direction, and after drying, the hardcoat composition is cured by irradiation with ultraviolet rays or heating.
  • the hard coat layer (functional layer 5) is arranged (formed) on one surface of the base material 4 in the thickness direction.
  • the base material layer 2 is prepared.
  • the antifouling layer 3 is arranged on the base material layer 2. Specifically, the antifouling layer 3 is arranged on one surface of the base material layer 2 in the thickness direction.
  • the surface of the base material layer 2 is subjected to, for example, a surface treatment from the viewpoint of improving the adhesion between the base material layer 2 and the antifouling layer 3.
  • a surface treatment examples include corona treatment, plasma treatment, frame treatment, ozone treatment, primer treatment, glow treatment, and saponification treatment, and plasma treatment is preferable.
  • Examples of the plasma treatment include plasma treatment with argon gas and plasma treatment with oxygen gas, and plasma treatment with oxygen gas is preferable.
  • the output power of the plasma processing is, for example, 80 W or more, and for example, 150 W or less.
  • Examples of the method for arranging the antifouling layer 3 on the base material layer 2 include a dry coating method and a wet coating method, and preferably, the viewpoint of adjusting the first integrated strength ratio to a predetermined value or less. Therefore, the dry coating method can be mentioned.
  • Examples of the dry coating method include a vacuum vapor deposition method, a sputtering method, and a CVD method, and preferably a vacuum vapor deposition method.
  • a vapor deposition source alkoxysilane compound having a perfluoropolyether group
  • a substrate layer 2 functional layer 5
  • the vapor deposition source is heated to evaporate or sublimate.
  • the vaporized or sublimated vapor deposition source is deposited on the surface of the substrate layer 2 (functional layer 5).
  • the temperature of the vapor deposition source is, for example, 200 ° C. or higher, preferably 250 ° C. or higher, and for example, 300 ° C. or lower.
  • the laminated body 1 is manufactured in which the antifouling layer 3 is arranged on one side of the base material layer 2 in the thickness direction, and the base material layer 2 and the antifouling layer 3 are sequentially provided on one side in the thickness direction.
  • the position of the center of gravity of the peak derived from the periodic arrangement in the in-plane direction of the perfluoropolyether group measured by the in-plane diffraction measurement in the micro-angle incident X-ray diffraction method of the antifouling layer 3 is, for example. It is 1.8 ⁇ -1 or less.
  • the position of the center of gravity is equal to or less than the above upper limit, deterioration of the antifouling property of the antifouling layer 3 can be suppressed even after wiping off the dirt adhering to the antifouling layer 3 (excellent in antifouling durability).
  • the alkoxysilane compound 20 having a perfluoropolyether group is deposited on one side of the base material layer 2 in the thickness direction.
  • the alkoxysilane compound 20 having such a perfluoropolyether group is oriented with respect to the base material layer 2.
  • the alkoxysilane compound 20A oriented perpendicularly to the base material layer 2, the alkoxysilane compound 20B tilted to the base material layer 2, and the alkoxysilane compound 20B oriented parallel to the base material layer 2.
  • Alkoxysilane compound 20C can be mentioned.
  • group 21 a plurality of alkoxysilane compounds 20 having perfluoropolyether groups oriented in the same direction are deposited to form group 21.
  • group 21A having a plurality of alkoxysilane compounds 20A oriented perpendicularly to the base material layer 2 and the group 21B having a plurality of alkoxysilane compounds 20B oriented inclined to the base material layer 2.
  • group 21C having a plurality of alkoxysilane compounds 20C oriented parallel to the substrate layer 2.
  • the position of the center of gravity is an index of the distance between the alkoxysilane compounds 20 having a perfluoropolyether group to be deposited in the group 21.
  • the position of the center of gravity of the antifouling layer 3 is preferably 1.8 ⁇ -1 or less. That is, the distance between the alkoxysilane compounds 20 having the perfluoropolyether group to be deposited in the group 21 is relatively wide. Then, even after the dirt adhering to the antifouling layer 3 is wiped off, the deterioration of the antifouling property of the antifouling layer 3 can be suppressed (excellent in antifouling durability).
  • the antifouling durability can be evaluated by the antifouling durability test described in detail in Examples described later. Specifically, when the amount of change in the contact angle obtained by the antifouling durability test is, for example, 30 ° or less, preferably 23 ° or less, more preferably 15 ° or less, the antifouling layer 3 is: Has excellent antifouling durability.
  • the same members and processes as those in the first embodiment are designated by the same reference numerals, and detailed description thereof will be omitted. Further, the second embodiment can exhibit the same effects as those of the first embodiment, except for special mention. Further, the first embodiment and the second embodiment can be combined as appropriate.
  • the laminate 1 includes a base material layer 2, an adhesion layer 6, an optical functional layer 7, and an antifouling layer 3 in order toward one side in the thickness direction. More specifically, the laminate 1 has a base material layer 2, an adhesion layer 6 directly arranged on the upper surface (one side in the thickness direction) of the base material layer 2, and an upper surface (one side in the thickness direction) of the adhesion layer 6. It is provided with an optical functional layer 7 directly arranged on the surface of the optical functional layer 7 and an antifouling layer 3 directly arranged on the upper surface (one surface in the thickness direction) of the optical functional layer 7.
  • the total light transmittance (JIS K 7375-2008) of the laminated body 1 is, for example, 80% or more, preferably 85% or more.
  • the thickness of the laminated body 1 is, for example, 250 ⁇ m or less, preferably 200 ⁇ m or less, and for example, 10 ⁇ m or more, preferably 20 ⁇ m or more.
  • the base material layer 2 is a base material for ensuring the mechanical strength of the laminated body 1.
  • the base material layer 2 has a film shape.
  • the base material layer 2 is arranged on the entire lower surface of the optical functional layer 7 so as to be in contact with the lower surface of the optical functional layer 7.
  • the base material layer 2 includes the base material 4 and the functional layer 5 as in the base material layer 2 in the first embodiment.
  • the total light transmittance (JIS K 7375-2008) of the base material layer 2 is, for example, 80% or more, preferably 85% or more.
  • the base material 4 has a film shape.
  • the base material 4 preferably has flexibility.
  • the base material 4 is arranged on the entire lower surface of the functional layer 5 so as to be in contact with the lower surface of the functional layer 5.
  • Examples of the base material 4 include the same base material as the base material 4 in the first embodiment, preferably a cellulose resin, and more preferably triacetyl cellulose.
  • the thickness of the base material 4 is the same as the thickness of the base material 4 in the first embodiment.
  • the functional layer 5 has a film shape.
  • the functional layer 5 is arranged on one side of the base material 4 in the thickness direction.
  • Examples of the functional layer 5 include the same hard coat layer as in the first embodiment.
  • the base material layer 2 includes the base material 4 and the hard coat layer in order toward one side in the thickness direction.
  • the thickness of the hard coat layer is the same as the thickness of the hard coat layer in the first embodiment.
  • the adhesion layer 6 is a layer for ensuring an adhesion between the base material layer 2 and the optical functional layer 7.
  • the adhesion layer 6 has a film shape.
  • the adhesion layer 6 is arranged on the entire upper surface of the base material layer 2 (functional layer 5) so as to be in contact with the upper surface of the base material layer 2 (functional layer 5).
  • Examples of the material of the adhesion layer 6 include metal.
  • Examples of the metal include indium, silicon, nickel, chromium, aluminum, tin, gold, silver, platinum, zinc, titanium, tungsten, zirconium, and palladium. Further, as the material of the adhesion layer 6, two or more kinds of alloys of the above metals and oxides of the above metals can also be mentioned.
  • Examples of the material of the adhesion layer 6 include silicon oxide (SiOx) and indium tin oxide (ITO) from the viewpoint of adhesion and transparency.
  • SiOx silicon oxide
  • ITO indium tin oxide
  • SiOx having a smaller oxygen content than the stoichiometric composition is preferably used, and more preferably SiOx having x of 1.2 or more and 1.9 or less is used. ..
  • the material of the adhesion layer 6 is more preferably indium tin oxide (ITO).
  • the thickness of the adhesion layer 6 is, for example, 1 nm or more, for example, 10 nm from the viewpoint of ensuring the adhesion between the base material layer 2 and the optical functional layer 7 and achieving both the transparency of the adhesion layer 6. It is as follows.
  • the optical functional layer 7 is an antireflection layer for suppressing the reflection intensity of external light.
  • optical functional layer 7 is an antireflection layer
  • the antireflection layer has two or more layers having different refractive indexes from each other. Specifically, the antireflection layer has a high refractive index layer having a relatively large refractive index and a low refractive index layer having a relatively small refractive index alternately in the thickness direction.
  • the net reflected light intensity is attenuated by the interference action between the reflected light at the plurality of interfaces in the plurality of thin layers (high refractive index layer, low refractive index layer) contained therein.
  • an interference effect for attenuating the reflected light intensity can be exhibited by adjusting the optical film thickness (product of the refractive index and the thickness) of each thin layer.
  • the first high refractive index layer 11, the first low refractive index layer 12, the second high refractive index layer 13, and the second low refractive index layer 14 are placed on one side in the thickness direction. Prepare in order.
  • the antireflection layer (specifically, a high refractive index layer and a low refractive index layer) is preferably one selected from the group consisting of metals, alloys, metal oxides, metal nitrides, and metal fluorides. , And more preferably one selected from the group consisting of metals, metal oxides, and metal nitrides. As a result, the antireflection layer can suppress the reflection intensity of external light.
  • Examples of the metal include silicon, nickel, chromium, aluminum, tin, gold, silver, platinum, zinc, titanium, tungsten, zirconium, niobium, and palladium.
  • Examples of the alloy include alloys of the above metals.
  • Examples of the metal oxide include the metal oxide of the above-mentioned metal.
  • Examples of the metal nitride include the metal nitride of the above-mentioned metal.
  • Examples of the metal fluoride include metal nitrides of the above-mentioned metal fluorides.
  • the material used for the antireflection layer is selected according to the desired refractive index.
  • the first high refractive index layer 11 and the second high refractive index layer 13 are each made of a high refractive index material having a refractive index of preferably 1.9 or more at a wavelength of 550 nm.
  • high refractive index materials include, for example, niobium oxide (Nb 2 O 5 ), titanium oxide, zirconium oxide, indium tin oxide (ITO), and , Antimonated tin oxide (ATO), preferably niobium oxide. That is, preferably, both the material of the first low refractive index layer 12 and the material of the second low refractive index layer 14 are niobium oxide.
  • the first low refractive index layer 12 and the second low refractive index layer 14 are each made of a low refractive index material having a refractive index of preferably 1.6 or less at a wavelength of 550 nm.
  • examples of the low refractive index material include silicon dioxide (SiO 2 ) and magnesium fluoride, preferably silicon dioxide. That is, preferably, the material of the first low refractive index layer 12 and the material of the second low refractive index layer 14 are both silicon dioxide.
  • the material of the second low refractive index layer 14 is silicon dioxide (in other words, if one side of the antireflection layer in the thickness direction is a layer containing silicon dioxide), the second low refractive index layer 14 And excellent adhesion between the antifouling layer 3 and the antifouling layer 3.
  • the thickness of the first high refractive index layer 11 is, for example, 1 nm or more, preferably 5 nm or more, and for example, 30 nm or less, preferably 20 nm or less.
  • the thickness of the first low refractive index layer 12 is, for example, 10 nm or more, preferably 20 nm or more, and for example, 50 nm or less, preferably 30 nm or less.
  • the thickness of the second high refractive index layer 13 is, for example, 50 nm or more, preferably 80 nm or more, and for example, 200 nm or less, preferably 150 nm or less.
  • the thickness of the second low refractive index layer 14 is, for example, 60 nm or more, preferably 80 nm or more, and for example, 150 nm or less, preferably 100 nm or less.
  • the ratio of the thickness of the second low refractive index layer 14 to the thickness of the second high refractive index layer 13 is, for example, 0.5 or more. It is preferably 0.7 or more, and for example, 0.9 or less.
  • the ratio of the thickness of the second high-refractive index layer 13 to the thickness of the first high-refractive index layer 11 is preferably 5 or more, for example. Is 7 or more, and is, for example, 15 or less, preferably 10 or less.
  • the ratio of the thickness of the second low refractive index layer 14 to the thickness of the first low refractive index layer 12 is preferably 1 or more, for example. Is 3 or more, and is, for example, 10 or less, preferably 8 or less.
  • the antireflection layer is formed by the method described later.
  • the thickness of the antireflection layer is, for example, 100 nm or more, preferably 150 nm or more, and for example, 300 nm or less, preferably 250 nm or less.
  • the thickness of the antireflection layer can be measured by TEM observation of the cross section.
  • the antifouling layer 3 has a film shape.
  • the antifouling layer 3 is arranged on the entire upper surface of the optical functional layer 7 (antireflection layer) so as to be in contact with the upper surface of the optical functional layer 7 (antireflection layer).
  • the antifouling layer 3 is formed of the above-mentioned alkoxysilane compound having a perfluoropolyether group (preferably, the above-mentioned alkoxysilane compound having a perfluoropolyether group represented by the general formula (2)).
  • the antifouling layer 3 contains an alkoxysilane compound having a perfluoropolyether group, preferably an alkoxysilane compound having a perfluoropolyether group.
  • the antifouling layer 3 is formed by the method described later.
  • the thickness, center of gravity position, strength ratio, full width at half maximum and water contact angle of the antifouling layer 3 are the same as the thickness, center of gravity position, strength ratio, full width at half maximum and water contact angle of the antifouling layer 3 in the first embodiment.
  • the position of the center of gravity is the type of alkoxysilane compound having a perfluoropolyether group, and the surface treatment method for the optical functional layer 7 (antireflection layer) in the fifth step described later (when the surface treatment method is plasma treatment).
  • the type of gas used for plasma treatment and the output power of plasma treatment when the surface treatment method thereof is plasma treatment, it can be adjusted to the above-mentioned predetermined value or less.
  • the manufacturing method of the laminated body 1 includes a third step of preparing the base material layer 2 and a fourth step of sequentially arranging the adhesion layer 6 and the optical functional layer 7 (antireflection layer) on the base material layer 2.
  • the optical functional layer 7 (antireflection layer) is provided with a fifth step of arranging the antifouling layer 3. Further, in this manufacturing method, each layer is arranged in order by, for example, a roll-to-roll method.
  • ⁇ Third step> In the third step, as shown in FIG. 5A, first, the base material 4 is prepared.
  • a diluted solution of the hardcoat composition is applied to one surface of the substrate 4 in the thickness direction, and after drying, the hardcoat composition is cured by irradiation with ultraviolet rays or heating.
  • the hard coat layer (functional layer 5) is arranged (formed) on one surface of the base material 4 in the thickness direction.
  • the base material layer 2 is prepared.
  • the adhesion layer 6 and the optical functional layer 7 are sequentially arranged on the base material layer 2. Specifically, the adhesion layer 6 and the optical functional layer 7 (antireflection layer) are sequentially arranged on one surface of the base material layer 2 in the thickness direction.
  • the base material layer 2 includes an adhesion layer 6, a first high refractive index layer 11, a first low refractive index layer 12, a second high refractive index layer 13, and a second low refractive index layer. 14 and 14 are arranged in order toward one side in the thickness direction.
  • the fourth step is a contact layer arranging step of arranging the adhesion layer 6 on the base material layer 2 and a first high refractive index layer arranging step of arranging the first high refractive index layer 11 on the adhesion layer 6.
  • a high refractive index layer arranging step and a second low refractive index layer arranging step of arranging the second low refractive index layer 14 on the second high refractive index layer 13 are provided.
  • each layer is arranged in order by, for example, a vacuum vapor deposition method, a sputtering method, a laminating method, a plating method, an ion plating method, preferably a sputtering method.
  • the surface of the base material layer 2 is subjected to, for example, a surface treatment from the viewpoint of improving the adhesion between the base material layer 2 and the adhesion layer 6.
  • a surface treatment from the viewpoint of improving the adhesion between the base material layer 2 and the adhesion layer 6.
  • the surface treatment include the surface treatment mentioned in the second step, and preferably plasma treatment.
  • the targets (each layer (adhesion layer 6, first high refractive index layer 11, first low refractive index layer 12, second high refractive index layer 13, and second low refractive index layer 13) are placed in the vacuum chamber.
  • the material of 14) and the base material layer 2 are arranged so as to face each other, gas is supplied and a voltage is applied from a power source to accelerate gas ions to irradiate the target, and the target material is ejected from the target surface to the target.
  • the material is deposited on the surface of the substrate layer 2 in order.
  • the gas examples include an inert gas (for example, argon). Further, if necessary, a reactive gas such as oxygen gas can be used in combination.
  • the flow rate ratio (sccm) of the reactive gas is not particularly limited, but for example, 0.1 flow rate% or more and 100 flow rate% or less with respect to the total flow rate ratio of the sputter gas and the reactive gas. Is.
  • the atmospheric pressure during sputtering is, for example, 0.1 Pa or more, and for example, 1.0 Pa or less, preferably 0.7 Pa or less.
  • the power supply may be, for example, any of a DC power supply, an AC power supply, an MF power supply, and an RF power supply, or may be a combination thereof.
  • the adhesion layer 6 and the optical functional layer 7 are sequentially arranged on one surface of the base material layer 2 in the thickness direction.
  • the antifouling layer 3 is arranged on the optical functional layer 7 (antireflection layer). Specifically, the antifouling layer 3 is arranged on one side of the optical functional layer 7 (antireflection layer) in the thickness direction.
  • the surface of the optical functional layer 7 is subjected to, for example, a surface treatment from the viewpoint of improving the adhesion between the optical functional layer 7 (antireflection layer) and the antifouling layer 3.
  • a surface treatment from the viewpoint of improving the adhesion between the optical functional layer 7 (antireflection layer) and the antifouling layer 3.
  • the surface treatment include the surface treatment mentioned in the second step, preferably plasma treatment, and more preferably plasma treatment with oxygen gas.
  • the same method as the method described as the method of arranging the antifouling layer 3 on the base material layer 2 of the second step can be mentioned.
  • a dry coating method more preferably a vacuum vapor deposition method can be mentioned.
  • a vapor deposition source alkoxysilane compound having a perfluoropolyether group
  • an optical functional layer 7 antireflection layer
  • the temperature of the vapor deposition source is, for example, 200 ° C. or higher, preferably 250 ° C. or higher, and for example, 300 ° C. or lower.
  • the antifouling layer 3 is arranged on one side of the optical functional layer 7 (antireflection layer) in the thickness direction, and the base material layer 2, the adhesion layer 6, the optical functional layer 7 (antireflection layer), and the antifouling layer are arranged.
  • a laminated body 1 having layers 3 in order toward one side in the thickness direction is manufactured.
  • the laminated body 1 includes an optical functional layer 7 (antireflection layer) between the base material layer 2 and the antifouling layer 3. Therefore, it is possible to suppress the reflection of external light.
  • optical functional layer 7 antireflection layer
  • one side of the optical functional layer 7 (antireflection layer) in the thickness direction is a layer containing silicon dioxide
  • a layer containing silicon dioxide for example, silicon dioxide
  • the hydrolyzing group in the alkoxysilane compound having the perfluoropolyether group of the antifouling layer 3 (-(OR) in the above formula (1). 3 ))
  • the silanol group generated in the process of hydrolysis and silicon in silicon dioxide undergo a dehydration condensation reaction.
  • an alkoxysilane compound having a perfluoropolyether group is formed on the optical functional layer 7 (antireflection layer) via a siloxane bond. This makes it possible to further improve the antifouling durability.
  • the laminate 1 includes the base material layer 2 and the antifouling layer 3, but as shown in FIG. 6, a primer layer is further provided between the base material layer 2 and the antifouling layer 3. 15 can also be provided. Specifically, the laminate 1 may be provided with the primer layer 15 on the other surface of the antifouling layer 3 in the thickness direction.
  • the laminated body 1 is provided with the base material layer 2, the primer layer 15, and the antifouling layer 3 in order toward one side in the thickness direction.
  • the primer layer 15 is a layer that adheres to the antifouling layer 3.
  • the material of the primer layer 15 is preferably silicon dioxide (SiO 2 ). More preferably, the primer layer 15 is made of silicon dioxide (SiO 2 ).
  • the material of the primer layer 15 is silicon dioxide (SiO 2 )
  • the hydrolyzing group (-(OR 3 ) in the above formula (1)) in the alkoxysilane compound having a perfluoropolyether group of the antifouling layer 3 The silanol group generated in the process of hydrolysis and silicon in silicon dioxide undergo a dehydration condensation reaction.
  • an alkoxysilane compound having a perfluoropolyether group is formed in the primer layer 15 via a siloxane bond. This makes it possible to further improve the antifouling durability.
  • the primer layer 15 is formed by, for example, a sputtering method, a plasma CVD method, a vacuum vapor deposition method, or the like.
  • the base material layer 2 includes the base material 4 and the functional layer 5 in order toward one side in the thickness direction.
  • the base material layer 2 does not include the functional layer 5 and may be made of the base material 4.
  • the antireflection layer includes two high refractive index layers having a relatively high refractive index and two low refractive index layers having a relatively low refractive index.
  • the number of high refractive index layers and low refractive index layers is not particularly limited.
  • Examples and comparative examples are shown below, and the present invention will be described in more detail.
  • the present invention is not limited to Examples and Comparative Examples.
  • specific numerical values such as the compounding ratio (content ratio), physical property values, parameters, etc. used in the following description are described in the above-mentioned "form for carrying out the invention", and the compounding ratios corresponding to them (Substitute the upper limit value (value defined as “less than or equal to” or “less than”) or the lower limit value (value defined as "greater than or equal to” or “excess”) such as content ratio), physical property value, parameter, etc. be able to.
  • a hard coat layer was placed on one side of the base material (TAC film) in the thickness direction.
  • the amount of silica particles with respect to 100 parts by mass of the resin component is added to the ultraviolet curable acrylic resin composition (manufactured by DIC, trade name "GRANDIC PC-1070", refractive index at a wavelength of 405 nm: 1.55).
  • Organo silica sol (“MEK-ST-L” manufactured by Nissan Chemical Co., Ltd., average primary particle size of silica particles (inorganic filler): 50 nm, particle size distribution of silica particles: 30 nm to 130 nm, solid 30% by weight) was added and mixed to prepare a hard coat composition.
  • the hardcourt composition was applied to one side of the substrate (TAC film) in the thickness direction so that the thickness after drying was 6 ⁇ m, and dried at 80 ° C. for 3 minutes. Then, using a high-pressure mercury lamp , ultraviolet rays having an integrated light intensity of 200 mJ / cm 2 were irradiated to cure the coating layer and form a hard coat layer. As a result, the base material layer was prepared.
  • ⁇ Fourth step> A roll-to-roll plasma processing apparatus was used to plasma-treat one surface of the base material layer (hardcoat layer) in the thickness direction under a vacuum atmosphere of 1.0 Pa.
  • argon gas was used as the inert gas, and the discharge power was set to 2400 W.
  • the adhesion layer and the antireflection layer were sequentially arranged (formed) on one surface in the thickness direction of the base material layer.
  • a roll-to-roll sputter film forming apparatus is used to form an indium tin oxide (ITO) layer having a thickness of 2.0 nm as an adhesion layer on the HC layer of the TAC film with an HC layer after plasma treatment.
  • ITO indium tin oxide
  • Nb 2 O 5 layer with a thickness of 12 nm as the first high refractive index layer SiO 2 layer with a thickness of 28 nm as the first low refractive index layer
  • Nb with a thickness of 100 nm as the second high refractive index layer.
  • the 2 O 5 layer and the SiO 2 layer having a thickness of 85 nm as the second low refractive index layer were sequentially arranged (formed).
  • an ITO target was used, an argon gas as an inert gas and 10 parts by volume of oxygen gas as a reactive gas with respect to 100 parts by volume of the argon gas were used, and the discharge voltage was set to 350 V.
  • the pressure in the film chamber was set to 0.4 Pa, and the ITO layer was formed by MFAC sputtering.
  • Nb target was used to form the first high refractive index layer. Further, 100 parts by volume of argon gas and 5 parts by volume of oxygen gas were used. Further, the discharge voltage was 415 V, the film forming pressure was 0.42 Pa, and the Nb 2 O 5 layer was formed by MFAC sputtering.
  • a Si target was used to form the first low index of refraction layer. Further, 100 parts by volume of argon gas and 30 parts by volume of oxygen gas were used. Further, the discharge voltage was 350 V, the film formation pressure was 0.3 Pa, and the SiO 2 layer was formed by MFAC sputtering.
  • Nb target was used to form the second high refractive index layer. Further, 100 parts by volume of argon gas and 13 parts by volume of oxygen gas were used. Further, the discharge voltage was set to 460 V, the film forming pressure was set to 0.5 Pa, and the Nb 2 O 5 layer was formed by MFAC sputtering.
  • a Si target was used to form the second low index of refraction layer. Further, 100 parts by volume of argon gas and 30 parts by volume of oxygen gas were used. Further, the discharge voltage was set to 340 V, the film forming pressure was set to 0.25 Pa, and the Nb 2 O 5 layer was formed by MFAC sputtering.
  • the adhesion layer and the antireflection layer were sequentially arranged (formed) on one surface in the thickness direction of the base material layer.
  • ⁇ Fifth step> An antifouling layer was placed on one side of the antireflection layer in the thickness direction.
  • plasma treatment with argon gas was carried out as a surface treatment on one surface of the antireflection layer in the thickness direction.
  • the output power of the plasma processing was 100 W.
  • an antifouling layer having a thickness of 7 nm was arranged on one side in the thickness direction of the antireflection layer by a vacuum vapor deposition method using an alkoxysilane compound containing a perfluoropolyether group as a vapor deposition source.
  • the vapor deposition source is a solid content obtained by drying Optool UD120 (manufactured by Daikin Industries, Ltd.).
  • the heating temperature of the vapor deposition source (crucible) in the vacuum vapor deposition method was set to 260 ° C. As a result, a laminated body was obtained.
  • Example 2 A laminate was produced according to the same procedure as in Example 1.
  • the surface treatment of one surface of the antireflection layer in the thickness direction was changed to plasma treatment with oxygen instead of plasma treatment with argon gas.
  • Example 3 A laminate was produced based on the same procedure as in Example 2.
  • the vapor deposition source was changed to KY1903-1 (manufactured by Shin-Etsu Chemical).
  • Comparative Example 1 A laminate was produced according to the same procedure as in Example 1.
  • the fifth step was changed as follows.
  • ⁇ Fifth step> Optool UD509 was applied to one surface of the antireflection layer in the thickness direction with a gravure coater so that the coating thickness was 8 ⁇ m. Then, it was heat-treated at a drying temperature of 60 ° C. for 60 seconds. As a result, an antifouling layer having a thickness of 7 nm was arranged on one side of the antireflection layer in the thickness direction.
  • Comparative Example 2 A laminate was produced according to the same procedure as in Example 1. However, in the fifth step, the output power of the plasma processing was changed to 4500 W.
  • In-plane diffraction (inplane) measurement was carried out for the antifouling layer of the laminated body of each Example and each Comparative Example by the micro-angle incident X-ray diffraction method based on the following conditions.
  • Example 2 The result of the in-plane diffraction (inplane) measurement of Example 2 is shown in FIG.
  • the position of the center of gravity was calculated from the results of the obtained in-plane diffraction (inplane) measurement.
  • the fitting method was used from the viewpoint of uniformly calculating the position of the center of gravity. The method will be described in detail by taking Example 2 as an example.
  • Peak intensity (n is an integer of 1 to 4.
  • a 1 indicates the peak intensity of peak A 1.
  • a 2 indicates the peak intensity of peak A 2.
  • a 3 indicates the peak intensity of peak A 3.
  • a 4 indicates the peak intensity of the peak A4.)
  • Q An indicates the position of the center of gravity (q A1 indicates the position of the center of gravity of the peak A1.
  • Q A2 indicates the position of the center of gravity of the peak A2.
  • ⁇ q A4 indicating the position of the center of gravity of the peak A3 is .Derutaq an indicating a.) indicating the position of the center of gravity of the peaks A4, the full width at half maximum ([Delta] q A1 is .Derutaq A2 indicating the full width at half maximum of the peak A1, the peak The half-value full width of A2 is indicated.
  • ⁇ q A3 indicates the half-value full width of the peak A3.
  • ⁇ q A4 indicates the half-value full width of the peak A4.).
  • the peak A1 is the peak showing the lamellar multilayer structure, the position of the center of gravity is 0.2 ⁇ -1 or 1.0 ⁇ -1 or less. Further, the peak A4 is a peak derived from the periodic arrangement of the perfluoropolyether group in the in-plane direction, and the position of the center of gravity is 1.8 ⁇ -1 or less.
  • the measured data in-plane diffraction (inplane) measurement
  • the measured data can be shown as the sum of the background and the peaks A1 to A4.
  • Table 1 shows the peak intensity, peak position, half-value full width, integrated intensity, and standardized integrated intensity.
  • the laminate of the present invention is suitably used, for example, in an antireflection film with an antifouling layer, a transparent conductive film with an antifouling layer, and an electromagnetic wave shielding film with an antifouling layer.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Metallurgy (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Laminated Bodies (AREA)
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