WO2016190415A1 - Couche mince stratifiée et procédé de fabrication de couche mince stratifiée - Google Patents

Couche mince stratifiée et procédé de fabrication de couche mince stratifiée Download PDF

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WO2016190415A1
WO2016190415A1 PCT/JP2016/065724 JP2016065724W WO2016190415A1 WO 2016190415 A1 WO2016190415 A1 WO 2016190415A1 JP 2016065724 W JP2016065724 W JP 2016065724W WO 2016190415 A1 WO2016190415 A1 WO 2016190415A1
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Prior art keywords
metal oxide
oxide particles
thin film
hard coat
layer
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PCT/JP2016/065724
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English (en)
Japanese (ja)
Inventor
行弘 小野
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デクセリアルズ株式会社
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Priority claimed from JP2016105680A external-priority patent/JP6825825B2/ja
Priority to CN202011380539.6A priority Critical patent/CN112442205B/zh
Priority to CN201680028850.XA priority patent/CN107615103B/zh
Priority to KR1020227014513A priority patent/KR102635617B1/ko
Priority to CN202011380675.5A priority patent/CN112442206B/zh
Priority to EP16800119.6A priority patent/EP3306356B1/fr
Application filed by デクセリアルズ株式会社 filed Critical デクセリアルズ株式会社
Priority to EP21169177.9A priority patent/EP3904921A1/fr
Priority to KR1020197033819A priority patent/KR102393911B1/ko
Priority to KR1020247004491A priority patent/KR20240023690A/ko
Priority to KR1020177033088A priority patent/KR102049216B1/ko
Priority to CN202011380849.8A priority patent/CN112415638B/zh
Priority to US15/576,920 priority patent/US10752808B2/en
Publication of WO2016190415A1 publication Critical patent/WO2016190415A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening 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
    • G02B1/113—Anti-reflection coatings using inorganic layer materials only
    • G02B1/115—Multilayers
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • C08J7/0423—Coating with two or more layers, where at least one layer of a composition contains a polymer binder with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/06—Coating with compositions not containing macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/123—Treatment by wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
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    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/67—Particle size smaller than 100 nm
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Definitions

  • the present invention relates to a laminated thin film having excellent adhesion between an organic layer and an inorganic layer, and a method for producing the laminated thin film.
  • This application includes Japanese Patent Application No. 2015-107978 filed on May 27, 2015 in Japan, and Japanese Patent Application No. 2016-105680 filed on May 26, 2016 in Japan. And claims this priority, which is incorporated herein by reference.
  • An example of a laminated thin film is an antireflection film in which an AR (Anti-Reflective) layer is formed on a hard coat layer having a relatively high surface hardness by a dry process (see, for example, Patent Document 1).
  • AR Anti-Reflective
  • the hard coat layer is an organic layer and the AR layer is an inorganic layer, it is difficult to obtain excellent adhesion.
  • the present invention has been proposed in view of such conventional circumstances, and provides a laminated thin film having excellent adhesion between an organic layer and an inorganic layer, and a method for producing the laminated thin film.
  • the inventor has exposed metal oxide particles on the surface of the hard coat layer containing the metal oxide particles, and the surface of the metal oxide is in the same oxygen deficiency state as the metal oxide particles. Or it discovered that the adhesiveness between an organic layer and an inorganic layer improved remarkably by forming into a film the adhesion layer which consists of metals.
  • the laminated thin film according to the present invention is formed on the hard coat layer with the metal oxide particles exposed on the surface, and the metal oxide particle exposed surface of the hard coat layer, and is the same kind as the metal oxide particles.
  • An oxygen deficient metal oxide containing metal or an adhesion layer made of the same kind of metal as the metal oxide particles is provided.
  • the method for producing a laminated thin film according to the present invention includes an exposing step of exposing the metal oxide particles on the surface of the hard coat layer containing the metal oxide particles, and an exposed surface of the metal oxide particles of the hard coat layer. And a film forming step of forming an oxygen deficient metal oxide having the same type of metal as the metal oxide particles or an adhesion layer made of the same type of metal as the metal oxide particles.
  • the adhesion layer strongly adheres to the resin of the hard coat layer and adheres more strongly to the exposed metal oxide particles, excellent adhesion can be obtained.
  • FIG. 1 is a cross-sectional view schematically showing a hard coat layer with exposed metal oxide particles according to the present embodiment.
  • FIG. 2 is a cross-sectional view schematically showing the laminated thin film according to the present embodiment.
  • FIG. 3 is a cross-sectional view schematically showing an antireflection film to which the present invention is applied.
  • FIG. 4 is a photograph showing an evaluation example of a cross-hatch test.
  • FIG. 4A shows a case where no peeling occurs
  • FIG. 4B shows a case where some peeling occurs
  • FIG. The case where peeling occurred in all cases is shown.
  • 5A is a photograph of the TEM cross section of Example 3
  • FIG. 5B is a photograph of the TEM cross section of Comparative Example 1.
  • FIG. 1 is a cross-sectional view schematically showing a hard coat layer from which metal oxide particles according to the present embodiment are exposed
  • FIG. 2 is a cross-sectional view schematically showing a laminated thin film according to the present embodiment. is there.
  • the laminated thin film according to the present embodiment is formed on the hard coat layer 10 with the metal oxide particles 11 exposed on the surface, and on the metal oxide particle exposed surface of the hard coat layer 10.
  • An oxygen deficient metal oxide or metal oxide particle 11 having the same kind of metal and an adhesion layer 12 made of the same kind of metal are provided.
  • a functional layer 20 formed of an inorganic layer is further provided on the adhesion layer 12.
  • the adhesion layer 12 strongly adheres to the resin of the hard coat layer 10 and more firmly adheres to the exposed metal oxide particles 11, so that the adhesion between the hard coat layer 10 and the adhesion layer 12 is achieved. And the scratch resistance of the laminated thin film can be improved.
  • Hard coat layer In the hard coat layer 10, metal oxide particles 11 are dispersed in a resin material, and the metal oxide particles 11 are exposed on the surface.
  • the resin material of the hard coat layer 10 include an ultraviolet curable resin, an electron beam curable resin, a thermosetting resin, a thermoplastic resin, and a two-component mixed resin. Among these, it is preferable to use an ultraviolet curable resin capable of efficiently forming the hard coat layer 10 by ultraviolet irradiation.
  • ultraviolet curable resin examples include acrylic, urethane, epoxy, polyester, amide, and silicone.
  • acrylic examples include acrylic, urethane, epoxy, polyester, amide, and silicone.
  • acrylic examples include acrylic, urethane, epoxy, polyester, amide, and silicone.
  • acrylic when a laminated thin film is used as an optical application, it is preferable to use an acrylic system that provides high transparency.
  • the acrylic ultraviolet curable resin is not particularly limited, and is in view of hardness, adhesion, workability, etc. from a bifunctional, trifunctional or higher polyfunctional acrylic monomer, oligomer, polymer component, etc. It can be properly selected and blended. Moreover, a photoinitiator is mix
  • bifunctional acrylate component examples include polyethylene glycol (600) diacrylate, dimethylol-tricyclodecane diacrylate, bisphenol AEO-modified diacrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, Propoxylated bisphenol A diacrylate, tricyclodecane dimethanol diacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, 1,4-butanediol diacrylate, polyethylene glycol (200) diacrylate, tetraethylene glycol diacrylate, polyethylene glycol (400) Diacrylate, cyclohexane dimethanol diacrylate, etc. are mentioned. Specific examples that can be obtained on the market include the trade name “SR610” of Sartomer Co., Ltd.
  • tri- or higher functional acrylate component examples include pentaerythritol triacrylate (PETA), 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-converted triacrylate, ⁇ -caprolactone-modified tris- (2-acrylic). Roxyethyl) isocyanurate, trimethylolpropane triacrylate (TMPTA), ⁇ -caprolactone-modified tris (acryloxyethyl) acrylate, and the like.
  • Specific examples that can be obtained in the market include Sartomer's trade name “CN968”, Sartomer's trade name “SR444”, and the like.
  • the photopolymerization initiator examples include alkylphenone photopolymerization initiators, acylphosphine oxide photopolymerization initiators, titanocene photopolymerization initiators, and the like. Specific examples that can be obtained on the market include 1-hydroxycyclohexyl phenyl ketone (IRGACURE184, BASF Japan Ltd.).
  • the acrylic ultraviolet curable resin preferably contains a leveling agent in order to improve smoothness.
  • the leveling agent include a silicone leveling agent, a fluorine leveling agent, and an acrylic leveling agent, and one or more of these can be used. Among these, it is preferable to use a silicone leveling agent from the viewpoint of coating properties.
  • Specific examples that can be obtained on the market include, for example, the trade name “BYK337” (polyether-modified polydimethylsiloxane) of Big Chemie Japan Co., Ltd.
  • the solvent used in the acrylic ultraviolet curable resin is not particularly limited as long as the coating property of the resin composition is satisfied, but is preferably selected in consideration of safety.
  • Specific examples of the solvent include propylene glycol monomethyl ether acetate, butyl acetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, Examples thereof include ethyl carbitol acetate, butyl carbitol acetate, and propylene glycol methyl ether, and one or more of these can be used.
  • acrylic UV curable resins include hue adjusters, colorants, UV absorbers, antistatic agents, various thermoplastic resin materials, refractive index adjusting resins, refractive index adjusting particles, and adhesion imparting. Functionality imparting agents such as resins can be contained.
  • the metal oxide particles 11 are particles of metal oxide, and the average particle size is preferably 800 nm or less, more preferably 20 nm or more and 100 nm or less. If the average particle diameter of the metal oxide particles 11 is too large, it will be difficult to make the laminated thin film into an optical application. If the average particle diameter is too small, the adhesion between the hard coat layer 10 and the adhesion layer 12 will be reduced. In addition, in this specification, an average particle diameter means the value measured by BET method.
  • the content of the metal oxide particles 11 is preferably 20% by mass or more and 50% by mass or less with respect to the entire solid content of the resin composition of the hard coat layer 10. If the content of the metal oxide particles 11 is too small, the adhesion between the hard coat layer 10 and the adhesion layer 12 is lowered, and if too much, the flexibility of the hard coat layer 10 is lowered.
  • solid content of a resin composition is all components other than a solvent, and a liquid monomer component is also contained in solid content.
  • the metal oxide particles 11 include SiO 2 (silica), Al 2 O 3 (alumina), TiO 2 (titania), ZrO 2 (zirconia), CeO 2 (ceria), MgO (magnesia), ZnO, Examples include Ta 2 O 5 , Sb 2 O 3 , SnO 2 , and MnO 2 .
  • silica that can provide high transparency.
  • Specific examples that can be obtained on the market include the product name “IPA-ST-L” (silica sol) of Nissan Chemical Co., Ltd.
  • metal oxide particles 11 are exposed and protruded on the surface of the hard coat layer 10.
  • the method for exposing the metal oxide particles 11 is not particularly limited as long as the resin of the hard coat layer 10 can be selectively etched as will be described later.
  • glow discharge treatment, plasma treatment, ion etching, alkali treatment is performed. Etc. can be used.
  • the average value of the protrusion ratio with respect to the average particle diameter of the metal oxide particles 11 exposed on the surface of the hard coat layer 10 is preferably 60% or less, more preferably 10% or more and 30% or less. If the protruding ratio of the metal oxide particles 11 is too large, the metal oxide particles 11 are easily peeled off from the resin, and the adhesion between the hard coat layer 10 and the adhesion layer 12 is lowered. If the protruding ratio is too small, the adhesion is decreased. Improvement effect cannot be obtained.
  • the hard coat layer 10 is made of an ultraviolet curable resin containing a urethane (meth) acrylate oligomer, a tri- or higher-functional (meth) acrylate monomer, a bifunctional (meth) acrylate monomer, and a photopolymerization initiator. Photopolymerization is preferred. By using such a photocurable resin composition, the hard coat layer 10 having excellent hardness can be obtained.
  • the adhesion layer 12 is formed on the exposed surface of the metal oxide particles of the hard coat layer 10 and is made of an oxygen-deficient metal oxide having the same kind of metal as the metal oxide particles 11 or the same kind of metal as the metal oxide particles 11.
  • the oxygen-deficient metal oxide include SiO x , AlO x , TiO x , ZrO x , CeO x , MgO x , ZnO x , TaO x , SbO x , SnO x , and MnO x .
  • the metal oxide in an oxygen deficient state refers to a metal oxide in which the number of oxygens is insufficient compared to the stoichiometric composition.
  • the metal examples include Si, Al, Ti, Zr, Ce, Mg, Zn, Ta, Sb, Sn, and Mn.
  • x in SiO x of the adhesion layer 12 is 0 or more and less than 2.0.
  • the degree of oxidation and the film thickness of the adhesion layer 12 can be appropriately designed according to the functional layer 20 formed on the adhesion layer 12.
  • the functional layer 20 is an antireflection layer (AR (Anti-Reflective) layer) and SiO 2 is used as the metal oxide particles 11
  • x in SiO x of the adhesion layer 12 is 0 or more and 1.9 or less.
  • the film thickness of the adhesion layer 12 is preferably smaller than 50% of the average particle diameter of the metal oxide particles 11 exposed on the surface of the hard coat layer 10, and specifically, 1 nm to 50 nm. It is preferably 1 nm to 30 nm, more preferably 1 nm to 10 nm.
  • the functional layer 20 is an inorganic layer formed on the adhesion layer 12.
  • Examples of the functional layer 20 include optical layers such as an antireflection layer, a retardation layer, and a polarizing layer. Since such an optical layer is an inorganic layer formed by sputtering, for example, thermal dimensional stability can be improved as compared with an organic layer.
  • the hard coat layer 10 and the adhesion layer 12 are firmly adhered to each other by the metal oxide particles 11, so that excellent adhesion can be obtained.
  • the average value of the protrusion ratio with respect to the average particle diameter of the metal oxide particles exposed on the surface of the hard coat layer 10 is 60% or less, more preferably 10% or more and 30% or less, the light resistance in the xenon lamp is reduced. Even in the property test, excellent adhesion can be obtained.
  • FIG. 3 is a cross-sectional view schematically showing an antireflection film to which the present invention is applied.
  • the antireflection film is formed on the base material 30, the hard coat layer 10 with the metal oxide particles 11 exposed on the surface, and the metal oxide particle exposed surface of the hard coat layer 10.
  • an adhesion layer 12 made of a metal oxide or metal in the same oxygen deficiency state as the metal oxide particles 11, an antireflection layer 40, and an antifouling layer 50.
  • the substrate 30 is not particularly limited, but specific examples include PET (Polyethylene terephthalate), a resin (COP) having an alicyclic structure in the main chain having a cycloolefin as a monomer, a cyclic olefin (for example, norbornenes) and ⁇ . -Resins (COC) obtained by addition polymerization with olefins (eg ethylene), TAC (triacetylcellulose) and the like.
  • the thickness of the substrate 30 varies depending on the type and performance of the optical device to which it is applied, but is usually 25 to 200 ⁇ m, preferably 40 to 150 ⁇ m.
  • the hard coat layer 10 and the adhesion layer 12 are the same as the laminated thin film described above.
  • the metal oxide particles 11 of the hard coat layer 10 are SiO 2
  • the adhesion layer 12 is SiO x (x is 0.5 or more and 1.9 or less).
  • the thickness of the hard coat layer 10 is usually 0.5 to 20 ⁇ m, preferably 1 to 15 ⁇ m, and the thickness of the adhesion layer 12 is preferably 10 nm or less.
  • the antireflection layer 40 is formed by alternately forming a high refractive index layer made of a dielectric and a low refractive index layer having a lower refractive index than the high refractive index layer by sputtering.
  • the dielectric of high refractive index Nb 2 O 5 or TiO 2, SiO 2 is preferably used as the dielectric of low refractive index.
  • the antifouling layer 50 is, for example, a coating layer of an alkoxysilane compound having a perfluoropolyether group.
  • an alkoxysilane compound having a perfluoropolyether group By coating with an alkoxysilane compound having a perfluoropolyether group, the water contact angle is 110 ° or more and water repellency can be exhibited, and the antifouling property can be improved.
  • the antireflection film having such a configuration is excellent in scratch resistance, it can be preferably used, for example, as a laminated film for a touch panel. Furthermore, by laminating such a laminated film for a touch panel on an image display element such as a liquid crystal display element or an organic EL display element, it can be preferably applied as an image display / input device for a smartphone or a personal computer.
  • an image display element such as a liquid crystal display element or an organic EL display element
  • the method for producing a laminated thin film according to the present embodiment includes an exposure step of exposing metal oxide particles on the surface of a hard coat layer containing metal oxide particles, and a metal oxide particle exposed surface of the hard coat layer. And a film forming step of forming an adhesion layer made of a metal oxide or metal of the same oxygen deficiency state as the metal oxide particles.
  • the exposure process and the film forming process will be described.
  • an ultraviolet curable resin composition is applied onto the substrate.
  • the coating method is not particularly limited, and a known method can be used.
  • Known coating methods include, for example, micro gravure coating method, wire bar coating method, direct gravure coating method, die coating method, dip method, spray coating method, reverse roll coating method, curtain coating method, comma coating method, knife coating method. And spin coating method.
  • the hard coat layer 10 is formed by drying and photocuring the ultraviolet curable resin composition on the substrate.
  • the drying conditions are not particularly limited, and may be natural drying or artificial drying that adjusts drying humidity, drying time, and the like.
  • wind is applied to the surface of the paint at the time of drying, it is preferable not to generate a wind pattern on the surface of the coating film. This is because, when a wind pattern is generated, the coating appearance is deteriorated and the surface thickness is uneven.
  • energy rays such as gamma rays, alpha rays, and electron beams can be applied as the light for curing the ultraviolet curable resin composition.
  • the method for exposing the metal oxide particles 11 is not particularly limited as long as the resin of the hard coat layer 10 can be selectively etched.
  • glow discharge treatment, plasma treatment, ion etching, alkali treatment, or the like is used. Can do. Among these, it is preferable to use a glow discharge treatment capable of a large area treatment.
  • the glow discharge treatment is performed by a treatment apparatus in which two flat plate electrodes facing each other are placed in a tank that can be evacuated to vacuum, and a film runs in parallel between the electrodes.
  • this processing apparatus may be installed in the film-forming apparatus.
  • the pressure in the processing chamber at this time is not particularly limited as long as glow discharge can be maintained, but is usually in the range of 0.1 to 100 Pa.
  • an inert gas is mainly used, but hydrogen, oxygen, nitrogen, fluorine, chlorine gas, or the like may be used. Moreover, these mixed gas may be sufficient.
  • the inert gas include helium, neon, argon, krypton, xenon, and radon. Among these, helium gas and argon gas are preferable from the viewpoint of availability, and argon gas is particularly preferable in terms of cost.
  • glow discharge is generated by applying a voltage of several hundred volts between the opposing electrodes.
  • the film is continuously passed through the region where the glow discharge is generated, whereby the film surface is reformed by the atmosphere gas ionized.
  • the intensity of the glow treatment can be shown by the energy density (W / m 2 ) at the time of discharge and the treatment time (min).
  • the processing time is a value obtained by dividing the length of the processing region (m) (the length of the electrode in the direction along the film) by the winding speed (m / min).
  • films with different processing strengths can be created by changing the input power and feed rate.
  • Processing force (power ⁇ treatment time / process area, unit: W ⁇ min / m 2) of the glow discharge treatment is preferably from 200 ⁇ 4150W ⁇ min / m 2 , is 420 ⁇ 2100W ⁇ min / m 2 It is more preferable. As the treatment strength increases, more plasma is generated on the surface of the hard coat layer, and the protrusion ratio of the metal oxide particles 11 increases.
  • the average value of the protrusion ratio with respect to the average particle diameter of the metal oxide particles 11 is preferably 60% or less, more preferably 10% or more and 30% or less.
  • the protruding ratio of the metal oxide particles 11 is too large, the metal oxide particles 11 are easily peeled off from the resin, the adhesion between the organic layer and the inorganic layer is lowered, and when the protruding ratio is too small, the effect of improving the adhesion is achieved. Cannot be obtained.
  • the arithmetic average roughness Ra of the hard coat layer surface after etching is preferably 2 nm or more and 12 nm or less, and more preferably 4 nm or more and 8 nm or less.
  • the arithmetic average roughness Ra of the hard coat layer surface is too small, the protruding ratio of the metal oxide particles 11 is not sufficient, and when the arithmetic average roughness Ra is too large, the metal oxide particles 11 are easily peeled off from the hard coat layer 10. There is a tendency.
  • an adhesion layer 12 made of a metal oxide or metal of the same oxygen deficiency state as the metal oxide particles 11 is formed on the metal oxide particle exposed surface of the hard coat layer 10.
  • a method for forming the adhesion layer 12 it is preferable to use sputtering using a target.
  • a target For example, when forming a SiOx film, it is preferable to use a silicon target and reactive sputtering in a mixed gas atmosphere of oxygen gas and argon gas.
  • the functional layer 20 such as an antireflection layer, a retardation layer, or a polarizing layer formed on the adhesion layer 12 can also be formed by sputtering, productivity can be improved.
  • adhesion layer 12 By forming the adhesion layer 12 on the hard coat layer 10 from which the metal oxide particles are exposed in this way, in addition to the large adhesion between the adhesion layer 12 and the resin of the hard coat layer 10, the adhesion layer 12 and the metal Since even greater adhesion with the oxide particles 11 is obtained, excellent adhesion can be obtained.
  • Example> In this example, an antireflection film was produced, and the adhesion between the hard coat layer and the AR layer was evaluated by a cross hatch test.
  • the present invention is not limited to these examples.
  • the alcohol wipe sliding test was performed by pressing a wipe coated with ethyl alcohol against the anti-reflection film with a load of 250 g / cm 2 against the cross hatch surface, and sliding it back and forth 500 times a distance of 10 cm.
  • Example 1 A photocurable resin composition in which the content of silica particles having an average particle diameter of 50 nm was 28% by mass with respect to the entire solid content of the resin composition was prepared. As shown in Table 1, the resin composition was prepared by dissolving silica particles, acrylate, leveling agent, and photopolymerization initiator in a solvent.
  • a PET film was used as a substrate, and the photocurable resin composition was applied onto the PET film with a bar coater, and then the resin composition was photopolymerized to form a 5 ⁇ m thick hard coat layer.
  • Table 2 shows the protrusion height of the filler on the surface of the hard coat layer in Example 1, the protrusion ratio of the filler, and the surface roughness Ra.
  • an adhesion layer made of SiO x having a thickness of 10 nm is formed by sputtering, and an AR layer made of an Nb 2 O 5 film, an SiO 2 film, an Nb 2 O 5 film, and an SiO 2 film on the adhesion layer was deposited. Further, an antifouling layer having a thickness of 10 nm made of an alkoxysilane compound having a perfluoropolyether group was formed on the AR layer, and the antireflection film of Example 1 was produced. The reflectance of this antireflection film was 0.5% or less, and the water contact angle was 110 degrees or more. Table 2 shows the evaluation of the cross-hatch test of the antireflection film in Example 1.
  • Example 2 An antireflection film was produced in the same manner as in Example 1 except that the surface treatment of the hard coat layer was performed with the glow discharge treatment intensity set to 4200 W ⁇ min / m 2 .
  • Table 2 shows the protrusion height of the filler on the surface of the hard coat layer in Example 2, the protrusion ratio of the filler, the surface roughness Ra, and the evaluation of the cross-hatch test of the antireflection film.
  • Example 3 An antireflection film was produced in the same manner as in Example 1 except that the surface treatment of the hard coat layer was performed with the glow discharge treatment intensity set to 2100 W ⁇ min / m 2 .
  • Table 2 shows the protrusion height of the filler on the hard coat layer surface in Example 3, the protrusion ratio of the filler, the surface roughness Ra, and the evaluation of the cross-hatch test of the antireflection film.
  • Example 4 An antireflection film was produced in the same manner as in Example 1 except that the surface treatment of the hard coat layer was performed with the glow discharge treatment intensity of 830 W ⁇ min / m 2 .
  • Table 2 shows the protrusion height of the filler on the surface of the hard coat layer in Example 4, the protrusion ratio of the filler, the surface roughness Ra, and the evaluation of the cross-hatch test of the antireflection film.
  • Example 5 An antireflection film was produced in the same manner as in Example 1 except that the surface treatment of the hard coat layer was performed with a glow discharge treatment intensity of 420 W ⁇ min / m 2 .
  • Table 2 shows the protrusion height of the filler on the hard coat layer surface in Example 5, the protrusion ratio of the filler, the surface roughness Ra, and the evaluation of the cross-hatch test of the antireflection film.
  • Example 6 An antireflection film was produced in the same manner as in Example 1 except that the surface treatment of the hard coat layer was performed with the glow discharge treatment intensity of 200 W ⁇ min / m 2 .
  • Table 2 shows the protrusion height of the filler on the surface of the hard coat layer in Example 6, the protrusion ratio of the filler, the surface roughness Ra, and the evaluation of the cross-hatch test of the antireflection film.
  • Example 7 Except that the surface treatment of the hard coat layer was performed with the treatment intensity of the glow discharge treatment being 420 W ⁇ min / m 2 and that the adhesion layer made of Si having a thickness of 10 nm was formed by sputtering after the glow discharge treatment.
  • An antireflection film was produced in the same manner as in Example 1.
  • Table 2 shows the protrusion height of the filler on the hard coat layer surface in Example 7, the protrusion ratio of the filler, the surface roughness Ra, and the evaluation of the cross-hatch test of the antireflection film.
  • Example 1 An antireflection film was produced in the same manner as in Example 1 except that the glow discharge treatment was not performed.
  • Table 2 shows the protrusion height of the filler on the surface of the hard coat layer in Comparative Example 1, the protrusion ratio of the filler, the surface roughness Ra, and the evaluation of the cross-hatch test of the antireflection film.
  • Example 2 Reflection was carried out in the same manner as in Example 1 except that no silica particles were blended in the resin composition and that the surface treatment of the hard coat layer was performed with the glow discharge treatment intensity set to 830 W ⁇ min / m 2. A prevention film was prepared. Table 2 shows the surface roughness Ra in Comparative Example 2 and the evaluation of the cross-hatch test of the antireflection film.
  • Example 3 An antireflection film was prepared in the same manner as in Example 1 except that the surface treatment of the hard coat layer was performed with a glow discharge treatment intensity of 830 W ⁇ min / m 2 and SiO 2 was formed as an adhesion layer. Produced. Table 2 shows the protrusion height of the filler on the hard coat layer surface in Comparative Example 3, the protrusion ratio of the filler, the surface roughness Ra, and the evaluation of the cross-hatch test of the antireflection film.
  • the average value of the protrusion ratio with respect to the average particle diameter of the metal oxide particles is 60% or less, particularly 10% or more and 30% or less, an excellent evaluation result can be obtained in a sliding test using an alcohol wipe. It was.
  • Second Embodiment> the influence of the average particle diameter of the filler of the hard coat layer and the addition amount on the adhesion was verified. Moreover, it verified about the influence on the adhesiveness of the filler of a hard-coat layer, and the kind of adhesion layer. In addition, surface treatment methods other than glow discharge treatment were studied. The evaluation of the anti-reflection film cross-hatch test was performed in the same manner as in the first example.
  • Example 8 As shown in Table 3, the content of silica particles having an average particle diameter of 100 nm (trade name: MEK-ST-Z, Nissan Chemical Industries, Ltd.) is 28% by mass with respect to the total solid content of the resin composition.
  • An antireflection film was produced in the same manner as in Example 4 except that a photocurable resin composition was prepared. Table 3 shows the evaluation of the cross-hatch test of the antireflection film in Example 8.
  • Example 9 As shown in Table 3, the content of silica particles having an average particle diameter of 20 nm (trade name: MEK-ST-40, Nissan Chemical Industries, Ltd.) is 28% by mass with respect to the entire solid content of the resin composition.
  • An antireflection film was produced in the same manner as in Example 4 except that a photocurable resin composition was prepared. Table 3 shows the evaluation of the cross-hatch test of the antireflection film in Example 9.
  • Example 10 As shown in Table 3, the content of silica particles having an average particle diameter of 100 nm (trade name: MEK-ST-Z, Nissan Chemical Industries, Ltd.) is 20% by mass with respect to the entire solid content of the resin composition.
  • An antireflection film was produced in the same manner as in Example 4 except that a photocurable resin composition was prepared. Table 3 shows the evaluation of the cross-hatch test of the antireflection film in Example 10.
  • Example 11 As shown in Table 3, the content of silica particles having an average particle diameter of 20 nm (trade name: MEK-ST-40, Nissan Chemical Industries, Ltd.) is 50% by mass with respect to the entire solid content of the resin composition.
  • An antireflection film was produced in the same manner as in Example 4 except that a photocurable resin composition was prepared. Table 3 shows the evaluation of the cross-hatch test of the antireflection film in Example 11.
  • Example 12 As shown in Table 3, the content of silica particles having an average particle size of 50 nm (IPA-ST-L, Nissan Chemical Co., Ltd.) is 20% by mass with respect to the total solid content of the resin composition.
  • An antireflection film was produced in the same manner as in Example 4 except that the resin composition was prepared. Table 3 shows the evaluation of the cross-hatch test of the antireflection film in Example 12.
  • Example 13 As shown in Table 3, the photocurability in which the content of silica particles having an average particle diameter of 50 nm (IPA-ST-L, Nissan Chemical Co., Ltd.) is 50% by mass with respect to the entire solid content of the resin composition.
  • An antireflection film was produced in the same manner as in Example 4 except that the resin composition was prepared.
  • Table 3 shows the evaluation of the cross-hatch test of the antireflection film in Example 13.
  • Example 7 As shown in Table 3, an antireflection film was produced in the same manner as in Example 4 except that 5% NaOH, 25 ° C., and 30 seconds of alkali treatment were performed instead of the glow discharge treatment. Table 3 shows the evaluation of the cross-hatch test of the antireflection film in Comparative Example 7.
  • Example 14 As shown in Table 3, an antireflection film was produced in the same manner as in Example 4 except that 5% NaOH, 45 ° C., and 2 minutes of alkali treatment were performed instead of the glow discharge treatment. Table 3 shows the evaluation of the cross-hatch test of the antireflection film in Example 14.
  • Example 15 As shown in Table 3, an antireflection film was produced in the same manner as in Example 4 except that 5% NaOH, 45 ° C., and 5 minutes of alkali treatment were performed instead of the glow discharge treatment. Table 3 shows the evaluation of the cross-hatch test of the antireflection film in Example 15.
  • silica particles having an average particle size of 20 nm or more and 100 nm or less are contained in the range of 20% by mass or more and 50% by mass or less based on the entire solid content of the resin composition as in Examples 8 to 15, alcohol wipes In the sliding test, the improvement in adhesion was observed.
  • the content of the silica particles is 50% by mass or less and 20% by mass or more of the entire solid content of the resin composition with respect to the average particle size of 20 nm to 100 nm of the silica particles
  • Xenon irradiation (xenon arc lamp, 7.5 kW)-Excellent adhesion was obtained in an alcohol wipe sliding test after the introduction of the environment for 60 hours.

Abstract

L'invention concerne : une couche mince stratifiée qui a une excellente adhésivité entre une couche organique et une couche inorganique ; et un procédé de production de la couche mince stratifiée. La présente invention comprend : une couche de revêtement dur (10) sur une surface de laquelle des particules d'oxyde métallique (11) sont exposées ; et une couche d'adhésion (12) formée sur la surface de la couche de revêtement dur sur laquelle les particules d'oxyde métallique (10) sont exposées, la couche d'adhésion (12) étant composée d'un métal ou un oxyde métallique, dans un état déficient en oxygène, dont l'espèce est la même que celle des particules d'oxyde métallique (11). En conséquence, la couche d'adhésion (12) adhère fortement à une résine de la couche de revêtement dur (10) et en outre adhère fortement aux particules d'oxyde métallique exposées (11) de telle sorte qu'une excellente adhésion peut être obtenue.
PCT/JP2016/065724 2015-05-27 2016-05-27 Couche mince stratifiée et procédé de fabrication de couche mince stratifiée WO2016190415A1 (fr)

Priority Applications (11)

Application Number Priority Date Filing Date Title
US15/576,920 US10752808B2 (en) 2015-05-27 2016-05-27 Laminated thin film and method for manufacturing the same
CN201680028850.XA CN107615103B (zh) 2015-05-27 2016-05-27 层叠薄膜及层叠薄膜的制造方法
KR1020227014513A KR102635617B1 (ko) 2015-05-27 2016-05-27 적층 박막, 및 적층 박막의 제조 방법
CN202011380675.5A CN112442206B (zh) 2015-05-27 2016-05-27 层叠薄膜
EP16800119.6A EP3306356B1 (fr) 2015-05-27 2016-05-27 Couche mince stratifiée et procédé de fabrication de couche mince stratifiée
CN202011380539.6A CN112442205B (zh) 2015-05-27 2016-05-27 层叠薄膜
EP21169177.9A EP3904921A1 (fr) 2015-05-27 2016-05-27 Film stratifié mince et son procédé de fabrication
KR1020197033819A KR102393911B1 (ko) 2015-05-27 2016-05-27 적층 박막, 및 적층 박막의 제조 방법
KR1020247004491A KR20240023690A (ko) 2015-05-27 2016-05-27 적층 박막, 및 적층 박막의 제조 방법
KR1020177033088A KR102049216B1 (ko) 2015-05-27 2016-05-27 적층 박막, 및 적층 박막의 제조 방법
CN202011380849.8A CN112415638B (zh) 2015-05-27 2016-05-27 层叠薄膜的制造方法

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JP7389259B2 (ja) 2020-07-13 2023-11-29 日東電工株式会社 防汚層付き光学フィルム
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