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WO2021199466A1 - Élément optique - Google Patents

Élément optique Download PDF

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Publication number
WO2021199466A1
WO2021199466A1 PCT/JP2020/037634 JP2020037634W WO2021199466A1 WO 2021199466 A1 WO2021199466 A1 WO 2021199466A1 JP 2020037634 W JP2020037634 W JP 2020037634W WO 2021199466 A1 WO2021199466 A1 WO 2021199466A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
refractive index
optical member
less
antireflection film
Prior art date
Application number
PCT/JP2020/037634
Other languages
English (en)
Japanese (ja)
Inventor
紗友里 若村
和俊 迎
加本　貴則
Original Assignee
日本電産株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日本電産株式会社 filed Critical 日本電産株式会社
Priority to JP2022511503A priority Critical patent/JP7468624B2/ja
Priority to CN202080098504.5A priority patent/CN115298576A/zh
Publication of WO2021199466A1 publication Critical patent/WO2021199466A1/fr

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Classifications

    • 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
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • 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
    • G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films

Definitions

  • the present invention relates to an optical member.
  • the optical member includes, for example, a translucent member and an antireflection film that covers the translucent member.
  • the antireflection film reduces the reflectance of the optical member.
  • optical members are required to have anti-fog properties.
  • an optical member having anti-fog property an optical member including a translucent member, an antireflection film covering the translucent member, and a hydrophilic film covering the antireflection film has been studied. When water adheres to the surface of the optical member provided with the hydrophilic film, the water wets and spreads without forming water droplets. Therefore, the optical member provided with the hydrophilic film is excellent in anti-fog property. Twice
  • a lens with a hydrophilic antireflection film having a hydrophilic antireflection film in which at least a base film and a hydrophilic film are laminated in this order on the surface of a glass lens has been proposed (Patented).
  • Document 1 The undercoat is a single layer selected from ZrO 2 , MgF 2 , Ta 2 O 5 , Nb 2 O 5 , and Y 2 O 3 , or ZrO 2 , MgF 2 , Ta 2 O 5 , Nb 2 O 5.
  • the hydrophilic film has a single layer of titanium oxide made of at least one of TIO 2 and Ti 3 O 5 or a single layer of titanium nitride made of TiN, or at least one of the titanium oxide and the titanium nitride on the surface of the base film. It is formed of a mixed layer containing 50% or more, and has a film thickness of 1 nm or more and 30 nm or less.
  • the present invention has been made in view of the above problems, and an object of the present invention is to provide an optical member having excellent hydrophilicity and low reflectance.
  • An exemplary optical member of the present invention includes a translucent member and an antireflection film that covers the translucent member.
  • the antireflection film has a low refractive index layer and a high refractive index layer which are alternately laminated along the thickness direction.
  • the first layer located on the outermost side of the low refractive index layer and the high refractive index layer is the low refractive index layer.
  • the first layer is a single layer containing photocatalyst particles, or is a multilayer having an A layer containing photocatalyst particles and a B layer laminated inside the A layer.
  • An exemplary invention can provide an optical member with excellent hydrophilicity and low reflectance.
  • FIG. 1 is a schematic view of an example of an optical member according to the first embodiment of the present invention.
  • FIG. 2 is a schematic enlarged view showing an example of the first layer in the optical member of FIG.
  • FIG. 3 is a schematic enlarged view showing an example of the first layer different from that of FIG. 2 in the optical member of FIG.
  • FIG. 4 is a schematic view of a modified example 1 of the optical member according to the first embodiment of the present invention.
  • FIG. 5 is a graph showing the spectral reflectance of the optical member of Example 1.
  • FIG. 6 is a graph showing the spectral reflectance of the optical member of Example 2.
  • FIG. 7 is a graph showing the spectral reflectance of the optical member of Example 3.
  • FIG. 8 is a graph showing the spectral reflectance of the optical member of Example 4.
  • FIG. 9 is a graph showing the spectral reflectance of the optical member of Example 5.
  • FIG. 10 is a graph showing the spectral reflectance of the optical member of Comparative Example 1.
  • FIG. 11 is a graph showing the spectral reflectance of the optical member of Comparative Example 2.
  • FIG. 12 is a graph showing the relationship between the refractive index of the A layer simulated in the example and the reflectance of the optical member.
  • the "film thickness" of each portion of the optical member indicates the length of the optical member in the optical axis direction.
  • the “outside” of the antireflection film refers to the side far from the surface of the translucent member.
  • the “inside” of the antireflection film refers to the side of the translucent member close to the surface.
  • the "refractive index” indicates the refractive index (Nd) with respect to the d line (light having a wavelength of 588 nm). Twice
  • the optical member according to the embodiment of the present invention includes a translucent member and an antireflection film that covers the translucent member.
  • the antireflection film has a low refractive index layer and a high refractive index layer which are alternately laminated along the thickness direction.
  • the first layer located on the outermost side of the low refractive index layer and the high refractive index layer is the low refractive index layer.
  • the first layer is a single layer containing photocatalyst particles, or a multilayer having an A layer containing photocatalyst particles and a B layer laminated inside the A layer.
  • the optical member according to the present embodiment is suitable as, for example, an optical member used for an optical unit including one or more optical members (particularly, an optical unit used outdoors).
  • the optical member according to the present embodiment is particularly suitable as an optical member (hereinafter, may be referred to as a first optical member) located closest to an object among one or a plurality of lenses included in the optical unit.
  • a first optical member located closest to an object among one or a plurality of lenses included in the optical unit.
  • the optical member according to the present embodiment is usually used with the surface on the antireflection film side facing the object side.
  • the optical member according to the present embodiment is particularly suitable as a lens for a lens unit of an in-vehicle camera for monitoring the surroundings of a vehicle. Twice
  • a general antireflection film has low refractive index layers and high refractive index layers that are alternately laminated along the thickness direction.
  • the first layer located on the outermost side of the low refractive index layer and the high refractive index layer of the antireflection film is usually a low refractive index layer.
  • the general antireflection film reduces the reflectance of the optical member by generating an interference action by the above-mentioned multilayer structure.
  • the antireflection film does not cause an interference effect as designed due to the influence of the refractive index of the hydrophilic film.
  • the hydrophilic film reduces the function of the antireflection film.
  • it has been studied to achieve both improvement of hydrophilicity and reduction of reflectance by making the hydrophilic film extremely thin.
  • the hydrophilic film is made extremely thin, it is difficult to sufficiently reduce the reflectance of the optical member.
  • the extremely thin hydrophilic film has low wear resistance, its practicality as a hydrophilic film is low. Twice
  • the layer containing the photocatalyst particles (hereinafter, may be referred to as a photocatalyst layer) has excellent hydrophilicity and can be adjusted to have a refractive index relatively close to that of the low refractive index layer of the antireflection film. I paid attention to that. Then, the present inventor does not form a hydrophilic film on the antireflection film, but replaces at least a part of the first layer of the antireflection film with a photocatalyst layer to improve the hydrophilicity of the optical member. It was judged that the reflectance would decrease. The present invention is based on the above findings.
  • a part or all of the first layer is a photocatalyst layer.
  • the photocatalyst layer functions as a hydrophilic film to improve the hydrophilicity of the optical member according to the present embodiment. Further, the photocatalyst layer functions as a part of the antireflection film, so that the reflectance of the optical member according to the present embodiment can be reduced. Further, the optical member according to the present embodiment does not need to have an excessively thin photocatalyst layer. From the above, the optical member according to the present embodiment has excellent hydrophilicity and low reflectance. Twice
  • the maximum reflectance of the optical member according to the present embodiment with respect to light having a wavelength of 480 nm or more and 780 nm or less is preferably 1.5% or less, more preferably 1.0% or less.
  • the lower the above-mentioned maximum reflectance the more the occurrence of image defects called ghost phenomenon and image defects called flare phenomenon can be suppressed.
  • the lower the above-mentioned maximum reflectance the more effectively the occurrence of the ghost phenomenon can be suppressed.
  • the above-mentioned maximum reflectance is 1.5% or less, the occurrence of the ghost phenomenon can be suppressed.
  • antireflection film refers to a film having a function of adjusting the maximum reflectance of an optical member with respect to light having a wavelength of 480 nm or more and 780 nm or less to 1.5% or less. Twice
  • FIG. 1 is a schematic view of an optical member 1 which is an example of an optical member according to the present embodiment.
  • the optical member 1 includes a translucent member 2 and an antireflection film 3 that covers the translucent member 2.
  • the antireflection film 3 has a low refractive index layer 4 and a high refractive index layer 5 that are alternately laminated along the thickness direction.
  • the first layer 41 located on the outermost side (upper side in FIG. 1) of the low refractive index layer 4 and the high refractive index layer 5 is the low refractive index layer 4. Twice
  • the translucent member 2 has translucency. That is, the translucent member 2 transmits light.
  • the translucent member 2 may be transparent or translucent.
  • the translucent member 2 contains, for example, glass or resin as a main component.
  • the translucent member 2 has a function as, for example, a lens (specifically, for example, a biconvex lens, a biconcave lens, a plano-convex lens, a plano-concave lens, a convex meniscus lens, and a concave meniscus lens).
  • a lens specifically, for example, a biconvex lens, a biconcave lens, a plano-convex lens, a plano-concave lens, a convex meniscus lens, and a concave meniscus lens.
  • the lens surface of the translucent member 2 may be spherical or aspherical.
  • the radius of curvature of the lens surface of the translucent member 2 is preferably 10 mm or more and 15 mm or less. Twice
  • the antireflection film 3 suppresses the reflection of light.
  • the optical member 1 is provided with the antireflection film 3 to prevent the light that is about to enter the translucent member 2 from the antireflection film 3 from being reflected by the surface on the antireflection film 3 side. ..
  • the antireflection film 3 has a multilayer structure. Specifically, the antireflection film 3 has a low refractive index layer 4 and a high refractive index layer 5 that are alternately laminated along the thickness direction.
  • the refractive index of the low refractive index layer 4 and the high refractive index layer 5 is not limited as long as the antireflection film 3 can exert an antireflection effect.
  • the refractive index of the low refractive index layer 4 is, for example, 2.00 or less.
  • the refractive index of the high refractive index layer 5 is, for example, more than 2.00.
  • the first layer 41 located on the outermost side of the low refractive index layer 4 and the high refractive index layer 5 is the low refractive index layer 4.
  • the innermost layer among the low refractive index layer 4 and the high refractive index layer 5 is the low refractive index layer 4. Twice
  • Each of the low refractive index layer 4 and the high refractive index layer 5 may have a single-layer structure or a multi-layer structure, respectively.
  • the low refractive index layer 4 having a multilayer structure and the high refractive index layer 5 having a multilayer structure will be described. For example, when two or more layers having a refractive index of 2.00 or less are continuously laminated, the two or more layers are collectively regarded as one low refractive index layer 4. Similarly, when two or more layers having a refractive index of more than 2.00 are continuously laminated, the two or more layers are collectively regarded as one high refractive index layer 5. Twice
  • the total film thickness of the antireflection film 3 is preferably 200 nm or more and 700 nm or less, and more preferably 300 nm or more and 450 nm or less.
  • the total film thickness of the antireflection film 3 is less than 200 nm, a sufficient antireflection effect tends not to be obtained.
  • the productivity of the optical member 1 tends to decrease. Further, when the total film thickness exceeds 700 nm, the production cost of the optical member 1 tends to increase. Twice
  • the film thickness of one layer of the low refractive index layer 4 is, for example, 10.0 nm or more and 190.0 nm or less.
  • the film thickness of one layer of the high refractive index layer 5 is, for example, 3.0 nm or more and 90.0 nm or less. Twice
  • the total number of layers of the low refractive index layer 4 and the high refractive index layer 5 is usually an odd number (for example, 3 layers, 5 layers, 7 layers, 9 layers, 11 layers or 13 layers).
  • the total number of layers of the low refractive index layer 4 and the high refractive index layer 5 is preferably 7, 9 or 11 layers. Twice
  • the refractive index of the low refractive index layer 4 may be less than the refractive index of the translucent member 2.
  • the refractive index of the low refractive index layer 4 is preferably 1.30 or more and 1.90 or less, and more preferably 1.40 or more and 1.60 or less.
  • the reflectance of the optical member 1 is further lowered. Twice
  • the refractive index of the high refractive index layer 5 may be greater than the refractive index of the translucent member 2.
  • the refractive index of the high refractive index layer 5 is preferably 2.40 or more and 3.00 or less, and more preferably 2.40 or more and 2.60 or less.
  • the refractive index of the high refractive index layer 5 is 2.40 or more and 3.00 or less, the reflectance of the optical member 1 is further lowered. Twice
  • the refractive indexes of the low refractive index layer 4 and the high refractive index layer 5 described above are merely examples and are not limited thereto.
  • the refractive index of the low refractive index layer 4 and the high refractive index layer 5 may be set to an optimum value with respect to the refractive index of the translucent member 2. Twice
  • FIG. 2 is a schematic enlarged view showing an example of the first layer 41 in the optical member 1 of FIG.
  • the first layer 41 is a multilayer having an A layer 6 containing photocatalytic particles and a B layer 7 laminated inside the A layer 6.
  • the layer A 6 is a photocatalyst layer, the hydrophilicity of the optical member 1 is improved.
  • the A layer 6 and the B layer 7 are integrated and play an optical role required for the low refractive index layer 4. Twice
  • the B layer 7 preferably contains substantially no photocatalytic particles.
  • substantially containing no photocatalyst particles means that no photocatalyst particles are confirmed when the cross section of the B layer 7 is observed with an electron microscope.
  • the content ratio of the photocatalyst particles in the B layer 7 is preferably 1.0% by mass or less, more preferably 0.1% by mass or less. Twice
  • FIG. 3 is a schematic enlarged view showing an example of the first layer 41 different from that of FIG. 2 in the optical member 1 of FIG.
  • the first layer 41 shown in FIG. 3 is a single layer containing photocatalytic particles.
  • the hydrophilicity of the optical member 1 is improved.
  • the first layer 41 independently plays the optical role required for the low refractive index layer 4. Twice
  • the first layer 41 shown in FIG. 2 corresponds to a layer in which a part of the first layer of the antireflection film is replaced with a photocatalyst layer (A layer 6) in a known optical member.
  • the first layer 41 shown in FIG. 3 corresponds to a layer in which the entire first layer of the antireflection film is replaced with a photocatalyst layer in a known optical member. Twice
  • the film thickness of the A layer 6 is preferably 25 nm or more and 120 nm or less, and more preferably 30 nm or more and 50 nm or less.
  • the film thickness of the A layer 6 is 25 nm or more, the abrasion resistance of the photocatalyst layer is improved.
  • the film thickness of the A layer 6 is 120 nm or less, the reflectance of the optical member 1 is further lowered. Further, as shown in FIG.
  • the film thickness of the first layer 41 is preferably 25 nm or more and 120 nm or less, and more preferably 100 nm or more and 120 nm or less.
  • the film thickness of the first layer 41 is 25 nm or more, the abrasion resistance of the photocatalyst layer is improved.
  • the film thickness of the first layer 41 is 120 nm or less, the reflectance of the optical member 1 is further lowered. Twice
  • the preferable film thickness of the first layer 41 depends on the total film thickness of the antireflection film 3. Therefore, in the following, the preferable film thickness of the first layer 41 is shown as a ratio to the total film thickness of the antireflection film 3. Further, the preferable film thickness of the first layer 41 also differs depending on the total number of layers of the antireflection film 3. Therefore, in the following, the preferable film thickness of the first layer 41 will be described separately for the case where the total number of layers of the antireflection film 3 is 7, 9 layers, and 11 layers. Twice
  • the first layer 41 is a multilayer, the ratio of the thickness of the A layer 6 to the total thickness of the antireflection film 3 and T A, film B layer 7 to the total thickness of the antireflection film 3 the ratio of thickness to T B. If the total layer number of the low refractive index layer 4 and the high-refractive index layer 5 is seven layers, T A is less 31.6% or more 6.7%, and T B is more than 0.2% 24.9 % preferably less is, T A is less by 12.0% to 7.0%, and T B is more preferably less 24.0% or more 18.0%.
  • T A is less 27.2% or more 5.7%, and T B is more than 0.2% 20.7 % preferably less is, T A is less 11.0% to 6.0%, and T B is more preferably less 20.0% 12.0%.
  • T A is at 21.4% or less than 5.1%, and T B is more than 0.2% 16.3 % preferably less is, T A is less 10.0% or more 5.5%, and T B is more preferably less 16.0% 10.0%.
  • the first layer 41 is preferably multi-layered.
  • a layer other than the photocatalyst layer is formed by a vacuum integrated process (for example, a vapor deposition method and a sputtering method), and then the photocatalyst layer is formed by a wet process. Is preferable.
  • the antireflection film 3 is formed by this method, it tends to be somewhat difficult to sufficiently secure the interlayer adhesion between the photocatalyst layer and the layers other than the photocatalyst layer due to the difference in the manufacturing method. be.
  • the photocatalyst layer and the high refractive index layer 5 tend to have a slightly low affinity due to the difference in materials. Therefore, as shown in FIG. 3, when the first layer 41 is a single layer composed of a photocatalyst layer, and the photocatalyst layer (first layer 41) and the high refractive index layer 5 are in direct contact with each other, the first layer 41 and the high The interlayer adhesion of the refractive index layer 5 tends to be slightly lowered. On the other hand, as shown in FIG. 2, when the first layer 41 is multi-layered, the photocatalyst layer (A layer 6) and the high refractive index layer 5 are laminated via the B layer 7, and therefore are in direct contact with each other. No.
  • the interlayer adhesion between the first layer 41 and the high refractive index layer 5 can be improved.
  • the photocatalyst layer (first layer 41) can be made as thick as possible, so that the wear resistance of the photocatalyst layer is improved. There are merits. Twice
  • the refractive index of the A layer 6 is 1.30 or more and 1.90 or less
  • the refractive index of the B layer 7 is 1.40 or more and 1. It is preferably 50 or less
  • the refractive index of layer A 6 is 1.40 or more and 1.50 or less
  • the refractive index of layer B 7 is 1.40 or more and 1.50 or less.
  • the refractive index of layer A 6 can be adjusted by, for example, the content ratio of the photocatalytic particles and the type of a component (for example, a binder) other than the photocatalyst particles.
  • photocatalytic particles tend to have a slightly higher refractive index.
  • the refractive index of anatase-type titanium oxide is about 2.52. Therefore, in order to adjust the refractive index of layer A 6 within the above numerical range, it is preferable to use a material having a relatively low content ratio of photocatalyst particles in the photocatalyst layer and a relatively low refractive index as a binder. .. Twice
  • the B layer 7 when the first layer 41 is multi-layered, the B layer 7 preferably contains SiO 2.
  • the B layer 7 containing SiO 2 exhibits excellent interlayer adhesion with both the photocatalyst layer (A layer 6) and the high refractive index layer 5. Therefore, when the B layer 7 contains SiO 2 , the interlayer adhesion between the first layer 41 and the high refractive index layer 5 can be further improved.
  • the static contact angle of the surface of the antireflection film 3 with respect to pure water is preferably 30.0 ° or less, more preferably 20.0 ° or less, still more preferably 10.0 ° or less.
  • the static contact angle with respect to pure water may be simply referred to as "contact angle”.
  • the contact angle on the surface of the antireflection film 3 is a value measured in an environment where the temperature is 23 ° C. ⁇ 3 ° C. and the relative humidity is 50% ⁇ 3%. Twice
  • the composition of the photocatalyst layer (A layer 6 shown in FIG. 2 or the first layer 41 shown in FIG. 3) will be described.
  • the photocatalyst layer contains photocatalyst particles.
  • the photocatalyst layer preferably further contains a binder.
  • the photocatalyst particles are particles containing a photocatalyst. At least a part of the photocatalytic particles may constitute secondary particles. As long as the photocatalyst particles contain the photocatalyst, the photocatalyst particles may further contain components other than the photocatalyst. Examples of the component other than the photocatalyst include a component having an electron capture effect. Examples of the substance having an electron capturing effect include gold, silver, copper, platinum, palladium, iron, nickel, cobalt, zinc and copper oxide.
  • the content ratio of the photocatalyst in the photocatalyst particles is preferably 90% by mass or more, more preferably 99% by mass or more, still more preferably 100% by mass.
  • Examples of the photocatalyst contained in the photocatalyst particles include titanium oxide, strontium titanate, zinc oxide, silicon carbide, gallium phosphate, cadmium sulfide, cadmium selenide and molybdenum trisulfide.
  • the photocatalytic particles preferably contain titanium oxide. When the photocatalyst particles contain titanium oxide, the hydrophilicity of the photocatalyst layer is further improved. Twice
  • titanium oxide examples include anatase-type titanium oxide, rutile-type titanium oxide, and brookite-type titanium oxide.
  • anatase-type titanium oxide is preferable from the viewpoint of photocatalytic activity. Twice
  • the average particle size of the primary particles of the photocatalyst particles is preferably 1 nm or more and 20 nm or less, and more preferably 5 nm or more and 18 nm or less.
  • the translucency of the optical member 1 is improved. Twice
  • the average particle size of the secondary particles of the photocatalyst particles is preferably 10 nm or more and 90 nm or less, and more preferably 10 nm or more and 50 nm or less.
  • the average particle size of the secondary particles of the photocatalyst particles is 10 nm or more, the hydrophilicity of the photocatalyst layer is further improved.
  • the average particle size of the secondary particles of the photocatalyst particles is 90 nm or less, the translucency of the photocatalyst layer is improved. Twice
  • the binder may be either an inorganic binder or an organic binder.
  • the inorganic binder include silica, silicate, titania phosphate and peroxotitanium.
  • the organic binder include a resin. From the viewpoint of suppressing decomposition of the binder by the photocatalytic activity of the photocatalytic particles, the binder is preferably an inorganic binder, and more preferably silica or silicate.
  • a layer other than the photocatalytic layer of the antireflection film 3 will be described. Specifically, as shown in FIG. 2, when the first layer 41 is multi-layered, the low refractive index layer 4 and the high refractive index layer 5 other than the B layer 7 and the first layer 41 are other than the photocatalytic layer. It is a layer. As shown in FIG. 3, when the first layer 41 is a single layer composed of a photocatalyst layer, the low refractive index layer 4 and the high refractive index layer 5 other than the first layer 41 are layers other than the photocatalyst layer.
  • the layers other than the photocatalytic layer of the antireflection film 3 can be the same as the known antireflection film.
  • the layer other than the photocatalytic layer of the antireflection film 3 is, for example, a vapor deposition film or a sputtering film.
  • the layers other than the photocatalytic layer of the antireflection film 3 contain a metal or a metal oxide.
  • a "metal” includes a semiconductor (for example, a silicon compound).
  • Examples of the components of the layer other than the photocatalytic layer of the antireflection film 3 include SiO 2 , MgF 2 , ZrO 2 , Al 2 O 3 , TIO 2 , Ti 3 O 5 , Ta 2 O 5 and Nb 2 O 5. Can be mentioned.
  • examples of the components of the low refractive index layer 4 other than the photocatalyst layer include SiO 2 , Al 2 O 3 and Mg F 2 .
  • SiO 2 is preferable as a component of the low refractive index layer 4 other than the photocatalyst layer.
  • Examples of the components of the high refractive index layer 5 include ZrO 2 , TIO 2 , Ti 3 O 5 , Ta 2 O 5 and Nb 2 O 5 .
  • the low refractive index layer 4 and the high refractive index layer 5 other than the photocatalyst layer contain one or more (preferably one or two) of the above-mentioned components in a content ratio of 95% by mass or more. Is preferable.
  • the optical member 101 includes a translucent member 102 and an antireflection film 103 that covers the translucent member 102.
  • the antireflection film 103 has a low refractive index layer 104 and a high refractive index layer 105 that are alternately laminated along the thickness direction.
  • the first layer 141 located on the outermost side (upper side in FIG. 4) of the low refractive index layer 104 and the high refractive index layer 105 is the low refractive index layer 104.
  • the innermost layer (lower side in FIG. 4) of the low refractive index layer 104 and the high refractive index layer 105 is the high refractive index layer 105.
  • the optical member 101 of FIG. 4 has an even total number of layers of the low refractive index layer 104 and the high refractive index layer 105 (for example, 4 layers, 6 layers, 8 layers, 10 layers, 12 layers or 14 layers), and the only difference is that the innermost layer among the low refractive index layer 104 and the high refractive index layer 105 is the high refractive index layer 105.
  • the optical member 101 of FIG. 4 corresponds to an optical member formed by adding a high refractive index layer 5 to the innermost side of the antireflection film 3 of the optical member 1 of FIG. Therefore, the description overlapping with the optical member 1 will be omitted.
  • the innermost layer of the antireflection film may be a low refractive index layer as shown in FIG. 1, depending on the optical characteristics required for the optical member.
  • a high refractive index layer may be used as shown in FIG. Twice
  • optical member according to the present embodiment has been described above with reference to the drawings.
  • the optical member according to the present embodiment is not limited to the optical member 1 shown in FIG. 1 and the optical member 101 shown in FIG.
  • the antireflection film may cover only one surface of the translucent member, or may cover both sides of the translucent member.
  • at least one of the antireflection films of the pair of antireflection films is a photocatalytic layer at least a part of the first layer as described above. Has been replaced.
  • the other antireflection film may be at least a part of the first layer replaced with a photocatalytic layer, or may be a known antireflection film.
  • the optical member may further include a member other than the translucent member and the antireflection film (for example, a protective film).
  • the antireflection film is preferably the outermost layer of the optical member.
  • the antireflection film may be covered with another film (for example, a protective film) as long as the antireflection effect can be exhibited. Twice
  • the optical member is manufactured by first step of forming a layer other than the photocatalyst layer on the translucent member and by applying a coating liquid for forming a photocatalyst layer to the laminate obtained in the first step. It includes a second step of forming a photocatalyst layer.
  • the layers other than the photocatalyst layer are the B layer, the low refractive index layer other than the first layer, and the high refractive index layer.
  • the layers other than the photocatalyst layer are a low refractive index layer other than the first layer and a high refractive index layer.
  • Examples of the method for forming a layer other than the photocatalyst layer in the first step include known vapor deposition methods and sputtering methods.
  • the photocatalyst layer may be formed by one coating on the laminate obtained in the first step, or the photocatalyst layer may be formed by two or more (for example, two) coatings. May be good.
  • a coating liquid for forming a photocatalyst layer containing photocatalyst particles, a binder raw material, and a solvent is applied.
  • the photocatalyst layer is formed by two coatings, in the second step, for example, after applying the first photocatalyst layer forming coating liquid containing the photocatalyst particles and the solvent, the second step containing the binder raw material and the solvent.
  • a coating liquid for forming a photocatalyst layer is further applied.
  • the photocatalyst layer by two coatings in the second step, at least a part of the photocatalyst particles is partially or completely covered with the binder. As a result, the wear resistance of the photocatalyst layer of the formed optical member is further improved. Twice
  • a wet process is preferable as a method for applying the coating liquid for forming a photocatalyst layer.
  • the wet process include a spin coating method, a roll coating method, a bar coating method, a dip coating method, a spray coating method, and a method in which two or more of these are combined (for example, a dip spin coating method).
  • a spin coating method, a dip coating method or a dip spin coating method is preferable. Twice
  • the rotation speed is preferably 500 rpm or more and 10000 rpm or less.
  • the solid content concentration of the coating liquid for forming the photocatalyst layer is preferably 1.0% by mass or more and 10.0% by mass or less. Twice
  • an aqueous solvent is preferable.
  • the aqueous solvent contains water and additives.
  • Additives include, for example, organic acids, alcohol compounds and ammonia.
  • the content ratio of the additive in the aqueous solvent is preferably more than 0% by mass and 20% by mass or less.
  • organic acids include formic acid, acetic acid, propionic acid, succinic acid, citric acid and malic acid.
  • the alcohol compound include methanol, ethanol, isopropyl alcohol, n-propyl alcohol and butanol. Twice
  • the heat treatment promotes the removal of volatile components in the coating liquid for forming the photocatalyst layer.
  • the heating conditions can be, for example, a treatment temperature of 60 ° C. or higher and 200 ° C. or lower, and a treatment time of 10 minutes or longer and 10 hours or lower. Twice
  • the second step it is preferable to further include a surface treatment step of treating the surface of the above-mentioned laminate before applying the coating liquid for forming the photocatalyst layer.
  • the surface treatment include plasma treatment, electron beam treatment, corona treatment and frame treatment.
  • the plasma treatment include high-frequency discharge plasma treatment and atmospheric pressure glow discharge plasma treatment. A plurality of these surface treatments can be used in combination. Twice
  • the laminate used in the second step can be manufactured from a known optical member (for example, a commercially available optical member).
  • a third layer for removing a part or all of the first layer (low refractive index layer located on the outermost side) of the antireflection film is removed.
  • the method for removing the first layer of the antireflection film in the third step include polishing treatment, ashing treatment (for example, oxygen plasma ashing treatment and argon plasma ashing treatment), and chemical treatment.
  • the film thickness of the photocatalyst layer formed in the second step is preferably substantially the same as the film thickness of the first layer of the antireflection film removed in the third step.
  • ⁇ Examination 1 Layer structure> Three types of optical members having different layer structures of the antireflection film were produced by the following methods, and their performances were evaluated. From this, the suitable layer structure of the antireflection film was examined. In addition, in the Example, the "Nth layer (N is an integer of 1 or more)" of the antireflection film is the Nth layer counted from the outside among the low refractive index layer and the high refractive index layer of the antireflection film. Indicates that it is a layer.
  • Example 1 The optical member of Example 1 was manufactured by the following method.
  • a lens (“TAFD-5G” manufactured by HOYA Corporation, composition: glass, diameter 12.9 mm, refractive index: 1.835) was prepared. This lens had a convex surface (radius of curvature 12 mm) on one surface and a concave surface (radius of curvature 3.07 mm) on the other surface.
  • An antireflection film having a layered structure shown in Table 1 below was formed on the convex surface of this lens.
  • the total number of low refractive index layers and high refractive index layers was nine.
  • the first layer, the third layer, the fifth layer, the seventh layer, and the ninth layer were low refractive index layers.
  • the second layer, the fourth layer, the sixth layer, and the eighth layer were high refractive index layers.
  • "OS-50" indicates Ti 3 O 5 (melt product).
  • layers other than the photocatalytic layer among the antireflection films are formed on the convex surface of the lens in the 9th layer, the 8th layer, the 7th layer, the 6th layer, the 5th layer, and the 4th layer.
  • the layer, the third layer, the second layer, and the B layer of the first layer were formed in this order.
  • the convex surface of the obtained laminate (the surface of the first layer on the B layer side) was surface-treated.
  • a plasma treatment using a plasma surface modifier was performed. Twice
  • the above-mentioned coating liquid for forming a photocatalyst layer was applied to the convex surface of the above-mentioned laminate. Specifically, 40 ⁇ L of a coating liquid for forming a photocatalyst layer was dropped on the optical axis of the laminate. Next, a spin coater (“MS-B100” manufactured by Mikasa Co., Ltd.) was used to rotate the laminate at a rotation speed of 5000 rpm. At this time, the rotation axis of the laminated body was aligned with the optical axis of the translucent member. After coating, heat treatment was performed at 80 ° C. for 30 minutes. As a result, a photocatalyst layer was formed.
  • MS-B100 manufactured by Mikasa Co., Ltd.
  • the obtained optical member of Example 1 had a maximum reflectance of 1.5% or less, as will be described later. Therefore, in the optical member of Example 1, it was determined that the photocatalyst layer functions as a part of the antireflection film (layer A of the first layer). Twice
  • Example 2 to 5 The optical members of Examples 2 to 5 were manufactured by the same method as the optical members of Example 1 except that the layer structure of the antireflection film was changed as shown in Tables 1 to 3 below.
  • the obtained optical members of Examples 2 to 5 had a maximum reflectance of 1.5% or less, as will be described later. Therefore, in the optical members of Examples 2 to 5, it was determined that the photocatalyst layer functions as a part of the antireflection film (layer A of the first layer).
  • the total number of layers of the low refractive index layer and the high refractive index layer was 9, 11, 13 or 7, respectively. Of these, the odd-numbered layer was a low refractive index layer.
  • the even layer was a high refractive index layer.
  • "-" indicates that the corresponding layer does not exist.
  • Comparative Examples 1 and 2 The optical members of Comparative Examples 1 and 2 were manufactured by the same method as in Example 1 except that the following points were changed.
  • the layer structure of the antireflection film of the optical members of Comparative Examples 1 and 2 is shown in Table 4 below.
  • the optical member of Comparative Example 1 corresponds to a known optical member including a translucent member and an antireflection film covering the translucent member. Twice
  • the film thickness of the photocatalyst layer was changed to 28.0 nm, and the film thickness of the B layer of the first layer was changed to 104.1 nm.
  • the optical member of Comparative Example 2 had a maximum reflectance of more than 1.5%. Therefore, in the optical member of Comparative Example 2, it was determined that the photocatalyst layer did not function as a part of the antireflection film.
  • the optical member of Comparative Example 2 corresponds to a known optical member including a translucent member, an antireflection film covering the translucent member, and a hydrophilic film covering the antireflection film. Twice
  • Example 1-5 and Comparative Examples 1-2 are summarized total layer number of the antireflection film, the total thickness of the antireflection film, the T A and T B in Table 5 below.
  • the spectral reflectances of the optical members of Examples 1 to 5 and Comparative Examples 1 and 2 are shown in FIGS. 5 to 11. Based on the graph of spectral reflectance, the maximum reflectance for incident light having a wavelength of 480 nm or more and 780 nm or less and the average reflectance for incident light having a wavelength of 480 nm or more and 500 nm or less were determined. In this embodiment, the maximum reflectance and the average reflectance of the optical member are determined to be good at 1.5% or less, and particularly good at 1.0% or less.
  • the optical members of Examples 1 to 5 had good contact angles, average reflectance, and maximum reflectance.
  • the optical member of Comparative Example 1 had a poor contact angle.
  • the optical member of Comparative Example 2 did not have good maximum reflectance and average reflectance. Twice
  • ⁇ Examination 2 Refractive index of photocatalytic layer>
  • the preferable refractive index of the A layer of the first layer of the antireflection film was examined by the following method. First, when the refractive index of the A layer of the first layer of the antireflection film is increased or decreased by using simulation software (“FILMSTAR” manufactured by FTG), the average reflectance of the optical member with respect to light having a wavelength of 480 nm or more and 500 nm or less is obtained. We analyzed how it increases and decreases. In the analysis, the film thickness of the A layer of the first layer was set to 30 nm. The refractive index of the translucent member was set to 1.847.
  • the film thickness and refractive index of the other layers of the antireflection film are the B layer of the first layer and the second to ninth layers shown in Table 1. It was set to be the same as the film thickness and the refractive index.
  • the incident light was set to be incident from the surface on the antireflection film side. The incident angle of the incident light was set to 0 degrees. The analysis results are shown in Table 7 and FIG. 12 below.
  • the average reflectance of the optical member was 1.5% or less by setting the refractive index of the photocatalyst layer to 2.00 or less. Further, it was found that the average reflectance of the optical member was 1.0% or less by setting the refractive index of the photocatalyst layer to less than 1.90. From the above, it is judged that the refractive index of the A layer of the first layer of the antireflection film is preferably 2.00 or less, and more preferably less than 1.90.
  • the peak of the reflectance for light having a wavelength of 480 nm or more and 780 nm or less appears at a position of a wavelength of 480 nm or more and 500 nm or less. Therefore, in this study, it can be considered that the average reflectance of the optical member for light having a wavelength of 480 nm or more and 500 nm or less is substantially the same as the maximum reflectance of the optical member for light having a wavelength of 480 nm or more and 780 nm or less. Twice
  • the present invention is suitable as an optical member for a sensor or a photographing device.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Laminated Bodies (AREA)

Abstract

Élément optique pourvu d'un élément émetteur de lumière et d'un film antireflet qui recouvre l'élément émetteur de lumière. Le film antireflet comporte des couches à faible indice de réfraction et des couches à indice de réfraction élevé qui sont empilées en alternance le long de la direction d'épaisseur. Des premières couches, qui parmi les couches à faible indice de réfraction et les couches à indice de réfraction élevé sont situées sur les côtés les plus à l'extérieur, sont des couches à faible indice de réfraction. Chacune des premières couches est une couche unique qui comprend des particules de photocatalyseur ou est une multicouche qui comporte une couche A, qui comprend des particules de photocatalyseur, et une couche B, qui est empilée vers l'intérieur de la couche A.
PCT/JP2020/037634 2020-03-31 2020-10-02 Élément optique WO2021199466A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1045435A (ja) * 1996-07-31 1998-02-17 Central Glass Co Ltd 低反射ガラス
JP2006195088A (ja) * 2005-01-12 2006-07-27 Pentax Corp 反射防止性光学物品
JP2007536137A (ja) * 2004-05-10 2007-12-13 サン−ゴバン グラス フランス 光触媒被覆物を有する基板
WO2018110017A1 (fr) * 2016-12-14 2018-06-21 コニカミノルタ株式会社 Produit optique

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103635838B (zh) * 2011-06-24 2016-08-10 柯尼卡美能达株式会社 光学反射膜
JP2014167620A (ja) * 2013-01-29 2014-09-11 Nitto Denko Corp 反射防止フィルムおよびその製造方法
JP6492412B2 (ja) * 2014-04-02 2019-04-03 凸版印刷株式会社 反射防止フィルム、それを用いた偏光板、画像表示装置、液晶表示装置、およびタッチパネル
JP6314627B2 (ja) * 2014-04-21 2018-04-25 リコーイメージング株式会社 反射防止膜、及びそれを有する光学部品

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1045435A (ja) * 1996-07-31 1998-02-17 Central Glass Co Ltd 低反射ガラス
JP2007536137A (ja) * 2004-05-10 2007-12-13 サン−ゴバン グラス フランス 光触媒被覆物を有する基板
JP2006195088A (ja) * 2005-01-12 2006-07-27 Pentax Corp 反射防止性光学物品
WO2018110017A1 (fr) * 2016-12-14 2018-06-21 コニカミノルタ株式会社 Produit optique

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