WO2021261225A1 - 親水性膜の製造方法、親水性膜及び光学部材 - Google Patents

親水性膜の製造方法、親水性膜及び光学部材 Download PDF

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Publication number
WO2021261225A1
WO2021261225A1 PCT/JP2021/021486 JP2021021486W WO2021261225A1 WO 2021261225 A1 WO2021261225 A1 WO 2021261225A1 JP 2021021486 W JP2021021486 W JP 2021021486W WO 2021261225 A1 WO2021261225 A1 WO 2021261225A1
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Prior art keywords
layer
hydrophilic
film
hydrophilic film
refractive index
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English (en)
French (fr)
Japanese (ja)
Inventor
靖 水町
一成 多田
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Konica Minolta Inc
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Konica Minolta Inc
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Priority to CN202180044588.9A priority Critical patent/CN115702369A/zh
Priority to JP2022531679A priority patent/JPWO2021261225A1/ja
Priority to US18/011,236 priority patent/US20230251401A1/en
Publication of WO2021261225A1 publication Critical patent/WO2021261225A1/ja
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films
    • 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
    • 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
    • G02B1/111—Anti-reflection coatings using layers comprising organic materials
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/113—Anti-reflection coatings using inorganic layer materials only
    • G02B1/115—Multilayers
    • 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
    • G02B27/00—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
    • G02B27/0006—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00 with means to keep optical surfaces clean, e.g. by preventing or removing dirt, stains, contamination, condensation

Definitions

  • the present invention relates to a method for producing a hydrophilic film, a hydrophilic film, and an optical member. More specifically, the present invention relates to a method for producing a hydrophilic film having a hydrophilic layer having excellent durability, scratch resistance, and antireflection function, a hydrophilic film, and an optical member.
  • optical members such as lenses, antibacterial cover members, antifungal coating members, and mirrors.
  • hydrophilic function deteriorates in a high temperature environment or temperature change (cold heat impact) of a lens, water droplets remain on the lens surface, which causes deterioration of image visibility.
  • a method of forming a hydrophilic film by a wet film forming method using an inorganic material 2) A method of forming a hydrophilic film by a wet film formation method using an organic material, 3) A method of forming a hydrophilic film by a dry film forming method using an inorganic material, And so on.
  • Patent Document 1 an antifogging material for an organic substrate containing a specific alcohol solvent and an organosilica sol is contacted or applied to the organic substrate. Further, there is disclosed a method of swelling the surface of an organic substrate with the solvent and allowing the organosilica sol to penetrate into the swelled surface to form a silica film exhibiting hydrophilicity. According to the method described in Patent Document 1, it is said that an organic substrate having a low water contact angle and excellent antifouling property, antifog property, adhesion and durability can be obtained.
  • the silica film formed on the surface is applied to an optical member, for example, an in-vehicle camera, salt water contained in sea breeze, acid rain, chemicals such as detergents and waxes used for car washing, etc.
  • an optical member for example, an in-vehicle camera
  • salt water contained in sea breeze, acid rain, chemicals such as detergents and waxes used for car washing, etc.
  • the silica (SiO 2 ) film formed by the wet film formation method as disclosed in Patent Document 1 has low adhesion to the substrate (lens base material), and SiO 2 is dissolved in the salt spray test. It is difficult to maintain the above performance.
  • the silica film has a problem that the adhesion to the substrate is weak and the wear resistance is lowered.
  • the formed hydrophilic film is manufactured by a wet film forming method, there is a problem in its effectiveness for the antireflection function.
  • Patent Document 2 discloses a substrate and an antireflection film having an antifouling layer (hydrophilic layer) formed of a dense layer and a nanoparticle film having a fine concavo-convex structure on the substrate, and has a fine concavo-convex structure.
  • a method of defining the average roughness in a specific range is disclosed.
  • a method of forming a hydrophilic layer by a wet film forming method has been proposed, but the thickness of the hydrophilic layer is in the range of 122 to 140 nm and has a considerably thick film structure, and is scratch resistant. I had a problem with my sexuality.
  • the present invention has been made in view of the above problems and situations, and the problem to be solved thereof is hydrophilicity capable of forming a hydrophilic film having excellent hydrophilicity, durability, scratch resistance, and antireflection function. It is a method of manufacturing a film, and a hydrophilic film and an optical member are provided.
  • the present inventor is a method for producing a hydrophilic film, which comprises a step of forming a hydrophilic layer containing SiO 2 as a main component on a substrate in a process of examining the cause of the above problem in order to solve the above problems.
  • At least one layer of the hydrophilic layer is formed on the substrate by a wet film forming method so that the layer thickness after drying is 10 nm or less in terms of optical layer thickness, and the hydrophilic film has an arithmetic average roughness. It has been found that a method for producing a hydrophilic film having a Ra of 3 nm or more can realize a method for producing a hydrophilic film having excellent hydrophilicity, durability, scratch resistance, and antireflection function. , The present invention has been achieved.
  • a method for producing a hydrophilic film which comprises a step of forming a hydrophilic layer containing SiO 2 as a main component on a substrate. At least one layer of the hydrophilic layer is formed on the substrate by a wet film forming method so that the layer thickness after drying is 10 nm or less in terms of optical layer thickness, and the arithmetic mean roughness of the hydrophilic film is obtained.
  • a method for producing a hydrophilic membrane characterized in that Ra is 3 nm or more.
  • hydrophilicity according to any one of items 1 to 4, wherein the hydrophilic layer is formed by a wet film forming method and then subjected to a sintering treatment at a temperature of 200 ° C. or higher.
  • Membrane manufacturing method
  • a first feature is that a reflectance adjusting layer unit is provided between the substrate and the hydrophilic layer, and the average light reflectance in the wavelength range of 450 to 780 nm is 3.0% or less.
  • a first reflectance adjusting layer unit composed of at least one low refractive index layer and at least one high refractive index layer
  • a hydrophilic membrane having at least a hydrophilic layer on the substrate is composed mainly of SiO 2 , the layer thickness after drying is 10 nm or less in terms of optical layer thickness, and the arithmetic average roughness Ra of the hydrophilic film is 3 nm or more. Hydrophilic membrane.
  • Item 2 The hydrophilic film according to Item 12, wherein the hydrophilic layer has a protective layer having an optical layer thickness of 10 nm or less.
  • a first feature is that a reflectance adjusting layer unit is provided between the substrate and the hydrophilic layer, and the average light reflectance in the wavelength range of 450 to 780 nm is 3.0% or less.
  • the hydrophilic membrane according to any one of items 12 to 15.
  • Item 6 The hydrophilic film according to Item 16, wherein at least one layer constituting the reflectance adjusting layer unit is a sodium-containing layer.
  • the reflectance adjusting layer unit is A first reflectance adjusting layer unit composed of at least one low refractive index layer and at least one high refractive index layer, A second reflectance adjusting layer unit including at least a low refractive index layer, a high refractive index layer and a sodium-containing layer is provided in this order.
  • hydrophilic film according to Item 18 wherein the hydrophilic film has pores that penetrate from the outermost surface layer to the upper surface of the photocatalyst layer and expose the surface of the photocatalyst layer.
  • An optical member comprising the hydrophilic film according to any one of the items 12 to 19.
  • optical member 21 The optical member according to Item 20, wherein the optical member is a lens, an antibacterial cover member, an antifungal coating member, or a mirror.
  • the mechanism of expression or mechanism of action of the effect of the present invention is inferred as follows.
  • at least one layer of the hydrophilic layer is dried after drying as a structure capable of satisfying the hydrophilicity, durability, scratch resistance and antireflection function. It was found that it can be obtained by forming the hydrophilic film by a wet film forming method and setting the arithmetic average roughness Ra of the hydrophilic film to 3 nm or more so that the layer thickness is 10 nm or less in terms of optical layer thickness. Is.
  • hydrophilic films have a structure having a hydrophilic layer composed of a nanoporous or nanoparticle film having a fine concavo-convex structure on a dense layer, but a hydrophilic film having such a structure is known.
  • the first problem is that the nanoporous or nanoparticle film uses a wet film formation method and is formed into a thick film, so it has poor scratch resistance and is used in a harsh environment such as an outdoor camera.
  • the second problem is that the environmental resistance is low, and because the thickness of the hydrophilic layer is thick, the optical characteristics are not stable due to the variation in the film thickness during manufacturing.
  • the present inventors have made the hydrophilic layer 10 nm.
  • excellent arithmetic average roughness Ra is exhibited, and it has hydrophilicity, durability, scratch resistance and antireflection function under various environments. It has been found that a hydrophilic layer exhibiting an excellent effect can be obtained.
  • a dry film forming method for example, a vacuum vapor deposition method is applied when forming a functional layer of a thin film
  • a flat film having few irregularities can be obtained as a surface physical property, so that a heat cycle under a harsh environment can be obtained.
  • resistance it was a characteristic that the hydrophilic quality required in an outdoor environment could not be maintained.
  • the wet film forming method it has been found that by applying the wet film forming method, a desired appropriate uneven structure can be obtained even if the film of the hydrophilic layer is 10 nm or less. Further, by setting the layer thickness of the hydrophilic layer to 10 nm or less, it was possible to obtain high adhesion and reduce the manufacturing variation of the antireflection ability.
  • FIG. 1 A perspective view showing an example of a three-dimensional image obtained by measuring the surface of the hydrophilic film of the present invention using an atomic force microscope (AFM).
  • Schematic diagram showing an example of a vacuum vapor deposition apparatus used in the IAD method Cross-sectional view showing another example of the basic configuration of the hydrophilic membrane of the present invention (Embodiment 2)
  • Cross-sectional view showing an example of a specific configuration of the first reflectance adjusting layer unit constituting the hydrophilic film.
  • Cross-sectional view showing an example of a specific configuration of the second reflectance adjusting layer unit constituting the hydrophilic film.
  • Flow chart of the process of forming pores in the hydrophilic membrane Cross-sectional view showing an example of a configuration in which pores are formed in a hydrophilic film to expose a photocatalyst layer (Embodiment 4).
  • Manufacturing flow showing an example of forming pores in a hydrophilic membrane
  • the method for producing a hydrophilic film of the present invention is a method for producing a hydrophilic film having a step of forming a hydrophilic layer containing SiO 2 as a main component on a substrate, and at least one layer of the hydrophilic layer is formed on the substrate.
  • a wet film forming method so that the layer thickness after drying is 10 nm or less in terms of optical layer thickness, and the arithmetic average roughness Ra of the hydrophilic film is 3 nm or more.
  • a spin coating method, a dip coating method or a spray coating method as a wet film forming method used for forming a hydrophilic layer, which is a large-scale thin film. It is preferable in that it does not require a forming device, can form a thin film having excellent coating film uniformity, and has more excellent hydrophilicity and optical properties.
  • forming a protective layer having an optical layer thickness of 10 nm or less on the hydrophilic layer by a dry film forming method can form an uneven structure of the hydrophilic layer in the lower layer. It is preferable in that it does not fill, the hydrophilic effect can be maintained, a dense thin film can be formed by a dry film forming method, and durability and scratch resistance can be further improved.
  • the hydrophilic membrane of the present invention is a hydrophilic membrane having at least a hydrophilic layer on the substrate.
  • the hydrophilic layer is composed mainly of SiO 2 , the layer thickness after drying is 10 nm or less in terms of optical layer thickness, and the arithmetic average roughness Ra of the hydrophilic film is 3 nm or more.
  • This feature is a technical feature common to or corresponding to the following embodiments.
  • hydrophilic film of the present invention it is possible to further contain a sodium atom in the range of 0.1 to 3.0 atm% in the hydrophilic layer for durability in a high temperature and high humidity environment (maintenance of hydrophilic effect). It is preferable in that it can exert an extremely excellent effect.
  • hydrophilic layer by a wet film forming method and then perform a sintering treatment on the hydrophilic layer at a temperature of 200 ° C. or higher, because durability and scratch resistance are further improved.
  • the protective layer it is preferable to form the protective layer at a temperature of 200 ° C. or higher by a dry film forming method in terms of further improving durability and scratch resistance. Further, it is preferable that the protective layer contains SiO 2 as a main component in that excellent durability and a hydrophilic effect can be obtained.
  • At least one reflectance adjusting layer unit between the substrate and the hydrophilic layer so that the average reflectance in the wavelength range of 450 to 780 nm is 3.0% or less. It is preferable in that a hydrophilic film having excellent permeability can be obtained.
  • At least one layer constituting the reflectance adjusting layer unit is a sodium-containing layer in that an excellent effect of high temperature and high humidity resistance can be exhibited.
  • a first reflectance adjusting layer unit composed of at least one low refractive index layer and at least one high refractive index layer, and at least a low refractive index layer and high
  • the second reflectance adjusting layer unit including the refractive index layer and the sodium-containing layer is provided in this order, and the layer at the position farthest from the substrate of the first reflectance adjusting layer unit is a metal oxide having a photocatalytic function. It is preferable to use a photocatalyst layer containing it in that an excellent photocatalyst effect can be exhibited.
  • the hydrophilic film of the present invention is applied to an optical member, and the fact that the optical member is a lens, an antibacterial cover member, an antifungal coating member or a mirror can sufficiently exhibit the effect of the present invention. ,preferable.
  • the hydrophilic film obtained by the method for producing a hydrophilic film of the present invention is a method for producing a hydrophilic film having a step of forming a hydrophilic layer containing SiO 2 as a main component on a substrate, and is a method for producing a hydrophilic film on the substrate. At least one layer of the hydrophilic layer is formed by a wet film forming method so that the layer thickness after drying is 10 nm or less in terms of optical layer thickness, and the arithmetic average roughness Ra of the hydrophilic film is 3 nm or more. It is characterized by being.
  • FIG. 1 is a cross-sectional view (Embodiment 1) showing an example of the basic configuration of the hydrophilic membrane of the present invention.
  • the hydrophilic film 1 shown in FIG. 1 has a hydrophilic layer 3 having the characteristics specified in the present invention on the substrate 2, and more preferably, a protective layer 4 is provided on the hydrophilic layer 3.
  • the arithmetic mean roughness Ra of the hydrophilic film is based on JIS B 0601-2001 and can be determined using an atomic force microscope.
  • the present invention is characterized in that the arithmetic average roughness Ra is 3 nm or more, preferably in the range of 3 to 20 nm, and in the embodiment of forming pores described later, in the range of 20 to 50 nm. be.
  • FIG. 2 is a perspective view showing an example of a three-dimensional image obtained by measuring the surface of the hydrophilic film of the present invention using an atomic force microscope (AFM) manufactured by Seiko Instruments.
  • AFM atomic force microscope
  • the dry film forming method conventionally applied fills the uneven structure formed on the surface, and the desired arithmetic mean roughness Ra cannot be obtained, but the hydrophilic layer of a thin film having a thickness of 10 nm or less cannot be obtained.
  • FIG. 3 is a graph showing the cross-sectional shape of the hydrophilic film measured using the atomic force microscope (AFM) shown in FIG. 2 on the AA cut surface of the three-dimensional image, and the hydrophilic film shown here is an arithmetic force.
  • the average roughness Ra is 3 nm or more.
  • the hydrophilic layer is formed by a wet film forming method so that the layer thickness after drying is 10 nm or less in terms of optical layer thickness, and the arithmetic mean of the hydrophilic film. It is characterized in that the roughness Ra is 3 nm or more.
  • the hydrophilic layer according to the present invention is composed mainly of SiO 2, and is formed by a wet film forming method so that the layer thickness after drying is 10 nm or less in terms of optical layer thickness, and the layer thickness after drying is optical. It is formed so as to be 10 nm or less in terms of layer thickness.
  • the main component of the hydrophilic layer is SiO 2
  • the ratio of SiO 2 to all the components constituting the hydrophilic layer is 80.0% by mass or more, preferably 90.0% by mass. As mentioned above, it is 99.9% by mass or less, and particularly preferably 97.0% by mass or more and 99.9% by mass or less.
  • the method for producing a hydrophilic film of the present invention is characterized in that the hydrophilic layer is formed by a wet film forming method, and the wet film forming method for forming the hydrophilic layer includes a spin coating method, a dip coating method or a spray coating method.
  • the method is a preferred embodiment.
  • hydrophilic layer constituting the hydrophilic membrane of the present invention will be further described.
  • the hydrophilic layer according to the present invention is characterized by being composed of SiO 2 as a main component, and further preferably contains a sodium atom in the range of 0.1 to 3.0 atm%. ..
  • a conventionally known analysis method for elemental components can be applied to obtain the sodium content.
  • the thickness of the hydrophilic layer is extremely thin, one method is the same as the method for forming the hydrophilic layer on the substrate, and the thickness of the hydrophilic layer for measuring the sodium content is about 200 nm. A single layer is formed, and this is used as a sample for measuring the sodium content in the hydrophilic layer, and the sodium content can be measured by the XPS composition analysis shown below.
  • XPS composition analysis in the same manner as described above.
  • the hydrophilic layer according to the present invention contains SiO 2 as a main component and, if necessary, a sodium atom as an element having an electronegativity smaller than Si, more specifically described above. As described above, it is preferable that the sodium atom is contained in the range of 0.1 to 3.0 atm%.
  • the hydrophilic layer according to the present invention is an element having an electronegativity smaller than Si.
  • the hydrophilic function is further improved, and a hydrophilic film having a low water contact angle can be formed.
  • SiO 2 incorporating a sodium atom develops polarity in the arrangement of electrons, and this is considered to be compatible with H 2 O, which is a polar molecule.
  • Na 2 O which is a sodium oxide
  • SiO 2 As a mixed vapor deposition material
  • NaOH derived from sodium is deliquescent, so it has the property of taking in water from the external environment and trying to become an aqueous solution, and is hydrophilic to take in water in a high temperature and high humidity environment. It is presumed that sex can be maintained for a long period of time.
  • the material for forming the hydrophilic layer containing a sodium atom according to the present invention is not particularly limited, but for example, it is preferable to apply Excel Pure "BD-S01" manufactured by Chuo Motor Co., Ltd. as a commercially available product.
  • the method for producing a hydrophilic film of the present invention is characterized in that the hydrophilic layer according to the present invention is formed by a wet film forming method.
  • the wet film forming method applicable to the present invention is not particularly limited, and is, for example, a spin coating method, a spray coating method, a dip coating method, a flow coating method, a bar coating method, a reverse coating method, a flexographic method, a printing method, and the like. Examples thereof include an inkjet printing method and a method using these methods in combination.
  • the spin coating method, the dip coating method or the spray coating method can obtain the uniformity of the hydrophilic layer of the thin film, the control of the film thickness, and the arithmetic mean roughness Ra of the desired hydrophilic film. It is preferable in that.
  • the desired film thickness control of the hydrophilic layer can be controlled, for example, by adjusting the substrate rotation speed and adjusting the concentration of the hydrophilic layer forming material when the spin coating method is applied.
  • the hydrophilic layer by a wet film forming method and then perform a sintering treatment at a temperature of 200 ° C. or higher, because the durability and scratch resistance are further improved.
  • the hydrophilic layer according to the present invention can be formed, for example, by a spin coating method, which is a wet film forming method shown below.
  • A) Constituent material charge Hydrophilic material composed of SiO 2 containing Na Product name; Excel Pure BD-SO1 manufactured by Chuo Motor Co., Ltd.
  • B) Method for forming a hydrophilic layer: Spin coating method (1) Dilute Excel Pure to an arbitrary concentration. For example, when the layer thickness is 10 nm and the arithmetic mean roughness Ra of the hydrophilic membrane is 3 nm or more, it is diluted with Excel Pure: Ethanol 1: 8 (mass ratio).
  • a hydrophilic layer is formed by spin coating at room temperature and a rotation speed of 3000 rpm.
  • a protective layer having an optical layer thickness of 10 nm or less is formed on the hydrophilic layer according to the present invention by a dry film forming method, and further, as a dry film forming method. , 200 ° C. or higher is a preferred embodiment. Further, the protective layer according to the present invention preferably has a configuration containing SiO 2 as a main component.
  • the protective layer according to the present invention preferably has the following characteristics.
  • the density of the protective layer is higher than the density of the hydrophilic layer. More specifically, the packing density of the protective layer is preferably 0.95 or more, and more preferably 0.98 or more. On the other hand, the packing density of the hydrophilic layer is preferably less than 0.95, more preferably less than 0.90.
  • the packing density of each of these layers can be determined by forming a single film on a Si substrate with a thickness of 100 nm and performing optical evaluation.
  • the cross section of the hydrophilic membrane can be measured by TEM observation.
  • the component of the protective layer is not particularly limited except that SiO 2 is the main component, but the sodium content is preferably less than 15 atm%, more preferably 0.1 to 15 atm%. Is within the range of.
  • the sodium content in the protective layer according to the present invention can be determined by applying the same method as the method for measuring the sodium content in the hydrophilic layer. That is, a protective layer can be formed on a silicon substrate with a thickness of 100 nm and measured by the XPS method. As another method, the measurement can be performed by using the three-dimensional atom probe method.
  • the surface composition of the hydrophilic film which is a laminated body composed of a substrate / reflectance adjusting layer unit / hydrophilic layer / protective layer in this order, has a sodium content in the range of 0.1 to 15 atm%. It is preferably in the range of 0.1 to 10 atm%, more preferably.
  • Examples of the material constituting the protective layer according to the present invention include SiO 2 , SiO 2- Na 2 O and the like.
  • the layer thickness of the protective layer according to the present invention is preferably 10 nm or less, more preferably in the range of 1 to 10 nm, and further preferably in the range of 2 to 6 nm.
  • the method for forming the protective layer according to the present invention is not particularly limited, but it is preferably formed by a dry film forming method. Examples thereof include an ion beam sputtering method and a magnetron sputtering method, and among them, an ion assisted vapor deposition method (hereinafter, also referred to as “IAD” in the present invention) or a sputtering method is preferable.
  • IAD ion assisted vapor deposition method
  • IAD method is a method in which the high kinetic energy of ions is applied during film formation to form a dense film, and the adhesion of the film is enhanced.
  • the ion beam method is an ionized gas irradiated from an ion source. This is a method of accelerating the adherend material with molecules to form a film on the surface of the substrate.
  • FIG. 4 is a schematic diagram showing an example of a vacuum vapor deposition apparatus using the IAD method, which is an example of a method for forming a protective layer.
  • the vacuum vapor deposition apparatus 101 using the IAD method shown in FIG. 4 (hereinafter, also referred to as an IAD vapor deposition apparatus in the present invention) includes a dome 103 in a chamber 102, and a substrate 104 is arranged along the dome 103.
  • the thin-film deposition source 105 is provided with an electron gun or a resistance heating device that evaporates the thin-film deposition material, and the thin-film deposition material 106 is scattered from the vapor-film deposition source 105 toward the substrate 104 and condenses and solidifies on the substrate 104.
  • the ion beam 108 is irradiated from the IAD ion source 107 toward the substrate, and the high kinetic energy of the ions is applied during the film formation to form a dense film or enhance the adhesion of the film.
  • the substrate 104 used in the present invention includes resins such as glass, polycarbonate resin, and cycloolefin resin, and is preferably an in-vehicle lens.
  • a plurality of thin-film deposition sources 105 are arranged at the bottom of the chamber 102.
  • one vapor deposition source is shown as the vapor deposition source 105, but the number of the vapor deposition sources 105 may be plural.
  • a protective layer is formed by generating a vapor-deposited substance 106 by using an electron gun or resistance heating for the film-forming material (deposited material) of the thin-film deposition source 105, and scattering and adhering the film-forming material to the substrate 104 installed in the chamber 102.
  • a film material such as SiO 2 is formed on the substrate 104.
  • a SiO 2 target on the vapor deposition source 105 to form a film containing SiO 2 as a main component.
  • the chamber 102 is provided with a vacuum exhaust system (not shown), whereby the inside of the chamber 102 is evacuated.
  • the degree of decompression in the chamber is usually in the range of 1 ⁇ 10 -4 to 1 ⁇ 10 -1 Pa, preferably 1 ⁇ 10 -3 to 1 ⁇ 10 ⁇ 2 Pa.
  • the dome 103 holds at least one holder (not shown) for holding the substrate 104, and is also called a thin-film deposition umbrella.
  • the dome 103 has an arcuate cross section, passes through the center of a chord connecting both ends of the arc, and has a rotationally symmetric shape that rotates with an axis perpendicular to the chord as a rotationally symmetric axis. As the dome 103 rotates about the axis, for example, at a constant speed, the substrate 104 held by the dome 103 via the holder revolves around the axis at a constant speed.
  • the dome 103 can hold a plurality of holders side by side in the radial direction of rotation (radial direction of revolution) and the direction of rotation (revolutionary direction). As a result, it becomes possible to simultaneously form a film on a plurality of substrates 104 held by a plurality of holders, and it is possible to improve the manufacturing efficiency of the laminated body.
  • the IAD ion source 107 is a device that introduces argon gas or oxygen gas into the main body to ionize them and irradiates the ionized gas molecules (ion beam 108) toward the substrate 104.
  • Argon gas and oxygen gas have positive charges accumulated on the substrate in order to prevent the phenomenon that the entire substrate is positively charged (so-called charge-up) due to the accumulation of positive ions emitted from the ion gun on the substrate. It is also used as a neutralizer that electrically neutralizes the gas.
  • the ion source As the ion source, Kaufman type (filament), hollow cathode type, RF type, bucket type, Duoplasmatron type, etc. can be applied.
  • the molecules of the film-forming material evaporating from a plurality of evaporation sources can be pressed against the substrate 104, and a film having high adhesion and denseness can be formed on the substrate.
  • a film can be formed on 104.
  • the IAD ion source 107 is installed at the bottom of the chamber 102 so as to face the substrate 104, it may be installed at a position deviated from the facing axis.
  • an ion beam having an acceleration voltage of 100 to 2000 V and an ion beam having a current density of 1 to 120 ⁇ A / cm 2 or an ion beam having an acceleration voltage of 500 to 1500 V and a current density of 1 to 120 ⁇ A / cm 2 are used.
  • the irradiation time of the ion beam can be, for example, 1 to 800 seconds, and the number of particles of the ion beam can be, for example, 1 ⁇ 10 13 to 5 ⁇ 10 17 pieces / cm 2 .
  • the ion beam used in the film forming step can be an oxygen ion beam, an argon ion beam, or an ion beam of a mixed gas of oxygen and argon.
  • the amount of gas introduced is 5 sccm or more.
  • the amount of oxygen introduced is preferably in the range of 30 to 60 sccm.
  • “Sccm” is an abbreviation for standard cc / min, and is a unit indicating how many cc flowed per minute at 1 atm (atmospheric pressure 10 13 hPa) and 0 ° C.
  • the monitor system (not shown) is a vacuum.
  • the monitor system also includes a quartz layer thickness monitor, and can monitor the physical layer thickness of the layer formed on the substrate 104.
  • This monitor system also functions as a control unit that controls ON / OFF switching of a plurality of evaporation sources 105, ON / OFF switching of the IAD ion source 107, and the like according to the monitoring result of the layer.
  • sputtering method For the film formation by the sputtering method, bipolar sputtering, magnetron sputtering, dual magnetron sputtering (DMS) using an intermediate frequency region, ion beam sputtering, ECR sputtering and the like can be used alone or in combination of two or more. Further, the target application method is appropriately selected according to the target type, and either DC (direct current) sputtering or RF (radio frequency) sputtering may be used.
  • DC direct current
  • RF radio frequency
  • the sputtering method may be multiple simultaneous sputtering using a plurality of sputtering targets.
  • the method for producing these sputtering targets and the method for producing a thin film using these sputtering targets for example, JP-A-2000-160331, JP-A-2004-068109, and JP-A-2013-047361. Etc. may be referred to as appropriate.
  • the protective layer according to the present invention can be formed, for example, according to the following method.
  • the substrate 2 applicable to the present invention is not particularly limited, and is preferably made of, for example, an inorganic material, an organic material, or a combination thereof.
  • the inorganic material include glass, fused silica glass, synthetic quartz glass, silicon, chalcogenide and the like.
  • the organic material include cycloolefin polymer (COP), cycloolefin copolymer (COC), polymethylmethacrylate resin (PMMA), polycarbonate resin (PC), polypropylene (PP), polyethylene (PE) and the like.
  • Examples of the ultraviolet curable resin include radical polymerization type acrylate resin, urethane acrylate, polyester acrylate, polybutadiene acrylate, epoxy acrylate, silicon acrylate, amino resin acrylate, en-thiol resin, cationic polymerization type vinyl ether resin, and alicyclic epoxy resin. , Glycidyl ether epoxy resin, urethane vinyl ether, polyester vinyl ether and the like, and examples of the thermosetting resin include epoxy resin, phenol resin, unsaturated polyester resin, urea resin, melamine resin, silicon resin, polyurethane and the like.
  • the substrate 2 may have a film made of an organic material formed on an inorganic material such as glass.
  • At least one reflectance adjusting layer unit U is provided between the substrate and the hydrophilic layer, and the average light reflectance in the wavelength range of 450 to 780 nm can be set to 3.0% or less. This is a preferred form.
  • FIG. 5 is a cross-sectional view showing another example of the basic configuration of the hydrophilic membrane of the present invention (Embodiment 2).
  • the hydrophilic film 1 shown in FIG. 5 is provided with a reflectance control layer unit U having an average light reflectance in the wavelength range of 450 to 780 nm of 3.0% or less on the substrate 2, and hydrophilicity is provided on the reflectance control layer unit U.
  • the layer 3 is formed, and the protective layer 4 is provided on the upper layer side of the hydrophilic layer 3.
  • At least one protective layer 4 is placed on the upper layer side of the hydrophilic layer 3 formed by the wet film forming method so that the layer thickness is 10 nm or less in terms of optical layer thickness.
  • the basic configuration is, but more specifically, the following layer arrangement can be mentioned.
  • the reflectance control layer unit U shown in FIG. 5 is at least low with the first reflectance adjusting layer unit 5 composed of at least one low refractive index layer and at least one high refractive index layer.
  • the second reflectance adjusting layer unit 6 including the refractive index layer, the high refractive index layer and the sodium-containing layer is provided in this order, and the first reflectance adjusting layer unit 5 is located at the farthest position from the substrate.
  • the layer is a photocatalyst layer containing a metal oxide having a photocatalyst function, for example, TiO 2.
  • FIG. 6 is a cross-sectional view (embodiment 3) showing an example of another configuration of the hydrophilic film 1 of the present invention.
  • the configuration shown in FIG. 6 shows an example in which the reflectance control layer unit U shown in FIG. 5 is composed of a first reflectance adjusting layer unit 5 and a second reflectance adjusting layer unit 6.
  • FIG. 7 is a cross-sectional view showing an example of a specific configuration of the first reflectance adjusting layer unit constituting the hydrophilic film 1 described in FIG.
  • the first reflectance adjusting layer unit 5 shown in FIG. 7 is composed of the following first low refractive index layer 11A, high refractive index layer 12, second low refractive index layer 11B, and photocatalyst layer 13. There is.
  • the first low refractive index layer and the second low refractive index layer according to the present invention are composed of a material having a refractive index of less than 1.7, and in the present invention, the layer may contain SiO 2 as a main component. preferable. However, it is also preferable to contain other metal oxides, and it is also preferable from the viewpoint of light reflectance that it is a mixture of SiO 2 and a part of Al 2 O 3 or Mg F 2.
  • the high refractive index layer is composed of a material having a refractive index of 1.7 or more, for example, a mixture of Ta oxide and Ti oxide, Ti oxide, Ta oxide, and the like. It is preferably a mixture of La oxide and Ti oxide.
  • the metal oxide used for the high refractive index layer preferably has a refractive index of 1.9 or more.
  • Ta 2 O 5 or TiO 2 is preferable, and Ta 2 O 5 is more preferable.
  • the thickness of the first reflectance adjusting layer unit composed of the high refractive index layer and the low refractive index layer is not particularly limited, but may be 500 nm or less from the viewpoint of antireflection performance. It is preferably and more preferably in the range of 50 to 500 nm. When the thickness is 50 nm or more, the optical characteristics of antireflection can be exhibited, and when the thickness is 500 nm or less, the error sensitivity is lowered and the good quality rate of the spectral characteristics of the lens can be improved.
  • Photocatalyst layer 13 In the first reflectance adjusting layer unit 5 according to the present invention, it is preferable to provide a photocatalyst layer having a photocatalytic function as the outermost layer.
  • the photocatalytic layer according to the present invention is preferably composed of TIO 2 as a metal oxide having a photocatalytic function, has a high refractive index, and is preferable in that the light reflectance of the dielectric multilayer film can be reduced. ..
  • the "photocatalytic function" in the present invention means the organic substance decomposition effect by the photocatalyst in the present invention. This is because when the photocatalytic TiO 2 is irradiated with ultraviolet light, active oxygen and hydroxyl radical ( ⁇ OH radical) are generated after electrons are emitted, and organic substances are decomposed by the strong oxidizing power of the active oxygen and hydroxyl radical ( ⁇ OH radical). be.
  • ⁇ OH radical active oxygen and hydroxyl radical
  • ⁇ OH radical active oxygen and hydroxyl radical
  • Whether or not it has a photocatalytic effect is determined by, for example, in an environment of 20 ° C. and 80% RH, a sample colored with a pen is irradiated with ultraviolet light with an integrated light amount of 20 J, and the color change of the pen is evaluated stepwise. You can judge by doing.
  • a specific photocatalyst performance test method for self-cleaning by irradiation with ultraviolet light, for example, a methylene blue decomposition method (ISO 10678 (2010)) and a resazurin ink decomposition method (ISO 21066 (2016)) can be mentioned.
  • a first reflectance adjusting layer unit composed of at least one low refractive index layer, at least one high refractive index layer, and a low refractive index layer on the substrate.
  • a second reflectance adjusting layer unit composed of a high refractive index layer and a sodium-containing layer is provided in this order, and the layer farthest from the substrate of the first reflectance adjusting layer unit is a metal having a photocatalytic function.
  • hydrophilic film having a structure of a photocatalyst layer containing an oxide, as will be described later, it penetrates from at least the layer below the hydrophilic layer to the upper surface of the photocatalyst layer to expose the surface of the photocatalyst layer. It is preferable to have a structure having pores in that a photocatalytic effect can be exhibited.
  • FIG. 8 shows an example of a specific configuration of the second reflectance adjusting layer unit constituting the hydrophilic film.
  • the second reflectance adjusting layer unit 6 preferably has at least a low refractive index layer, a high refractive index layer, a salt spray protection layer, and a sodium-containing layer.
  • a low refractive index layer preferably has at least a low refractive index layer, a high refractive index layer, a salt spray protection layer, and a sodium-containing layer.
  • FIG. 8 an example of the configuration in which the following constituent layers (7 layers) are laminated is shown from the lower part (board side).
  • the average light reflectance of the hydrophilic film can be obtained under desired conditions, for example. It can be controlled to 3.0% or less.
  • a first reflectance adjusting layer unit composed of a low refractive index layer and a high refractive index layer, a low refractive index layer, a high refractive index layer, a salt spray protection layer, and a sodium-containing layer.
  • the method for forming a film of the second refractive index adjusting layer unit composed of the above is not particularly limited, but a dry film forming method is preferable.
  • Examples of the dry film forming method applicable to the present invention include a vacuum vapor deposition method, an ion beam vapor deposition method, an ion plating method and the like for the vapor deposition system, and a sputtering method, an ion beam sputtering method, a magnetron sputtering method and the like for the sputtering system.
  • a vacuum vapor deposition method an ion beam vapor deposition method, an ion plating method and the like for the vapor deposition system
  • a sputtering method, an ion beam sputtering method, a magnetron sputtering method and the like for the sputtering system.
  • the ion-assisted deposit method (IAD method) or the sputtering method described above is preferable.
  • a first reflectance adjusting layer unit composed of at least one low refractive index layer and at least one high refractive index layer is provided on the substrate.
  • a second reflectance adjusting layer unit including at least a low refractive index layer, a high refractive index layer and a sodium-containing layer is provided in this order, and the layer at the position farthest from the substrate of the first reflectance adjusting layer unit is a photocatalyst.
  • One of the preferred embodiments is to use a photocatalyst layer containing a functional metal oxide, and to form pores that penetrate at least from the layer below the hydrophilic layer to the upper surface of the photocatalyst layer and expose the surface of the photocatalyst layer.
  • FIG. 9 is a flowchart showing an example of a step of manufacturing a hydrophilic film and a step of forming pores.
  • the present invention is not limited to the manufacturing method described below.
  • Step S11 A first reflectance adjusting layer unit 5 composed of a low refractive index layer, a high refractive index layer, and the like is formed on the substrate 2 by, for example, a dry film forming method.
  • a photocatalyst layer 13 is formed on the outermost surface layer of the first reflectance adjusting layer unit 5 by a dry film forming method.
  • Step S13 Next, on the photocatalyst layer 13 constituting the first reflectance adjusting layer unit 5, a second reflection composed of a low refractive index layer, a high refractive index layer, a salt spray protection layer and a sodium-containing layer by a dry film forming method.
  • the rate adjusting layer unit 6 is formed.
  • Step S14 Next, the mask 10 is formed on the second reflectance adjusting layer unit 6.
  • Examples of the mask 10 include a metal mask composed of a metal portion and an exposed portion.
  • Step S15 Next, through the mask 10, the surface side is penetrated from the outermost surface layer to the upper surface portion of the photocatalyst layer 13 by etching from the surface side to form pores 14 that expose the surface of the photocatalyst layer.
  • Step S16 Next, the mask 10 formed on the surface is removed.
  • Step S17 a hydrophilic layer 3 having an optical layer thickness of 10 nm or less is formed on the second reflectance adjusting layer unit 6 in which the pores 14 are formed by using a wet film forming method, for example, a spin coating method.
  • a protective layer having a thickness of 10 nm or less is formed on the hydrophilic layer 3 by using a dry film forming method, for example, an IAD method.
  • FIG. 10 is a cross-sectional view (embodiment 5) showing an example of a configuration in which pores are formed in a hydrophilic film to expose a photocatalyst layer.
  • a first reflectance adjusting layer unit 5 having a photocatalyst layer 13 on the uppermost layer is formed on the substrate 2, and then a second is formed on the first reflectance adjusting layer unit 5.
  • the reflectance adjusting layer unit 6 is laminated, and the hydrophilic layer 3 and the protective layer 4 are laminated thereon to form the hydrophilic film 1 shown in FIG.
  • the second reflectance adjusting layer unit 6 After the second reflectance adjusting layer unit 6 is laminated, it penetrates from the outermost surface layer to the upper surface of the photocatalyst layer 13 by reactive etching treatment or physical etching treatment using a mask according to the following method.
  • the pores 10 that expose the surface of the photocatalyst layer are formed, and finally, the hydrophilic layer 3 and the protective layer 4 are laminated to prepare a hydrophilic film.
  • FIG. 11 is a manufacturing flow chart showing an example of a method of forming pores in a hydrophilic membrane.
  • step 1 of FIG. 11 the hydrophilic film 1 having a structure in which the second reflectance adjusting layer unit 6 described with reference to FIG. 10 is laminated is prepared.
  • the metal mask 10 is composed of a metal portion and an exposed portion.
  • the layer thickness of the metal mask 10 is in the range of 1 to 30 nm. Although it depends on the film forming conditions, for example, when the metal mask 10 is formed into a film so that the layer thickness is 2 nm by using a thin film deposition method, it becomes particulate.
  • the metal mask 10 when a metal mask 10 is formed so that the layer thickness is 12 to 15 nm by using a thin-film deposition method, the metal mask 10 tends to have a leaf vein shape. Further, for example, when a film is formed so that the layer thickness is 10 nm by using a sputtering method, the metal mask 10 tends to have a porous shape.
  • the metal mask 10 is formed of, for example, Ag, Al, or the like, and is particularly silver, and the film formation temperature is controlled within the range of 20 ° C. to 400 ° C. and the thickness is controlled within the range of 1 to 30 nm. It is preferable from the viewpoint of controlling the shape of the pores.
  • step 3 the etching apparatus E is used to penetrate from the outermost surface layer to the upper surface of the photocatalyst layer 13 by etching to form pores 14 that expose the surface of the photocatalyst layer.
  • step 3 for etching, a reactive dry etching using an etching apparatus E or an apparatus in which an etching gas is introduced into an IAD vapor deposition apparatus is used.
  • the pore forming step for example, CHF 3 , CF 4 , COF 2 and SF 6 are used as the etching gas.
  • a plurality of pores 14 are formed by etching from the outermost surface layer to the upper surface of the photocatalyst layer 13 with a predetermined size to expose the surface of the photocatalyst layer 13. That is, the constituent layer corresponding to the exposed portion of the metal mask 10 is etched to form the pores 14, and the surface of the photocatalyst layer 13 is partially exposed.
  • the metal mask 10 is removed. Specifically, the metal mask 10 is removed by wet etching using chemicals such as acetic acid, iodine, and potassium iodide. Further, the metal mask 10 may be removed by dry etching using, for example, Ar or O 2 as an etching gas.
  • the wet film forming apparatus W is used on the first reflectance adjusting layer unit 5 and the second reflectance adjusting layer unit 6 in which the pores 14 are formed, and the optical layer thickness is reduced to 10 nm or less. As such, it forms a hydrophilic layer.
  • the hydrophilic layer forming component is applied on the second reflectance adjusting layer unit 6 other than the pores 14, and hardly penetrates into the pores 14.
  • a protective layer is formed on the second reflectance adjusting layer unit 6 on which the hydrophilic layer is formed so that the thickness of the optical layer is 10 nm or less by using the dry film forming apparatus D.
  • the protective layer forming component is applied on the hydrophilic layer other than the pore 14, and hardly reaches the inside of the pore 14.
  • a hydrophilic film 1 having a plurality of pores 14 and having an arithmetic mean roughness Ra of 3 nm or more can be obtained.
  • the method for producing a hydrophilic film and the method for forming pores after forming each constituent layer, a plurality of layers for penetrating from the outermost surface layer to the upper surface of the photocatalyst layer 13 to exhibit the photocatalytic function of the photocatalyst layer.
  • a plurality of layers for penetrating from the outermost surface layer to the upper surface of the photocatalyst layer 13 to exhibit the photocatalytic function of the photocatalyst layer By forming the pores 14, it is possible to achieve both superhydrophilicity and photocatalytic function.
  • the hydrophilic film of the present invention is a hydrophilic film having low light reflectance, hydrophilicity and photocatalytic properties, and also having excellent properties such as salt water resistance and scratch resistance.
  • the hydrophilic film of the present invention is used.
  • the optical member is preferably a lens, an antibacterial cover member, an antifungal coating member or a mirror, for example, an in-vehicle lens, a communication lens, or an endoscope.
  • a white plate glass substrate (refractive index: 1.523) manufactured by SCHOTT was prepared.
  • First Reflectance Adjusting Layer Unit 5 On a white plate glass substrate, by the following vacuum vapor deposition method, as shown in FIG. 7, from the substrate 2 side. 1) First low refractive index layer 11A (SiO 2 , layer thickness: 22 nm), 2) High refractive index layer 12 (Ta 2 O 5 + TiO 2 , 18 nm), 3) First low refractive index layer 11B (SiO 2 , layer thickness: 33 nm), 4) Photocatalyst layer 13 (TiO 2 , layer thickness: 112 nm) Was sequentially laminated to form the first reflection adjusting layer unit 5.
  • the specific film formation conditions are as follows.
  • Formation of First Reflectance Adjusting Layer Unit 5 ⁇ Formation of the first low refractive index layer 11A> Film formation material for the first low refractive index layer 11A: SiO 2 (Canon Optron trade name SiO 2 )
  • SiO 2 Canon Optron trade name SiO 2
  • the above substrate is installed in an IAD vacuum vapor deposition apparatus, SiO 2 is loaded as a film forming material in the first evaporation source, vapor deposition is carried out at a film forming speed of 3 ⁇ / sec, and the first low refractive index layer 11A having a layer thickness of 22 nm. Formed.
  • IAD conditions an acceleration voltage 1000V, acceleration current 1000 mA, suppressor voltage 500V, neutralization current 1500 mA, IAD introduced gas was carried out O 2 50 sccm, Ar gas 0 sccm, under the condition of the neutral gas Ar10sccm.
  • High-refractive index layer 12 film-forming material Ta 2 O 5- TiO 2 (Canon Optron trade name OA-600)
  • the film forming material is loaded into the second evaporation source of the IAD vacuum vapor deposition apparatus, vapor deposition is performed at a film forming rate of 4 ⁇ / sec, and a high refractive index layer 12 having a layer thickness of 22 nm is formed on the first low refractive index layer 11A. Formed.
  • the high refractive index layer 12 was formed by the IAD method in the same manner as described above under heating conditions of 370 ° C.
  • IAD conditions an acceleration voltage 1000V, acceleration current 1000 mA, suppressor voltage 500V, neutralization current 1500 mA, IAD introduced gas was carried out O 2 50 sccm, Ar gas 0 sccm, under the condition of the neutral gas Ar10sccm. At this time, O 2 gas is introduced from the auto pressure controller (hereinafter abbreviated as “APC”) so that the chamber pressure becomes 2 ⁇ 10 ⁇ 2 Pa by controlling the gas.
  • APC auto pressure controller
  • Film formation material for the second low refractive index layer 11B SiO 2 (Canon Optron trade name SiO 2 )
  • SiO 2 Canon Optron trade name SiO 2
  • the above substrate is installed in an IAD vacuum vapor deposition apparatus, SiO 2 is loaded as a film forming material in the first evaporation source, vapor deposition is carried out at a film forming speed of 3 ⁇ / sec, and a second low refractive index layer 11B having a layer thickness of 29 nm. Formed.
  • IAD conditions an acceleration voltage 1000V, acceleration current 1000 mA, suppressor voltage 500V, neutralization current 1500 mA, IAD introduced gas was carried out O 2 50 sccm, Ar gas 0 sccm, under the condition of the neutral gas Ar10sccm.
  • Film formation material for photocatalyst layer 13 TiO 2 (Fuji Titanium Industry Co., Ltd. product name TOP (Ti 3 O 5 ))
  • the substrate is installed in an IAD vacuum vapor deposition apparatus, the film forming material is loaded into a third evaporation source, vapor deposition is carried out at a film forming rate of 2 ⁇ / sec, and the thickness is 112 nm on the second low refractive index layer 11B.
  • a photocatalyst layer was formed.
  • the photocatalyst layer was similarly formed by the IAD method and heating conditions at 370 ° C.
  • IAD conditions acceleration voltage 300 V, accelerating current 300 mA, suppressor voltage 1000V, neutralization current 600 mA, IAD introduced gas was carried out by O 2 50 sccm, Ar gas 10 sccm, the neutral gas Ar10sccm conditions. At this time, gas was controlled and O 2 gas was introduced from APC so that the chamber pressure became 3 ⁇ 10 ⁇ 2 Pa.
  • the second reflectance adjusting layer unit 6 was formed on the first reflectance adjusting layer unit 5 by the following method according to the following method.
  • Film formation material for low refractive index layer SiO 2 (Canon Optron trade name SiO 2 )
  • SiO 2 Canon Optron trade name SiO 2
  • the substrate formed up to the first reflectance adjusting layer unit 5 is installed in the IAD vacuum vapor deposition apparatus, the film forming material is loaded into the second evaporation source, and the film is deposited at a film forming speed of 3 ⁇ / sec, and the layer thickness is 14 nm.
  • the first low refractive index layer 7A was formed.
  • IAD conditions an acceleration voltage 1000V, acceleration current 1000 mA, suppressor voltage 500V, neutralization current 1500 mA, IAD introduced gas was carried out O 2 50 sccm, Ar gas 0 sccm, under the condition of the neutral gas Ar10sccm. This was done under 50 ° C. heating conditions.
  • the substrate formed up to the first low refractive index layer 7A is installed in an IAD vacuum vapor deposition apparatus, the film forming material of the first sodium-containing layer 9A is loaded into the first evaporation source, and vapor deposition is performed at a film forming rate of 3 ⁇ / sec. Then, a first sodium-containing layer 9A having a layer thickness of 14 nm and a Na content of 5% by mass was formed.
  • IAD conditions an acceleration voltage 1000V, acceleration current 1000 mA, suppressor voltage 500V, neutralization current 1500 mA, IAD introduced gas is O 2 50 sccm, Ar gas 0 sccm, under the condition of the neutral gas Ar10sccm, was carried out by heating conditions 50 ° C..
  • Film formation material for high refractive index layer 8 TiO 2 (Fuji Titanium Industry Co., Ltd. product name TOP (Ti 3 O 5 ))
  • the substrate formed up to the first sodium-containing layer 9A is installed in a vacuum vapor deposition apparatus, the film-forming material is loaded into the third evaporation source, vapor deposition is carried out at a film-forming rate of 2 ⁇ / sec, and the film is deposited on the first sodium-containing layer 9A.
  • a high refractive index layer 8 having a thickness of 1 nm was formed.
  • the formation of the high refractive index layer was similarly carried out by the IAD method and heating conditions at 370 ° C.
  • IAD conditions acceleration voltage 300 V, accelerating current 300 mA, suppressor voltage 1000V, neutralization current 600 mA, IAD introduced gas was carried out by O 2 50 sccm, Ar gas 10 sccm, the neutral gas Ar10sccm conditions. At this time, gas was controlled and O 2 gas was introduced from APC so that the chamber pressure became 3 ⁇ 10 ⁇ 2 Pa.
  • Film formation material of the second sodium-containing layer 9B Toshima Manufacturing Co., Ltd., trade name: SiO 2- Na 2 O (Na content: 10% by mass)
  • the substrate formed up to the high refractive index layer 8 is installed in an IAD vacuum vapor deposition apparatus, the film forming material is loaded into the first evaporation source, and the film is deposited at a film forming rate of 3 ⁇ / sec.
  • the layer thickness is 29 nm, and Na.
  • a secondary sodium-containing layer 9B having a content of 10% by mass was formed.
  • IAD conditions an acceleration voltage 1000V, acceleration current 1000 mA, suppressor voltage 500V, neutralization current 1500 mA, IAD introduced gas is O 2 50 sccm, Ar gas 0 sccm, under the condition of the neutral gas Ar10sccm, was carried out by heating conditions 50 ° C..
  • Film formation material for the second low refractive index layer 7B SiO 2 (Canon Optron trade name SiO 2 )
  • the substrate formed up to the second sodium-containing layer 9B is installed in an IAD vacuum vapor deposition apparatus, the film forming material is loaded into the second evaporation source, and the film is vapor-deposited at a film forming rate of 3 ⁇ / sec.
  • the low refractive index layer 7B was formed.
  • IAD conditions an acceleration voltage 1000V, acceleration current 1000 mA, suppressor voltage 500V, neutralization current 1500 mA, IAD introduced gas was carried out O 2 50 sccm, Ar gas 0 sccm, under the condition of the neutral gas Ar10sccm. This was done under 50 ° C. heating conditions.
  • Film formation material for salt spray protective layer 15 TiO 2 (Fuji Titanium Industry Co., Ltd. product name TOP (Ti 3 O 5 )) The film forming material is loaded into the second evaporation source of the IAD vacuum vapor deposition apparatus, vapor deposition is performed at a film forming rate of 4 ⁇ / sec, and a salt spray protective layer 15 having a layer thickness of 1 nm is formed on the second low refractive index layer 7B. Formed.
  • the salt spray protective layer 15 was formed by the IAD method under 370 ° C. heating conditions in the same manner as described above.
  • IAD conditions an acceleration voltage 1000V, acceleration current 1000 mA, suppressor voltage 500V, neutralization current 1500 mA, IAD introduced gas was carried out O 2 50 sccm, Ar gas 0 sccm, under the condition of the neutral gas Ar10sccm. At this time, O 2 gas is introduced from the auto pressure controller (hereinafter abbreviated as “APC”) so that the chamber pressure becomes 2 ⁇ 10 ⁇ 2 Pa by controlling the gas.
  • APC auto pressure controller
  • tertiary sodium-containing layer 9C Film formation material for the tertiary sodium-containing layer 9C: Toshima Manufacturing Co., Ltd., trade name: SiO 2- Na 2 O (Na content: 10% by mass)
  • the substrate formed up to the salt spray protective layer 15 is installed in an IAD vacuum vapor deposition apparatus, the film forming material is loaded into the first evaporation source, and vapor deposition is carried out at a film forming rate of 3 ⁇ / sec.
  • a tertiary sodium-containing layer 9C having a content of 10% by mass was formed.
  • IAD conditions an acceleration voltage 1000V, acceleration current 1000 mA, suppressor voltage 500V, neutralization current 1500 mA, IAD introduced gas is O 2 50 sccm, Ar gas 0 sccm, under the condition of the neutral gas Ar10sccm, was carried out by heating conditions 50 ° C..
  • hydrophilic film 2 In the preparation of the hydrophilic film 1, the hydrophilic layer was formed by immersing the Excelpia diluted solution in a sponge instead of the spin coating method, and then applying the hydrophilic layer onto the second reflectance layering unit by a hand coating method.
  • the hydrophilic membrane 2 was produced in the same manner except for the above.
  • hydrophilic membrane 3 In the preparation of the hydrophilic film 1, the hydrophilic film 3 was prepared in the same manner except that a protective layer was further formed on the hydrophilic layer according to the following method.
  • a protective layer was formed on the hydrophilic layer according to the following method.
  • hydrophilic film 4 In the preparation of the hydrophilic film 3, the formation of the hydrophilic layer is performed by using a known dip coater (wet film formation 3) for the Excelpia diluted solution instead of the spin coating method (wet film formation 1). The hydrophilic film 4 was produced in the same manner except that it was applied on the reflectance layer shaping unit.
  • hydrophilic film 5 In the production of the hydrophilic film 3, the hydrophilic film 5 was produced in the same manner except that the film forming conditions (deposition rate, film formation time) were appropriately adjusted and the layer thickness of the protective layer was changed to 20 nm. ..
  • hydrophilic membrane 6 In the preparation of the hydrophilic membrane 3, the hydrophilic membrane 6 was prepared in the same manner except that the sodium content in the hydrophilic layer was changed to 0.02 atm%.
  • hydrophilic film 7 In the preparation of the hydrophilic membrane 3, the hydrophilic membrane 7 was prepared in the same manner except that the sodium content in the hydrophilic layer was changed to 5.0 atm%.
  • hydrophilic film 8 In the production of the hydrophilic film 3, the hydrophilic film 8 was produced in the same manner except that the firing temperature at the time of forming the hydrophilic layer was changed from 370 ° C to 100 ° C.
  • hydrophilic film 9 In the production of the hydrophilic film 7, the hydrophilic film 9 was produced in the same manner except that the film formation temperature of the protective layer was changed from 370 ° C to 80 ° C.
  • hydrophilic film 10 In the production of the hydrophilic film 3, the hydrophilic film 10 was produced in the same manner except that the film-forming material of the protective layer was changed to HP-3 shown below.
  • hydrophilic film 11 In the production of the hydrophilic film 3, the hydrophilic film 11 was produced in the same manner except that the second reflectance layer-forming unit was not formed.
  • hydrophilic film 12 In the production of the hydrophilic film 3, the sodium-containing layer 9A, which is formed by using a single SiO 2 (for example, a trade name of Canon Optron, trade name: SiO 2) and constitutes a second reflectance stratification unit, The hydrophilic membrane 12 was prepared in the same manner except that 9B and 9C were not formed.
  • SiO 2 for example, a trade name of Canon Optron, trade name: SiO 2
  • hydrophilic film 13 In the preparation of the hydrophilic film 3, the hydrophilic film 13 was prepared in the same manner except that the pores were formed according to the following method.
  • pores were formed according to the following method after the formation of the second reflectance layer-forming unit and before the formation of the hydrophilic layer.
  • the detailed pore formation conditions are as follows.
  • step 2 described in FIG. 11 a film forming apparatus (BMC-800T, manufactured by Syncron Co., Ltd.) was used for Ag film formation, and the film was formed under the following conditions to form an Ag mask.
  • BMC-800T manufactured by Syncron Co., Ltd.
  • step 3 described in FIG. 11 an etching apparatus (CE-300I) (manufactured by ULVAC, Inc.) was used for etching, and a film was formed under the following conditions. By changing the etching time, the width length of the pores was set to 25 to 50 ⁇ m. The depth of the pores 14 was set as a condition for exposing the interface of the photocatalyst layer 13.
  • hydrophilic film 14 In the preparation of the hydrophilic film 13, the hydrophilic film 14 was produced in the same manner except that the width of the silver mask at the time of forming the pores was halved and the width length of the pores 14 was 0.5 ⁇ m. ..
  • hydrophilic film 15 In the preparation of the hydrophilic film 12, the hydrophilic film 15 was prepared in the same manner except that the hydrophilic layer and the protective layer were not formed.
  • hydrophilic film 16 In the production of the hydrophilic film 1, the hydrophilic film 16 was produced in the same manner except that the formation of the hydrophilic layer was changed to the dry vapor deposition method used in the formation of the hydrophilic film 3.
  • hydrophilic film 17 In the preparation of the hydrophilic film 1, the hydrophilic film 17 was prepared in the same manner except that the Na content of the hydrophilic layer was 2.0 atm% and the layer thickness was changed to 140 nm.
  • the sodium content (atm%) in the hydrophilic layer used to prepare each of the above hydrophilic films was measured by the following method.
  • a single layer of the hydrophilic layer for measuring the sodium content having a layer thickness of 200 nm was formed, and this was used as a sample for measuring the sodium content in the hydrophilic layer, which is described below.
  • the sodium content was measured by the XPS composition analysis shown.
  • the contact angle measuring device G-1 manufactured by Elma
  • 10 ⁇ L of pure water was dropped on the surface of the hydrophilic film in an environment of 23 ° C. and 50% RH, and the static contact angle 5 seconds after the drop was measured. This was defined as the contact angle A.
  • the measured contact angle A was ranked according to the following criteria.
  • ⁇ Contact angle A is less than 10 ° ⁇ : Contact angle A is 10 ° or more and less than 30 ° ⁇ : Contact angle A is 30 ° or more and less than 60 ° ⁇ : Contact angle A is , 60 ° or more.
  • Average light reflectance is less than 3.0% ⁇ : Average light reflectance is 3.0% or more and less than 5.0% ⁇ : Average light reflectance is 5.0% or more and 8.0% Less than ⁇ : Average light reflectance is 8.0% or more
  • ⁇ Contact angle B is maintained at less than 30 ° even if it exceeds 1000 hours ⁇ : Contact angle B is maintained at less than 30 ° after 500 hours or more and less than 1000 hours ⁇ : Contact angle B is maintained at 100 hours or more and less than 500 hours Maintain less than 30 ° ⁇ : The time that the contact angle B can maintain 30 ° is less than 100 hours.
  • ⁇ Treatment 2 Cold impact treatment (heat cycle resistance)>
  • For each hydrophilic membrane after maintaining at 65 ° C. for 4 hours as a high temperature environment, lowering the temperature from 65 ° C. to -15 ° C. under the condition of 1 ° C./1 minute, and then maintaining at -15 ° C. for 4 hours as an extremely low temperature environment. The temperature was raised to 65 ° C. under the condition of 1 ° C./1 minute, and this was set as one cycle, and repeated from 0 to 6 cycles.
  • the contact angle C was measured for each cycle by the same method as described above, the number of cycles capable of maintaining the contact angle C of 15 ° or less was determined, and the heat cycle resistance was evaluated according to the following criteria.
  • ⁇ Contact angle C was 20 ° or less even in 6 cycles
  • ⁇ Contact angle C was 20 ° or less in 3 cycles or more and 5 cycles or less
  • ⁇ Contact angle C was 20 in 1 cycle or more and 2 cycles or less It was less than ° ⁇ : The contact angle C exceeded 20 ° even in one cycle.
  • ⁇ Contact angle D is less than 10 ° ⁇ : Contact angle D is 10 ° or more and less than 30 ° ⁇ : Contact angle D is 30 ° or more and less than 60 ° ⁇ : Contact angle D is , 60 ° or more.
  • Average light reflectance is less than 3.0% ⁇ : Average light reflectance is 3.0% or more and less than 5.0% ⁇ : Average light reflectance is 5.0% or more and 8.0% Less than ⁇ : Average light reflectance is 8.0% or more
  • each hydrophilic film is marked with magic ink (The Visualiser manufactured by Inkintilegen), stored for 10 hours in an environment of 85 ° C. and 85% RH, and then the accumulated ultraviolet light amount in an environment of 20 ° C. and 80% RH. As a result, if the magic ink on the surface of the hydrophilic film disappeared by irradiating with ultraviolet rays under the condition of 20J, it was determined that the photocatalytic function was "existent".
  • magic ink The Visualiser manufactured by Inkintilegen
  • the hydrophilic film of the present invention has excellent optical performance, heat cycle resistance and high temperature and high humidity resistance, as well as scratch resistance on the surface, as compared with the comparative examples. It can be seen that it has excellent characteristics. Further, it was confirmed that the hydrophilic films 12 and 13 having pores penetrating from the surface portion to the upper surface portion of the photocatalyst layer had an excellent photocatalyst function.
  • the hydrophilic film produced by the method for producing a hydrophilic film of the present invention is excellent in durability, scratch resistance, and antireflection function, and can be used for optical members such as lenses, antibacterial cover members, antifungal coating members, and mirrors. It is preferable to apply.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Laminated Bodies (AREA)
PCT/JP2021/021486 2020-06-23 2021-06-07 親水性膜の製造方法、親水性膜及び光学部材 Ceased WO2021261225A1 (ja)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2023124219A (ja) * 2022-02-25 2023-09-06 コニカミノルタ株式会社 機能性膜及び機能性膜の製造方法
WO2024195370A1 (ja) * 2023-03-23 2024-09-26 コニカミノルタ株式会社 機能性膜及び機能性膜の製造方法
WO2025126699A1 (ja) * 2023-12-11 2025-06-19 コニカミノルタ株式会社 機能性膜、機能性膜の製造方法及び積層体

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000289134A (ja) * 1999-02-01 2000-10-17 Nippon Sheet Glass Co Ltd 親水性表面を有する物品およびその製造方法
JP2017062371A (ja) * 2015-09-25 2017-03-30 リコーイメージング株式会社 反射防止膜を有する光学部材及びその反射防止膜の製造方法
WO2018190408A1 (ja) * 2017-04-14 2018-10-18 Hoya株式会社 光学素子及び光学薄膜
JP2019151076A (ja) * 2018-03-06 2019-09-12 大日本印刷株式会社 離型性積層体、並びに、それを用いた転写シート、工程用シート及び物品
WO2019240040A1 (ja) * 2018-06-14 2019-12-19 コニカミノルタ株式会社 光学素子の製造方法及び光学素子

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6830785B1 (en) * 1995-03-20 2004-12-14 Toto Ltd. Method for photocatalytically rendering a surface of a substrate superhydrophilic, a substrate with a superhydrophilic photocatalytic surface, and method of making thereof
KR100342150B1 (ko) * 1995-03-20 2002-10-25 도토기키 가부시키가이샤 기재의표면을광촉매적으로초친수성이되게하는방법,초친수성의광촉매성표면을갖는기재및그의제조방법
EP0887179B1 (en) * 1996-12-09 2005-12-21 Nippon Sheet Glass Co., Ltd. Non-fogging article and process for the production thereof
JP3700358B2 (ja) * 1996-12-18 2005-09-28 日本板硝子株式会社 防曇防汚ガラス物品
JP2000226234A (ja) * 1998-12-03 2000-08-15 Toto Ltd 親水性部材
US20010026859A1 (en) * 1999-11-30 2001-10-04 Toru Nakamura Functional films, their use, articles having the films and processes for producing these
JP2010167744A (ja) * 2009-01-26 2010-08-05 Sumitomo Osaka Cement Co Ltd 耐指紋性に優れた製品およびその製造方法
JP5903848B2 (ja) * 2011-11-25 2016-04-13 三菱マテリアル株式会社 反射防止膜付きガラス基材
KR101507208B1 (ko) * 2012-11-07 2015-04-07 (주)엘지하우시스 실록산 화합물을 포함하는 초친수성 반사방지 코팅 조성물, 이를 이용한 초친수성 반사방지 필름 및 이의 제조방법
CN108463745B (zh) * 2015-09-29 2019-12-06 富士胶片株式会社 亲水性多层膜及其制造方法和摄像系统
JP6794633B2 (ja) * 2016-02-23 2020-12-02 東洋紡株式会社 積層フィルム
CN109641431A (zh) * 2016-08-26 2019-04-16 三井化学株式会社 防反射性层叠体
CN120630360A (zh) * 2017-04-12 2025-09-12 富士胶片株式会社 防反射膜及光学部件
CN110790294A (zh) * 2019-11-22 2020-02-14 华南理工大学 一种NaAl3(SO4)2(OH)6超亲水薄膜及其制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000289134A (ja) * 1999-02-01 2000-10-17 Nippon Sheet Glass Co Ltd 親水性表面を有する物品およびその製造方法
JP2017062371A (ja) * 2015-09-25 2017-03-30 リコーイメージング株式会社 反射防止膜を有する光学部材及びその反射防止膜の製造方法
WO2018190408A1 (ja) * 2017-04-14 2018-10-18 Hoya株式会社 光学素子及び光学薄膜
JP2019151076A (ja) * 2018-03-06 2019-09-12 大日本印刷株式会社 離型性積層体、並びに、それを用いた転写シート、工程用シート及び物品
WO2019240040A1 (ja) * 2018-06-14 2019-12-19 コニカミノルタ株式会社 光学素子の製造方法及び光学素子

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2023124219A (ja) * 2022-02-25 2023-09-06 コニカミノルタ株式会社 機能性膜及び機能性膜の製造方法
WO2024195370A1 (ja) * 2023-03-23 2024-09-26 コニカミノルタ株式会社 機能性膜及び機能性膜の製造方法
WO2025126699A1 (ja) * 2023-12-11 2025-06-19 コニカミノルタ株式会社 機能性膜、機能性膜の製造方法及び積層体

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