Member, optical member, optical apparatus, imaging device, and method for manufacturing member

Abstract

A member 10 comprises a substrate 100, an organic resin layer 101, a porous layer 102, and an aluminum oxide layer 104 in this order, wherein the organic resin layer 101 includes a polymer having an aromatic ring in the main chain and / or a polymer having an imide ring in the main chain, the porous layer 102 includes at least a first porous layer 112 containing a material different from amorphous aluminum oxide, and the aluminum oxide layer 104 contains crystalline aluminum oxide having an uneven structure 114a.

Description

Components, optical components, optical instruments, imaging devices, and methods for manufacturing components.

[0001] This disclosure relates to a component having an uneven structure and a method for manufacturing the same. Furthermore, this disclosure relates to an optical component using the component for optical applications, and to an optical instrument and imaging device using the optical component.

[0002] A component is known that uses an aluminum oxide layer containing aluminum oxide crystals having an uneven structure. Patent Document 1 discloses that such a component is used as an optical component, and in order to achieve both productivity and anti-reflective properties, an intermediate layer consisting of an organic resin layer containing polyimide and a porous layer mainly composed of aluminum oxide is provided on the substrate.

[0003] Japanese Patent Publication No. 2013-47780

[0004] This component may require repair during manufacturing for any reason, and it was desirable to be able to perform this repair work more easily.

[0005] A first embodiment for solving the above problems is a member comprising a base material, an organic resin layer, a porous layer, and an aluminum oxide layer in this order, wherein the organic resin layer contains a polymer having an aromatic ring in its main chain and / or a polymer having an imide ring in its main chain, the porous layer contains at least a first porous layer containing a material different from amorphous aluminum oxide, and the aluminum oxide layer contains crystalline aluminum oxide having an uneven structure.

[0006] A second embodiment for solving the above problems is a method for manufacturing a member comprising a base material, an organic resin layer, a porous layer, and an aluminum oxide layer in this order, the method comprising: applying a first coating solution of a polymer having an aromatic ring in its main chain and / or an imide ring in its main chain onto the base material to form an organic resin layer; applying a second coating solution containing a material different from amorphous aluminum oxide onto the organic resin layer to form a porous layer; applying a third coating solution of an aluminum oxide precursor sol onto the porous layer and curing the third coating solution to obtain a coating film; and immersing the coating film in hot water to form an aluminum oxide layer containing crystalline aluminum oxide having an uneven structure.

[0007] This disclosure provides a component that allows for easier regeneration and a method for manufacturing the same. Furthermore, this disclosure provides an optical component using the component for optical applications, an optical instrument using the optical component, and an imaging device.

[0008] A schematic cross-sectional view of a member according to the first embodiment, cut from the stacking direction. A partially enlarged view of the area enclosed by rectangle AA in Figure 1. A schematic diagram showing an example of the refractive index of an aluminum oxide layer. A schematic cross-sectional view of a member according to the second embodiment, cut from the stacking direction. A schematic cross-sectional view of a member according to the third embodiment, cut from the stacking direction. A schematic cross-sectional view of a member according to the fourth embodiment, cut from the stacking direction. A schematic cross-sectional view of a member according to a modified example of the fourth embodiment, cut from the stacking direction. A schematic diagram of an imaging device according to the fifth embodiment. A flowchart showing one embodiment of a method for manufacturing the member.

[0009] In Patent Document 1, the intermediate layer between the aluminum oxide layer and the substrate is formed by a coating method. Many optical components have curved main surfaces, and films formed by coating methods tend to be thicker at the periphery of the curved surface than at the center. Therefore, defects such as cracks may occur at the periphery of the curved surface of the optical component. If defects occur, instead of discarding the component, a regeneration process is required in which the formed film is wiped off with a solvent, the film is completely removed from the substrate, and then the film is re-formed. However, the inventors of this application have found that when a porous layer containing an organic resin layer containing polyimide and an amorphous aluminum oxide layer is used as the intermediate layer, the polyimide mixes with the amorphous aluminum oxide, changing the film quality of the organic resin layer and making it difficult to peel off.

[0010] This disclosure is made in view of the above-mentioned background and provides a component using an aluminum oxide layer containing crystalline aluminum oxide having an uneven structure that facilitates regeneration work.

[0011] [First Embodiment] [Optical Member] The member of this disclosure has at least one of the following functions: optical properties, antifouling properties, hydrophilicity, antibacterial properties, antiviral properties, and decorative properties. First, the optical member will be described.

[0012] Figure 1 is a schematic cross-sectional view of a member according to the first embodiment, cut from the lamination direction. The member 10 of this disclosure is a member comprising a base material 100, an organic resin layer 101, a porous layer 102, and an aluminum oxide layer 104 in this order. The porous layer 102 may include a first porous layer 112 containing a material different from amorphous aluminum oxide, and a second porous layer 113 containing amorphous aluminum oxide. As an optical member, it is easy to recycle and can achieve excellent anti-reflective performance regardless of the material of the base material 100.

[0013] (Base material) The base material 100 has a main surface 100A and a main surface 100B located on the opposite side of the main surface 100A. In the first embodiment, an organic resin layer 101, a porous layer 102, and an aluminum oxide layer 104 are provided in this order on the main surface 100A side.

[0014] The material of the substrate 100 is not particularly limited, and any material such as glass, ceramics, resin, metal, or semiconductor can be used. Its shape is also not limited, and it can be a flat plate, a curved shape with concave or convex surfaces, a film, or a sheet. The substrate 100 is preferably a transparent substrate. As a transparent substrate, resin or glass can be used. In this specification, "transparent" means that the transmittance of light in the wavelength range of 400 nm to 780 nm is 10% or more. As a transparent substrate, glass is preferred, and for example, general optical glass such as silicate glass, borosilicate glass, or phosphate glass, as well as quartz glass or glass ceramics, can be used.

[0015] Glass and ceramics are so-called composite oxides, and for example, they contain zirconium oxide, titanium oxide, tantalum oxide, niobium oxide, hafnium oxide, lanthanum oxide, gadolinium oxide, silicon oxide (silica), calcium oxide, barium oxide, sodium oxide, potassium oxide, boron oxide, and aluminum oxide. The manufacturing method of the base material 100 is not particularly limited and can be produced by grinding and polishing, molding, or float molding, for example.

[0016] As the resin, it is preferable to use a thermoplastic resin or a thermosetting resin. Examples of thermoplastic resins include polyethylene terephthalate, PET (polyethylene naphthalate), PP (polypropylene), triacetylcellulose, PC (polycarbonate), cycloolefin polymer, and polyvinyl alcohol. Examples of thermosetting resins include urethane resins.

[0017] As for the metal, you can use one that consists of a single metallic element or an alloy containing two or more metallic elements.

[0018] Examples of semiconductors include elemental semiconductors such as silicon and germanium, as well as gallium phosphide and indium phosphide.

[0019] The refractive index ns of the d-line of the substrate 100 is, for example, greater than 1.43 and less than 2.20. Using a substrate with a refractive index ns within this range makes it possible to meet a wide range of optical application needs. Preferably, the range is 1.45 to 2.05.

[0020] The substrate 100 also includes an undercoat layer provided on the main surface 100A of the aforementioned substrate, such as glass. The undercoat layer is preferably less than 15 nm thick so as not to peel off during restoration work by solvent wiping or affect light interference. If there is an undercoat layer, an organic resin layer 101 is provided on top of the undercoat layer. The undercoat layer is composed of, for example, an adhesive layer, a primer layer, an oxide, nitride and fluoride to prevent the diffusion of impurities from the substrate, a polymer that does not have an aromatic ring in its main chain, and a polymer that does not have an imide ring in its main chain.

[0021] (Organic resin layer) The organic resin layer 101 contains polymers having aromatic rings in the main chain and / or polymers having imide rings in the main chain. Examples of aromatic rings and imide rings include structures represented by the following chemical formulas. On the other hand, polymers having imide rings or aromatic rings in the side chain or pendant group, such as polystyrene and polybenzyl methacrylate, are not included.

[0022]

[0023] Polymers having aromatic rings in their main chain and polymers having imide rings in their main chain have planar structures, so when these structures are introduced into the main chain of an organic resin, the molecular chains tend to orient parallel to the substrate during film formation. Therefore, even when the organic resin layer 101 is used with a thickness of 50 nm or less, the uniformity of thickness and refractive index is high. Furthermore, because it has excellent mechanical properties even without curing at high temperatures, it is suitable as a lower layer when laminating each layer.

[0024] The thickness ta of the organic resin layer 101 is preferably 5 nm to 50 nm, and can be varied within this range according to the refractive index ns of the d line of the substrate 100. If the thickness ta of the organic resin layer 101 is less than 5 nm, the anti-reflective performance may not be sufficient. On the other hand, if the thickness of the organic resin layer 101 exceeds 50 nm, the solvent may not reach the interface between the substrate 100 and the organic resin layer 101 during the regeneration process, making it difficult to peel the organic resin layer 101 from the substrate 100. Thus, although the molecular chains of the organic resin layer 101 are sufficiently intertwined, by setting the thickness within the above range, it can be more easily peeled off from the substrate 100 by wiping with a solvent.

[0025] Polymers having aromatic rings in the main chain and polymers having imide rings in the main chain can be either thermosetting resins or thermoplastic resins. Thermoplastic resins are more preferred from the viewpoint that the refractive index and thickness do not change under baking conditions (curing conditions, drying conditions) and that there is less residue of uncured monomers.

[0026] Suitable examples of polymers having aromatic rings in the main chain and polymers having imide rings in the main chain include thermoplastic polyimides, aromatic polyamides, melamine polymers, polymaleimides, as well as aromatic polyethers such as polyetherketones and polyethersulfones, aromatic polyesters such as polyethylene terephthalate, aromatic polycarbonates, aromatic polyurethanes, and aromatic polyureas. Thermoplastic polyimides are particularly preferred because they are easy to regenerate by wiping with solvents and have a high refractive index.

[0027] The refractive index n1 of the d-line of the organic resin layer 101 is preferably in the range of 1.50 to 1.90. Satisfying this refractive index range increases the degree of freedom in optical design through combination with the upper layer, and enables anti-reflective effects over a wide range, from substrates with low refractive indices to those with high refractive indices. A good example of a material satisfying this refractive index range is a branched polymer having a melamine structure. Branched polymers with a melamine skeleton have a high refractive index exceeding 1.80 and excellent compatibility with other polymers, allowing for the formation of intermediate layers with a wide refractive index range from medium to high by polymer blending. A more preferred range is 1.55 to 1.85, and an even more preferred range is 1.60 to 1.80.

[0028] Polymers having an aromatic ring in their main chain and polymers having an imide ring in their main chain are preferably soluble in at least one solvent selected from cyclohexanone, cyclopentanone, and γ-butyrolactone, and insoluble in at least one solvent selected from acetate esters. In this specification, solubility in a solvent means that 1 g or more of the polymer dissolves in 100 g of solvent at 20°C. On the other hand, insolubility in a solvent means that the amount of polymer that dissolves is less than 1 g per 100 g of solvent at 20°C, or that precipitation or turbidity occurs due to undissolved material. When a polymer with such solubility is used in the organic resin layer 101, the dissolution of the organic resin layer 101 can be minimized when a first porous layer 112 containing a material different from amorphous aluminum oxide, as described later, is applied to the organic resin layer 101.

[0029] (Porous layer) In the first embodiment, the porous layer 102 includes a first porous layer 112 containing a material different from amorphous aluminum oxide, and a second porous layer 113 containing amorphous aluminum oxide.

[0030] <First Porous Layer> Figure 2 is a partially enlarged view of the region enclosed by rectangle AA in Figure 1, and is a schematic diagram showing one embodiment of the first porous layer 112. In Figure 2, the first porous layer 112 consists of particles 131 bound together by a binder 132. There are also voids 133 between the particles 131 and the binder 132.

[0031] The first porous layer 112 is preferably made of an inorganic compound. The first porous layer 112 can be made of a porous material in which multiple inorganic compound particles (inorganic particles) are bound together with a binder. By providing the first porous layer 112 between the organic resin layer 101 and the second porous layer 113 containing amorphous aluminum oxide, the organic resin layer 101 is less likely to react with the amorphous aluminum oxide in the second porous layer 113 even when a solvent is used. As a result, the change in the film quality of the organic resin layer 101 can be suppressed more than the configuration disclosed in Patent Document 1. Furthermore, because it is porous, when a solvent is used on the finished component 10, it easily penetrates into the underlying organic resin layer 101, and as a result, the organic resin layer 101 can be easily peeled off the substrate 100. In addition, the optical interference between the organic resin layer 101 and the first porous layer 112 increases the degree of freedom in optical design, and a high anti-reflective effect can be achieved regardless of the material of the substrate 100.

[0032] If the first porous layer 112 is a porous layer in which multiple inorganic compound particles are bound together by a binder and have voids between the particles, the refractive index can be adjusted by the material of the particles and binder, and the amount of voids (porosity). The porosity can be adjusted by the size and shape of the particles and the amount of binder.

[0033] It is preferable to use inorganic compound particles having a refractive index of less than 1.50 in at least a portion of the visible light range. The inorganic compound is preferably one particle selected from the group consisting of silicon dioxide (silica), magnesium fluoride, lithium fluoride, calcium fluoride, and barium fluoride. Silica particles are particularly preferred from the viewpoint of having high hydrophilicity for incorporating solvents. The particle composition can be determined by analyzing the cross-section of the layer using energy-dispersive X-ray analysis (EDX). The particles may be solid particles, cocoon-shaped particles, barrel-shaped particles, chain-like particles, or hollow particles having voids inside the particle, but cocoon-shaped particles or chain-like particles that can contain many voids in the layer are preferred. Chain-like particles refer to secondary particles in which multiple primary particles such as solid particles are bound together and linked in a straight line or while bending. It is preferable that the inorganic compound particles are in a state that is easy to pre-treat so that desired functions can be imparted by modifying their surface. The binder that binds the particles together is preferably an inorganic material of the same quality as the particles. When silica particles are used as the particles, silica is preferred as the binder, and silicon dioxide compounds are preferred as the binder component.

[0034] Furthermore, the surface of inorganic compound particles can be modified to impart desired functions. Specifically, surface treatment can be used to improve the alignment of inorganic compound particles or to suppress the adsorption of chemical contaminants and moisture, for example, to prevent changes in optical performance under high humidity conditions. As for surface modification methods, for example, surface treatment components can be directly added to the coating solution in which the particles are dispersed, or the surface can be treated by exposing it to an atmosphere after film formation. When surface treatment is performed by exposing it to an atmosphere after film formation, each layer can be treated individually, or the entire film can be treated at once after all layers have been formed. Examples of surface treatment include hydrophobicization and hydrophilicization. A specific example of hydrophobicization is the addition of fluoromethyl groups or methylsilyl groups to the surface of inorganic compound particles. By hydrophobicizing the surface of the particles, the adsorption of chemical contaminants and moisture can be suppressed.

[0035] The refractive index n2 of the d-line of the first porous layer 112 is preferably 1.60 or less. If the refractive index n2 is 1.60 or less, a sufficient reflection reduction effect can be obtained from the optical design based on the relationship between the substrate 100, the organic resin layer 101, the second porous layer 113, and the aluminum oxide layer 104. The refractive index n2 of the d-line of the first porous layer 112 is preferably 1.10 or more and 1.60 or less, more preferably 1.20 or more and 1.50 or less, still more preferably 1.25 or more and 1.45 or less, and particularly preferably 1.30 or more and 1.40 or less.

[0036] The thickness tb of the first porous layer 112 may be determined by an optical design based on the refractive index n2, the wavelength of light to prevent reflection, and the relationship between the substrate 100, the organic resin layer 101, the second porous layer 113, and the aluminum oxide layer 104. However, a high antireflection effect can be expected if it is in the range of 5 nm or more and 100 nm or less. Further, from the viewpoint of facilitating the regeneration operation, the thickness tb of the first porous layer 112 is more preferably in the range of 5 nm or more and 50 nm or less, and still more preferably in the range of 5 nm or more and 30 nm or less.

[0037] It is preferable that the thickness ta of the organic resin layer 101 and the thickness tb of the first porous layer 112 satisfy the relationship of 0.2 < ta / tb < 1.0 and 20 nm < ta + tb < 58 nm. By satisfying the above relationship, both optical characteristics and ease of regeneration operation can be achieved. Further, it is preferable because the options of solvents that can be used for the regeneration operation are expanded.

[0038] <Second Porous Layer> The second porous layer 113 containing amorphous aluminum oxide is preferably a porous layer formed from amorphous material having aluminum oxide as a main component. From the viewpoint of simplifying the manufacturing method, the second porous layer 113 is preferably formed integrally with the aluminum oxide layer 104. The thickness of the second porous layer 113 is not particularly limited, but from the viewpoint of facilitating the regeneration operation, it is preferably thinner than the thickness of the first porous layer 112. The means for forming integrally will be described in the section of the manufacturing method.

[0039] (Aluminum Oxide Layer) The aluminum oxide layer 104 contains crystalline aluminum oxide having a concavo-convex structure 114a. The concavo-convex structure 114a of the aluminum oxide layer 104 has a cone shape whose thickness becomes thinner toward the atmosphere with a refractive index of 1.0. That is, the aluminum oxide layer 104 is a concavo-convex structure (concavo-convex structure film) having a region that changes substantially continuously. Here, "substantially continuously changing" means that the effective refractive index changes not because the refractive index of the film material itself changes continuously, but because the space filling rate of a fine concavo-convex structure with an average pitch of 400 nm or less changes continuously. This is due to the property that light does not recognize concavo-convex shapes smaller than its own wavelength and recognizes the concavo-convex structure as a medium with an effective refractive index.

[0040] The concavo-convex structure 114a is preferably formed from a crystal mainly composed of aluminum oxide. The amorphous aluminum oxide of the second porous layer 113 and the crystalline aluminum oxide of the aluminum oxide layer 104 can be distinguished, for example, by a transmission electron microscope.

[0041] The aluminum oxide layer 104 is preferably a layer in which the refractive index continuously increases from the surface layer side toward the substrate 100 side. FIG. 3 is a schematic diagram showing an example of the refractive index of the aluminum oxide layer 104. As shown in FIG. 3, the refractive index with respect to the film thickness (the thickness of the aluminum oxide layer) can be represented by, for example, a straight line as in (a) or curves as in (b) and (c). By the refractive index continuously rising from the surface layer side toward the substrate side, the reflectance reduction effect becomes larger compared to when layers with higher refractive indices are laminated in order from the surface layer side.

[0042] The aluminum oxide layer 104 is preferably formed from a crystal mainly composed of aluminum oxide, hydroxide, or hydrate thereof. Boehmite is a particularly preferred crystal. In this specification, aluminum oxide, hydroxide, or hydrate thereof is referred to as "aluminum oxide." Furthermore, the aluminum oxide layer 104 has crystals of various sizes arranged randomly, with their upper ends forming protrusions. Therefore, it is necessary to control the precipitation and growth of the crystals in order to change the height, size, angle, and spacing of the protrusions. The aluminum oxide layer 104 may be divided into protrusions and a lower layer. Such a lower layer may consist of aluminum oxide alone or aluminum oxide with ZrO ２ SiO ２ , TiO ２ It may also contain 30 mol% or less of either ZnO or MgO. Alternatively, the lower layer may be a porous layer containing amorphous aluminum oxide, which is the second porous layer 113.

[0043] The thickness of the aluminum oxide layer 104 is not particularly limited, but is preferably in the range of 20 nm to 1000 nm, and more preferably in the range of 50 nm to 1000 nm. When the thickness of the aluminum oxide layer 104 is within the above range, the anti-reflective performance due to the protrusions of the uneven structure is effective, there is no risk of the mechanical strength of the protrusions of the uneven structure being impaired, and the manufacturing cost of the protrusions of the uneven structure is also advantageous. Furthermore, it is more preferable because it further enhances the anti-reflective performance.

[0044] The aluminum oxide layer 104 may contain phosphoric acid. In this case, the phosphoric acid generally tends to make the regeneration process difficult, but with the configuration in which the porous layer 112 is provided on top of the organic resin layer 101 described above, the regeneration process can be carried out without any problems even if the aluminum oxide layer contains phosphoric acid.

[0045] As described above, the optical member 10 of the first embodiment comprises a base material 100, an organic resin layer 101, a porous layer 102, and a crystalline aluminum oxide layer 104 having an uneven structure, in this order, wherein the organic resin layer 101 contains a polymer having an aromatic ring in its main chain and / or a polymer having an imide ring in its main chain. Furthermore, the porous layer 102 includes at least a first porous layer containing a material different from amorphous aluminum oxide. Therefore, in the regeneration process of peeling off each layer with a solvent, the organic resin layer 101 is less likely to react with amorphous aluminum oxide, and the film quality of the organic resin layer 101 is less likely to change. In addition, since the solvent easily penetrates from the porous layer 102 into the organic resin layer 101, it promotes the dissolution of the organic resin layer and makes it easy to peel off. Therefore, the regeneration process using a solvent can be easily carried out. Furthermore, the refractive index and thickness of each layer of the optical member 10 can be easily adjusted by the coating liquid or application conditions used to form each layer. For example, by determining the coating liquids that form the organic resin layer 101, the first porous layer 112, and the second porous layer 113, it becomes possible to realize a low-reflectivity component simply by adjusting the application conditions of the coating liquids for each layer to achieve the thickness required for the optical design, regardless of the material (refractive index) of the substrate. As a result, it becomes easier to adapt to changes in the substrate 100, and productivity is improved.

[0046] [Second Embodiment] Figure 4 is a schematic cross-sectional view of the member according to the second embodiment, cut in the lamination direction. The member 10A of the second embodiment differs from that of the first embodiment in that it includes a third porous layer 202 between the first porous layer 112 and the second porous layer 113. The differences from the first embodiment will be described below.

[0047] (Third porous layer) The third porous layer 202 is a mixed layer consisting of the components contained in the first porous layer 112 and the components contained in the second porous layer 113. From the viewpoint of making it easier to design the optical properties, it is preferable that the thickness of the third porous layer 202 is thinner than the thickness of the first porous layer 112. From the same viewpoint, it is preferable that the thickness of the third porous layer 202 is thinner than the thickness of the second porous layer 113.

[0048] The third porous layer 202 serves to enhance the adhesion between the first porous layer 112 and the second porous layer 113. Therefore, when performing a regeneration operation using a solvent, the first porous layer 112, the third porous layer 202, and the second porous layer 113 of member 10A can be easily peeled off together without peeling at the lamination interface. Thus, member 10A can be regenerated more easily than member 10.

[0049] [Third Embodiment] Figure 5 is a schematic cross-sectional view of the member according to the third embodiment, cut in the direction of lamination. The member 10B of the third embodiment differs from that of the first embodiment in that it has an aluminum oxide layer 104 on top of the first porous layer 112B. The differences from the first embodiment will be described below.

[0050] (First porous layer 112B) The first porous layer 112B includes a material different from amorphous aluminum oxide and an amorphous aluminum oxide material. The first porous layer 112B has fewer voids than the first porous layer 112 which does not contain the amorphous aluminum oxide layer. Because member 10B has the first porous layer 112B, it has fewer intermediate layers than member 10. If there are many layers, there will be many interfaces between the laminated layers, but in that case, the possibility of solvent clogging will increase. If clogging occurs, the solvent may not be able to reach the organic resin layer 101 easily. However, because member 10B has fewer intermediate layers, the solvent can reach the organic resin layer 101 more easily. Therefore, the recycling process can be performed more easily on member 10B than on member 10.

[0051] [Fourth Embodiment] Figure 6A is a schematic cross-sectional view of a member according to the fourth embodiment, cut from the lamination direction. Figure 6B is a schematic cross-sectional view of a member according to a modified example of the fourth embodiment, cut from the lamination direction. The members 10C and 10D of the fourth embodiment differ from those of the first embodiment in that they are provided with functional layers 105C and 105D on top of the aluminum oxide layer 104. The differences from the first embodiment will be described below.

[0052] (Functional layer) The functional layer 105 has one of the functions selected from the group consisting of antifouling, hydrophilicity, antibacterial properties, antiviral properties, protection, and decoration. The surface of the functional layer 105 may be flat, as shown by part number 105C in Figure 6A, or it may have a shape that follows the uneven structure 114a, as shown by part number 105D in Figure 6B.

[0053] Preferred functional layers with antifouling properties (antifouling layers) include, for example, layers containing fluoropolymers, fluorosilane monolayers, and layers containing titanium dioxide particles. Layers with water-repellent properties, such as fluoroalkylsilanes and alkylsilanes, also possess antifouling properties.

[0054] As a functional layer having hydrophilicity (hydrophilic layer), for example, a hydrophilic polymer layer is preferred, and a layer containing a polymer having amphoteric hydrophilic groups such as sulfobetaine groups, carbobetine groups, and phosphorcholine groups is particularly preferred.

[0055] Examples of functional layers with antibacterial and antiviral properties include layers with antibacterial properties such as copper compounds and silver compounds.

[0056] As a functional protective layer (protective layer), a layer containing phosphoric acid or a layer containing a hard coat resin is preferred. Although using a protective layer containing phosphoric acid generally tends to make regeneration work difficult, the configuration in which a porous layer 112 is provided on top of the organic resin layer 101 as described above allows for regeneration work to be performed without problems even if the protective layer contains phosphoric acid.

[0057] The decorative functional layer (decorative layer) is preferably a layer containing resin. The design can be enhanced by providing a textured surface with the same scale as, or a different size than, the textured surface of the aluminum oxide layer. The textured surface may also be formed by dimples.

[0058] Furthermore, if another layer is provided on top of the functional layer 105, the functional layer 105 functions as an adhesive layer. Suitable adhesive layers include, for example, acrylic resin and epoxy resin.

[0059] [Optical Equipment and Imaging Devices] The following explanation uses interchangeable lenses and single-lens reflex digital cameras as examples, but the devices are not limited to these; smartphones and compact digital cameras are also acceptable.

[0060] Figure 7 shows the configuration of the imaging device, a single-lens reflex digital camera 600. In Figure 7, the camera body 602 and the lens barrel 601, which is an optical component, are connected. The lens barrel 601 is a so-called interchangeable lens that can be attached to and detached from the camera body 602.

[0061] Light from the subject is captured when it passes through an optical system consisting of multiple lenses 603, 605, etc., which are examples of components arranged on the optical axis of the imaging optical system inside the housing of the lens barrel 601, and is received by the image sensor. Here, lens 605 is supported by the inner barrel 604 and is movablely supported relative to the outer barrel of the lens barrel 601 for focusing and zooming.

[0062] During the observation period before shooting, light from the subject is reflected by the main mirror 607, which is an example of a component inside the camera body housing 621, passes through the prism 611, and the image is projected onto the photographer through the viewfinder lens 612. The main mirror 607 is, for example, a half-mirror, and the light that passes through the main mirror is reflected by the sub-mirror 608 towards the AF (autofocus) unit 613, and this reflected light is used, for example, for distance measurement. The main mirror 607 is also attached and supported to the main mirror holder 640 by adhesive or the like. During shooting, the main mirror 607 and sub-mirror 608 are moved out of the optical path via a drive mechanism (not shown), the shutter 609 is opened, and the image of the photographic light incident from the lens barrel 601 is projected onto the image sensor 610. The aperture 606 is configured to change the brightness and depth of field during shooting by changing the aperture area.

[0063] The optical elements 10, 10A, and 10B described above can be used in at least one of the lenses 603 and 605. When optical elements 10, 10A, and 10B are used in an imaging optical system, the reflection of light from the surface of the elements is suppressed as light from the outside passes through the imaging optical system and is formed on the image sensor, improving light transmittance and significantly reducing flare and ghosting. As a result, it becomes possible to acquire high-quality images.

[0064] [Sixth Embodiment] Next, the manufacturing method of member 10 will be described, and the manufacturing methods of members 10A and 10B will also be mentioned along the way. Note that the manufacturing method of member 10 is not limited to the method exemplified below.

[0065] (Method for Manufacturing the Component) Figure 8 is a flowchart showing one embodiment of the method for manufacturing the component 10, and the method for manufacturing the component may include the following steps: (S01) Step of preparing a substrate (S02) Step of applying a first coating solution, which is a solution of a polymer having an aromatic ring in its main chain and / or a polymer having an imide ring in its main chain, onto the substrate to form an organic resin layer (S03) Step of applying a second coating solution, which contains a material different from amorphous aluminum oxide, onto the organic resin layer to form a porous layer (S04) Step of applying a third coating solution, which is an aluminum oxide precursor sol, onto the porous layer and curing the third coating solution to obtain a coating film (S05) Step of immersing the coating film in hot water to form an aluminum oxide layer containing crystalline aluminum oxide having an uneven structure (S06) Step of wiping the component with a solvent to remove the multilayer film and regenerate it when a manufacturing defect occurs after the aluminum oxide layer has been formed

[0066] The following describes each step.

[0067] [(S01) Step of preparing the substrate] First, prepare the substrate 100. The substrate 100 may be washed with a solvent, UV cleaning, etc., as needed.

[0068] [(S02) Step of forming an organic resin layer by applying a first coating solution of a polymer having an aromatic ring in its main chain and / or a polymer having an imide ring in its main chain onto a substrate] The polymer having an imide ring used to form the organic resin layer 101 can be produced by the following method, except for polyimide. For example, it can be synthesized by a monomer having an aromatic ring alone or by a polyaddition reaction or polycondensation reaction between a bifunctional monomer having an aromatic ring and a bifunctional monomer with a different functional group. The type of polymer varies depending on the type of functional group. For example, aromatic polycarbonate is synthesized by a polycondensation reaction between an aromatic monomer such as bisphenol A and phosgene. Aromatic polyurethane is synthesized by a polyaddition reaction between diphenylmethane diisocyanate and a diol. Although polyimide can also be synthesized from a monomer having an imide ring by a polyaddition reaction or polycondensation reaction, it is generally synthesized by a polyaddition reaction and dehydration condensation reaction between an acid dianhydride and a diamine. A key feature is the ability to select combinations from various monomers to satisfy the required properties. For example, by introducing aliphatic chains, alicyclic structures, or fluoroalkyl groups into diamines and / or acidic dianhydrides, thermoplastic polyimides that are transparent in the visible light region and soluble in solvents can be obtained. In particular, by using acidic dianhydrides that have alicyclic structures and introducing various structures such as siloxane structures, aliphatic chains, alicyclic structures, and aromatic rings into the diamine, either individually or in combination, the refractive index can be arbitrarily changed from 1.50 to 1.90.

[0069] Examples of acid dianhydrides used in the synthesis of thermoplastic polyimides include pyromellitic anhydride, 3,3'-biphthalic anhydride, 3,4'-biphthalic anhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 4,4'-oxydiphthalic anhydride, and other aromatic acids, as well as anhydrides, meso-butane-1,2,3,4-tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, and 1,2,3,4-cyclopentanetetracarboxylic dianhydride. Examples of aliphatic acid dianhydrides include 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, bicyclo[2.2.2]octo-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic acid dianhydride, bicyclo[2.2.1]heptane-2,3,5,6-tetracarboxylic acid dianhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, and 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride. From the viewpoint of improving the solubility, coatability, and transparency of the polyimide, 3,3',4,4'-diphenylsulfontetracarboxylic dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.1]heptane-2,3,5,6-tetracarboxylic dianhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexen-1,2-dicarboxylic anhydride, and 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride are more preferred.

[0070] Examples of diamines used in the synthesis of thermoplastic polyimides include m-phenylenediamine, p-phenylenediamine, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, o-tolidine, m-tolidine, 4,4'-diaminobenzophenone, 1,1-bis(4-aminophenyl)cyclohexane, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, 4,4'-bis(3-aminophenoxy)biphenyl, bis[4-( Examples include aromatic diamines such as 4-aminophenoxy)phenyl]sulfone, 9,9-bis(4-aminophenyl)fluorene, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, and 2,2'-bis(trifluoromethyl)benzidine; aliphatic diamines such as 1,4-diaminobutane, 1,5-diaminopentane, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 4,4'-methylenebis(cyclohexylamine), 4,4'-methylenebis(2-methylcyclohexylamine), and 1,4-bis(aminomethyl)cyclohexane; and diamines containing a -Si-O-Si- group such as 1,3-bis(3-aminopropyl)tetramethyldisiloxane and 1,4-bis(3-aminopropyldimethylsilyl)benzene. From the viewpoint of adhesion to inorganic substrates such as glass, it is more preferable to include at least a -Si-O-Si- group-containing diamine such as 1,3-bis(3-aminopropyl)tetramethyldisiloxane or 1,4-bis(3-aminopropyldimethylsilyl)benzene.

[0071] Any solvent that dissolves both the monomer and the synthesized polymer can be used as the solvent for the synthesis of polymers having an imide ring in the main chain. For example, aprotic polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone can be used.

[0072] The solution after polymer synthesis can be used as is, but it may also be used after reprecipitation in a poor solvent, filtering and drying the polymer powder, and then dissolving it again in the solvent. It is preferable to reprecipitation in alcohols to remove various chemicals used during polymerization and unreacted monomers. It is also preferable to dry the polymer solution or isolated polymer powder in air or under reduced pressure at a temperature range of 50°C to 150°C to remove the solvent and other contaminants.

[0073] Suitable solvents for use in the first coating solution, which is a solution of a polymer having an aromatic ring and / or an imide ring in its main chain, are cyclopentanone, cyclohexanone, and γ-butyrolactone, and it is preferable that the total amount of these solvents is in the range of 50% by mass or more and 100% by mass or less of the total solvent.

[0074] In addition to the solvents mentioned above, other solvents include ketones such as 2-butanone and methyl isobutyl ketone; esters such as ethyl acetate, n-butyl acetate, 1-methoxy-2-acetoxypropane, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, methyl lactate, ethyl lactate, and propyl lactate; ethers such as tetrahydrofuran, dioxane, and diisopropyl ether; various aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; chlorinated hydrocarbons such as chloroform, methylene chloride, and tetrachloroethane; and other solvents such as N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and sulfolane. Furthermore, alcohols such as 1-butanol, methyl cellosolve, diglyme, and methoxypropanol can also be mixed and used.

[0075] In a polymer solution containing a polymer having an imide ring in its main chain, which is an example of a first coating liquid, components other than the polymer having an imide ring in its main chain can be mixed. In this case, it is preferable that the polymer having an imide ring in its main chain constitutes 60% to 100% by mass of the total nonvolatile content including the polymer.

[0076] Polymers without imide or aromatic rings in their main chain can be added if they are compatible with polymers having imide rings in their main chain. Examples of polymers without imide or aromatic rings include various polyacrylates, various polymethacrylates, polystyrene, aliphatic polyesters, aliphatic polyurethanes, aliphatic polyethers, and polycycloolefins. The content of polymers without imide rings in their main chain is in the range of 0% by mass or more and less than 40% by mass of the total nonvolatile content including the polymer; if it exceeds 40% by mass, the solvent resistance and mechanical properties will be significantly reduced. More preferably, it is in the range of 0% by mass or more and less than 20% by mass.

[0077] The polymer solution, which is the first coating liquid, can contain components other than the polymer. However, it is preferable that the amount of nonvolatile components, including the polymer, be less than 20% by mass. If it exceeds 20% by mass, transparency, film strength, and thickness uniformity will be impaired. To suppress changes in the film quality of the organic resin layer during the regeneration process, it is more preferable that the amount be in the range of 0% by mass or more and less than 10% by mass.

[0078] As a method for applying the polymer solution, which is the first coating liquid, known coating methods such as dipping, spin coating, spraying, printing, flow coating, and combinations thereof can be appropriately employed. In the step of forming an organic resin layer containing a polymer having an imide ring in its main chain, the applied polymer solution may be dried at 20°C to 150°C at atmospheric pressure or reduced pressure. It is preferable to form the organic resin layer 101 and the first porous layer 112 simultaneously. This involves applying a coating liquid containing a material different from amorphous aluminum oxide before drying the coating liquid containing a polymer having an aromatic ring in its main chain and / or a polymer having an imide ring in its main chain, and then drying. This improves the adhesion between the organic resin layer 101 and the first porous layer 112, making the regeneration work more efficient.

[0079] Furthermore, the following step of applying a coating liquid containing a material different from amorphous aluminum oxide onto the organic resin layer (S03) to form a first porous layer may be carried out continuously. The drying method may be appropriately selected from air drying by standing or rotating, or irradiation by hot air circulation oven, muffle oven, infrared rays, microwaves, or other light, radiation, or electromagnetic waves.

[0080] [(S03) Step of forming a porous layer by applying a second coating liquid containing a material different from amorphous aluminum oxide onto the organic resin layer] Next, the coating liquid for forming the first porous layer by applying a second coating liquid containing a material different from amorphous aluminum oxide will be described.

[0081] The second coating solution for forming the first porous layer 112 comprises components that constitute the particles 131 and binder 132 of the first porous layer 112, and a solvent. While organic solvents or water can be used as the solvent, when applied by spin coating, organic solvents are preferred because they allow for the formation of a uniform coating film. A coating solution containing a mixture of organic solvent and water can also be used, but the water content is preferably less than the organic solvent content. The water content is preferably in the range of 0.1 parts by mass to 20 parts by mass per 100 parts by mass of the solvent component of the coating solution, and more preferably in the range of 0.5 parts by mass to 15 parts by mass. If the water content is less than 0.1 parts by mass per 100 parts by mass of the solvent component, it becomes difficult to use the water-dispersed particle slurry directly in the coating solution. The water must be removed by solvent substitution or distillation before use, which may increase the cost of the coating solution and complicate the manufacturing process. If the water content exceeds 20 parts by mass per 100 parts by mass of the solvent component, it becomes difficult to form a uniform coating film, which may result in radial unevenness in the coating or the liquid accumulating at the edges of the substrate, making it difficult to form a uniform coating film.

[0082] The material, shape, and size of the particles contained in the coating solution are as described above. The average particle diameter of the particles contained in the coating solution can be calculated by extracting particles from the coating solution, washing them, drying them, obtaining images using TEM, measuring the Ferret diameter for 50 or more particles, and taking the average value of these measurements.

[0083] The binder that binds the particles together is preferably an inorganic material of the same nature as the particles. When silica particles are used as the particles, silica is preferred as the binder, and the binder component is preferably a silicon dioxide compound. By making all the solid components (solutes) contained in the coating liquid inorganic materials, the affinity with the solid components of the first coating liquid is reduced. Therefore, even if the second coating liquid that forms the first porous layer is applied before the organic resin layer hardens, the solutes remain substantially separated, making it possible to form individual layers. A preferred example of a silicon dioxide compound is a silicon dioxide oligomer obtained by hydrolysis and condensation of silicic acid esters.

[0084] Silica particles inherently possess silanol (Si-OH) groups on their surface. However, by mixing them with silicon oxide oligomers in the second coating solution, the number of silanol groups on the surface can be increased. As a result, the surface of the particles becomes more easily bonded. When the second coating solution is applied and then cured, multiple particles are bonded together by the cured silicon oxide oligomers, resulting in a film with high mechanical strength.

[0085] The content of the binder component in the second coating solution is preferably in the range of 0.2 parts by mass to 20 parts by mass per 100 parts by mass of solid components contained in the coating solution. More preferably, it is in the range of 1 part by mass to 15 parts by mass, and even more preferably, it is in the range of 3.0 parts by mass to 15 parts by mass. If the content of the binder component is in the range of 0.2 parts by mass to 20 parts by mass, it is possible to suppress weakening of particle bonding and a decrease in mechanical strength, as well as an increase in refractive index due to a high content of the binder component. Furthermore, it is also possible to suppress the disruption of particle arrangement by the binder component and the deterioration of visible light scattering of the resulting film.

[0086] The organic solvent used in the second coating solution should not cause particle aggregation or rapid thickening during the process. If the particles in the second coating solution remain uniformly dispersed, a coating film with uniformly distributed particles can be formed on the substrate. Conversely, if the particles in the second coating solution are aggregated, the substrate will be coated with aggregated particles, disrupting the particle arrangement and preventing the desired refractive index from being obtained. Furthermore, if the particle arrangement is disrupted, the wiping solvent used during the regeneration process will not penetrate easily and will not reach the underlying organic resin layer sufficiently.

[0087] Specific examples of organic solvents include the following: monohydric alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methylpropanol, 1-pentanol, 2-pentanol, cyclopentanol, 2-methylbutanol, 3-methylbutanol, 1-hexanol, 2-hexanol, 3-hexanol, 4-methyl-2-pentanol, 2-methyl-1-pentanol, 2-ethylbutanol, 2,4-dimethyl-3-pentanol, 3-ethylbutanol, 1-heptanol, 2-heptanol, 1-octanol, and 2-octanol; and dihydric or more alcohols such as ethylene glycol and triethylene glycol. Ether alcohols such as methoxyethanol, ethoxyethanol, propoxyethanol, isopropoxyethanol, butoxyethanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-propoxy-2-propanol, and 3-methoxy-1-butanol; ethers such as dimethoxyethane, diglyme (diethylene glycol dimethyl ether), tetrahydrofuran, dioxane, diisopropyl ether, dibutyl ether, and cyclopentyl methyl ether; esters such as ethyl formate, ethyl acetate, n-butyl acetate, methyl lactate, ethyl lactate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, and propylene glycol monomethyl ether acetate; various aliphatic or alicyclic hydrocarbons such as n-hexane, n-octane, cyclohexane, cyclopentane, and cyclooctane; and various aromatic hydrocarbons such as toluene, xylene, and ethylbenzene. Various ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone. Various chlorinated hydrocarbons such as chloroform, methylene chloride, carbon tetrachloride, and tetrachloroethane. Aprotic polar solvents such as N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and ethylene carbonate. It is also possible to use a mixture of two or more of these solvents.

[0088] From the viewpoint of particle dispersibility and coating properties, it is preferable that the organic solvent contained in the second coating solution is a water-soluble solvent having hydroxyl groups with 4 to 6 carbon atoms, comprising 30% or more of the solvent. In particular, a solvent containing one or more selected from the group consisting of ethoxyethanol, propoxyethanol, isopropoxyethanol, butoxyethanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-propoxy-2-propanol, 3-methoxy-1-butanol, and ethyl lactate is preferred.

[0089] Furthermore, the second coating solution may contain a surface treatment agent to improve particle dispersibility and stability over time, or to impart desired functions. Specifically, this could be an acid, but a fluorine-containing organic acid having two or more acidic groups on its surface is more preferable. When using silica particles, using silica particles to which a fluorine-containing organic acid has been added, which has two or more acidic groups on its surface, allows for the formation of a coating film in which the silica particles are aligned and deposited without disrupting the arrangement of the silica particles. Also, since the acidic groups modify the particles, for example, if there are two acidic groups, it is assumed that one acid can modify two adjacent particles. Therefore, bonding between particles via an acid with two or more acidic groups is also possible, increasing the number of bonds between particles and resulting in high film strength. In addition, by using silica particles to which a fluorine-containing organic acid has been added, chemical contamination and moisture adhesion can be suppressed, thus suppressing changes in optical performance in high-humidity environments. Chemical contamination can be expected to occur both from outside the substrate having the optical interference layer and from inside the substrate having the optical interference layer, but it can be suppressed in both cases. Therefore, regardless of the material of the component, changes in optical performance under high humidity conditions can be suppressed. Specific examples of organic acids containing fluorine and having two or more acidic groups on their surface include tetrafluorosuccinic acid, hexafluoroglutaric acid, octafluoroadipic acid, dodecafluorosuberic acid, and hexadecafluorosebatic acid. The organic acid containing fluorine and having two or more acidic groups on its surface is preferably included in an amount of 0.01 parts by mass to 10 parts by mass per 100 parts by mass of particles, and more preferably in an amount of 0.1 parts by mass to 5 parts by mass. If the amount of organic acid containing fluorine with two or more acidic groups on its surface is less than 0.01 parts by mass, moisture and chemical contaminants may be more easily adsorbed onto the particles. If the amount of organic acid containing fluorine with two or more acidic groups on its surface is greater than 10 parts by mass, the acidity of the acidic groups is not equal, so if it is present in excess, the reaction of the first acidic group may be prioritized, making it difficult to bond between particles.Therefore, moisture and chemical contaminants may be more easily adsorbed. Furthermore, the strength of the film may decrease.

[0090] The method for applying the second coating solution is not limited as long as it can be controlled to the desired thickness. Specifically, examples include spin coating, blade coating, roll coating, slit coating, printing, gravure coating, and dip coating. When manufacturing articles with three-dimensionally complex shapes such as concave surfaces, the spin coating method is particularly preferred because it is easier to obtain a coating film of uniform thickness. In the case of the spin coating method, the thickness can be controlled by adjusting the rotation speed, the concentration of the solid component of the coating solution, etc.

[0091] [(S04) Step of applying a third coating solution of aluminum oxide precursor sol onto the porous layer and curing the third coating solution to obtain a coating film] In the step of forming a second porous layer 113 containing amorphous aluminum oxide, the aluminum oxide precursor sol (third coating solution) placed on the first porous layer 112 is dried and / or fired at a temperature in the range of 50°C to 250°C. By doing so, a second porous layer 113 containing amorphous aluminum oxide can be formed. The higher the heat treatment temperature, the easier it is for the film to become denser, but if the heat treatment temperature exceeds 250°C, damage such as deformation will occur to the substrate. More preferably, it is 100°C to 200°C. The heating time depends on the heating temperature, but 10 minutes or more is preferable. A layer mainly composed of aluminum oxide can be formed on the first porous layer 112 by known CVD, PVD gas phase methods, liquid phase methods such as the sol-gel method, hydrothermal synthesis using inorganic salts, etc. A method is preferred in which a uniform anti-reflective layer can be formed on large areas and non-planar substrates, by coating an aluminum oxide precursor sol containing aluminum oxide, forming a gel film, and then treating the film with hot water to grow aluminum oxide crystals in a protruding manner. In other words, it is preferable that the second porous layer 113 and the aluminum oxide layer 104 be formed almost simultaneously by the hot water treatment of the gel film. By changing the hot water treatment conditions and proceeding with the reaction, a third porous layer 202 can be formed, as in member 10A, which consists of components contained in the first porous layer 112 and components containing the second porous layer 113. Furthermore, by proceeding with the reaction while forming the third porous layer 202, so that the second porous layer 113 becomes thinner, a morphology can be formed in which the components contained in the second porous layer 113 are included in the first porous layer 112, as in member 10B.

[0092] The raw materials for the gel film obtained from the aluminum oxide precursor sol include an aluminum compound and / or at least one compound of each of Zr, Si, Ti, Zn, and Mg together with the aluminum compound. ２ O ３ , ZrO ２ SiO ２ , TiO ２, as raw materials for ZnO and MgO, salt compounds such as various metal alkoxides, chlorides, and nitrates can be used. From the perspective of film-forming properties, especially for ZrO ２ , SiO ２ , TiO ２ it is preferable to use metal alkoxides as raw materials.

[0093] Examples of aluminum compounds include aluminum ethoxide, aluminum isopropoxide, aluminum - n - butoxide, aluminum - sec - butoxide, aluminum - tert - butoxide, aluminum acetylacetonate. Also, oligomers thereof, aluminum nitrate, aluminum chloride, aluminum acetate, aluminum phosphate, aluminum sulfate, aluminum hydroxide can be mentioned.

[0094] Specific examples of zirconium alkoxide include the following: zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetra n - propoxide, zirconium tetra isopropoxide, zirconium tetra n - butoxide, zirconium tetra t - butoxide.

[0095] As silicon alkoxide, various ones represented by the general formula Si(OR) ４ can be used. R includes the same or different lower alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, etc.

[0096] Examples of titanium alkoxide include tetramethoxy titanium, tetraethoxy titanium, tetra n - propoxy titanium, tetra isopropoxy titanium, tetra n - butoxy titanium, tetra isobutoxy titanium.

[0097] Examples of zinc compounds include zinc acetate, zinc chloride, zinc nitrate, zinc stearate, zinc oleate, zinc salicylate, and especially zinc acetate and zinc chloride are preferable.

[0098] Examples of magnesium compounds include magnesium alkoxides such as dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, and dibutoxymagnesium, as well as magnesium acetylacetonate and magnesium chloride.

[0099] Suitable solvents for the third coating solution include alcohols with 3 to 7 carbon atoms, such as 2-propanol, 1-butanol, 2-butanol, isobutanol, 1-pentanol, 2-pentanol, 3-pentanol, cyclopentanol, 3-methyl-1-butanol, 4-methyl-2-pentanol, 2-ethyl-1-butanol, 2,4-dimethyl-3-pentanol, methyl cellosolve, ethyl cellosolve, propyl cellosolve, isopropyl cellosolve, butyl cellosolve, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-propoxy-2-propanol, 1-butoxy-2-propanol, and 3-methoxy-1-butanol. It is preferable that the total amount of these solvents is 80% to 100% by mass of the total solvent.

[0100] Other solvents that can be used in combination include methanol, ethanol, ethylene glycol, n-hexane, n-octane, cyclohexane, cyclopentane, cyclooctane, toluene, xylene, ethylbenzene, ethyl acetate, butyl acetate, 1-methoxy-2-acetoxypropane, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, butyl formate, amyl formate, hexyl formate, methyl lactate, ethyl lactate, propyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dimethoxyethane, tetrahydrofuran, dioxane, diisopropyl ether, chloroform, methylene chloride, carbon tetrachloride, tetrachloroethane, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, and ethylene carbonate.

[0101] When using alkoxide raw materials, aluminum, zirconium, and titanium alkoxides, in particular, are highly reactive with water and undergo rapid hydrolysis upon contact with moisture in the air or the addition of water, resulting in turbidity and precipitation of the solution. Furthermore, aluminum salt compounds, zinc salt compounds, and magnesium salt compounds are difficult to dissolve in organic solvents alone, leading to low solution stability. To prevent these issues, it is preferable to add stabilizers to stabilize the solution.

[0102] Examples of stabilizers include β-diketone compounds such as acetylacetone, dipivaloylmethane, trifluoroacetylacetone, hexafluoroacetylacetone, benzoylacetone, dibenzoylmethane, 3-methyl-2,4-pentanedione, and 3-ethyl-2,4-pentanedione; β-ketoester compounds such as methyl acetoacetate, ethyl acetoacetate, allyl acetoacetate, benzyl acetoacetate, iso-propyl acetoacetate, tert-butyl acetoacetate, iso-butyl acetoacetate, 2-methoxyethyl acetoacetate, and methyl 3-keto-n-valericate; and alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine. The amount of stabilizer added is preferably about 1 molar ratio to the alkoxide or salt compound. Furthermore, after adding the stabilizer, it is preferable to add a catalyst to promote part of the reaction in order to form a suitable precursor. Examples of catalysts include nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, and ammonia.

[0103] The third coating solution, an aluminum oxide precursor sol, can be applied onto the first porous layer 112. The application method can be any known method, such as dipping, spin coating, spraying, printing, flow coating, or a combination thereof.

[0104] [(S05) Step of immersing the coating film in hot water to form an aluminum oxide layer containing crystalline aluminum oxide having an uneven structure] The coating film mainly composed of aluminum oxide formed on the porous layer by the above method precipitates aluminum oxide crystals when immersed in hot water or exposed to steam, and an uneven structure 114a like protrusions is formed on the surface. In this method, an amorphous aluminum oxide layer may remain below the protrusions in the layer having protrusions. By immersing the layer mainly composed of aluminum oxide in hot water, the surface of the layer mainly composed of aluminum oxide undergoes papillosis, etc., and some components dissolve. Due to the difference in the solubility of various hydroxides in hot water, crystals mainly composed of aluminum oxide precipitate and grow on the surface. The temperature of the hot water is preferably in the range of 40°C to 100°C. The hot water treatment time is about 5 minutes to 24 hours.

[0105] TiO ２ , ZrO ２ SiO ２ In layers primarily composed of aluminum oxide with added oxides such as ZnO and MgO, crystallization is achieved by utilizing the difference in the solubility of each component in hot water. Therefore, unlike the case of single-component aluminum oxide, the size of the protrusions can be controlled over a wide range by changing the composition of the inorganic components. As a result, it becomes possible to control the protrusions formed by the crystals over the aforementioned wide range. Furthermore, when ZnO is used as a minor component, co-deposition with aluminum oxide becomes possible, allowing for even wider control of the refractive index and achieving excellent anti-reflective performance.

[0106] [(S06) A process to regenerate the component by wiping it with a solvent to remove the multilayer film when a manufacturing defect occurs after forming the aluminum oxide layer.] This process is performed only when a manufacturing defect such as cracks or stains occurs after the above steps (S01) to (S05). This process involves wiping the manufactured component with a solvent to peel off all layers from the substrate in one go, making it ready for immediate regeneration. The solvent required for the regeneration process is not particularly limited as long as it can easily peel off all layers from the substrate in one go and return the substrate to its pre-film formation state without damaging it, but it is preferable that it is non-toxic and low-cost. In addition, the solvent required for the regeneration process can be a mixture of two or more solvents suitable for the type of substrate.

[0107] As described above, according to the manufacturing method of this disclosure, before forming an aluminum oxide layer containing crystalline aluminum oxide having an uneven structure, first, a first coating solution of a polymer having an aromatic ring in its main chain and / or an imide ring in its main chain is applied to the substrate to form an organic resin layer. Subsequently, a second coating solution containing a material different from amorphous aluminum oxide is applied to the organic resin layer to form a porous layer. Therefore, in the regeneration process in which each layer is peeled off with a solvent, the organic resin layer 101 is less likely to react with amorphous aluminum oxide, and the film quality of the organic resin layer 101 is less likely to change. In addition, since the solvent easily penetrates from the porous layer 102 into the organic resin layer 101, the dissolution of the organic resin layer is promoted and it is easy to peel off. Therefore, the regeneration process using a solvent can be carried out easily.

[0108] As shown below, components according to each example or comparative example were prepared and evaluated by sequentially applying coating liquids for forming each layer constituting the component onto the substrate.

[0109] <Fabrication of Components> The following flat glass and a spherical lens with a concave surface were prepared as base materials. In the following examples and comparative examples, an organic resin layer, a porous layer, and an aluminum oxide layer were provided on each base material to produce components with optical functions. Table 1 shows the type of glass and refractive index of the base materials used in each example or comparative example. Flat glass 1: φ30 mm, thickness 1 mm, one side polished Spherical lens 1: φ30 mm, radius of curvature 18.4 mm, center thickness 2 mm Components were produced by forming layers on the polished surface of the flat glass 1 and on the spherical lens 1. The coating liquid for forming each layer was applied using the spin coating method.

[0110] The fabricated components were evaluated using the following method.

[0111] <Evaluation of Material Film Thickness> The refractive index and film thickness of each layer of the material were evaluated using a high-speed spectroscopic ellipsometer (M-2000, manufactured by J.A. Wollam Japan). A flat glass plate 1 was placed in the high-speed spectroscopic ellipsometer, and the incident angle was changed within the range of 50° to 70°. The film thickness was calculated from the measurement results.

[0112] <Evaluation of Reflectance of Materials> The reflectance of perpendicularly incident light at the center of the flat glass 1 and at a half-opening angle of 30° of the spherical lens 1 was measured using a reflectometer (USPM-RU III, manufactured by Olympus Corporation). The reflectance was calculated as the average reflectance in the visible light region (400-700 nm) for the flat glass 1 and the spherical lens 1, and evaluated according to the following criteria: A: Average reflectance of 0% or more and 0.2% or less B: Average reflectance of greater than 0.2% and 0.6% or less C: Average reflectance of greater than 0.6% Materials with an evaluation of A or B were judged to have a good anti-reflective effect.

[0113] <Evaluation of wipeability with solvent (regeneration process)> The evaluation of wipeability with solvent (regeneration process) was performed as follows. After forming layers and fabricating the components, 200 g / cm³ was applied to the surface of the film applied to the polished surfaces of the flat glass 1 and spherical lens 1. ２The restoration process was evaluated by applying a moderate load and pressing cleaning paper (Nikon's Silbon paper) soaked in a solvent (a mixture of isohexane and ethanol in a 7:3 ratio) against the lens to wipe off all layers. The evaluation criteria were as follows: A: All layers were cleanly peeled off and wiped away, making it ready for immediate restoration and use. B: All layers were peeled off and wiped away except for a small portion, making it ready for restoration and use if the solvent wiping was repeated. C: All layers were peeled off and wiped away except for a small portion, making it ready for restoration and use if the solvent wiping was repeated with cleaning paper soaked in an abrasive. D: All layers were not cleanly peeled off, and some parts remained even after repeated solvent wiping with cleaning paper soaked in an abrasive, making it unusable for restoration. <Appearance Evaluation> The spherical lens 1 with the film applied was observed visually, and its appearance was evaluated. In particular, cracks in the peripheral area were evaluated. The peripheral area here refers to a 2 mm wide area along the outer edge of the concave surface. The appearance was evaluated according to the following criteria. A: Peripheral reflections are barely noticeable. B: Peripheral reflections are noticeable. C: Peripheral reflections are quite noticeable. For lenses rated A, there is almost no change in appearance from the center to the periphery of the lens, indicating that a good anti-reflective effect has been achieved. For lenses rated B, the anti-reflective effect is considered to be less than that of lenses rated A, but still sufficient. For lenses rated C, the anti-reflective effect is considered insufficient.

[0114] <Reliability Evaluation under High Temperature and High Humidity> Flat glass 1 with a film and spherical lens 1 were exposed to high temperature and high humidity conditions of 60°C and 90% for 1000 hours to evaluate the change in reflectance and appearance. The change in reflectance was evaluated according to the following criteria. The change in average reflectance after exposure to high temperature and high humidity was calculated relative to the average reflectance in the visible light region (400-700 nm) of flat glass 1 before exposure to high temperature and high humidity. A: Almost no change in reflectance (change in average reflectance less than 20%) B: Slight change in reflectance is observed (change in average reflectance between 20% and 50%) C: Large change in reflectance (change in average reflectance between 20% and 50%) The change in appearance was evaluated according to the following criteria. The spherical lens 1 after exposure to high temperature and high humidity was observed visually to evaluate the change in appearance. A: Almost no change in appearance B: Slight change in appearance, including minor scratches C: Significant change in appearance, including scratches, peeling, and clouding. Lenses rated A show almost no change in optical properties or appearance from the center to the periphery, indicating good reliability. Lenses rated B are inferior to those rated A, but still offer sufficient reliability. Lenses rated C are considered unreliable. The following provides a detailed explanation of the examples and comparative examples.

[0115] [Example 1] (Coating solution 1a, which is the first coating solution for forming an organic resin layer) 200 g of 4,4'-methylenebis(aminocyclohexane) (hereinafter referred to as DADCM, manufactured by Tokyo Chemical Industry Co., Ltd.) was gradually dissolved by adding hexane under reflux. After stopping the heating and leaving it at room temperature for several days, the precipitate was filtered off and dried under reduced pressure. 58 g of white solid alicyclic diamine DADCM was obtained.

[0116] Three types of diamines—the alicyclic diamine DADCM, the aromatic diamine 4,4'-bis(4-aminophenoxy)biphenyl (product name BODA: manufactured by Wakayama Seika Kogyo), and the siloxane-containing diamine 1,3-bis(3-aminopropyl)tetramethyldisiloxane (product name PAM-E: manufactured by Shin-Etsu Chemical Co., Ltd.)—were dissolved in N,N-dimethylacetamide (hereinafter referred to as DMAc) to a total of 12 mmol.

[0117] Approximately 12 mmol of dianhydride was added to this diamine solution while cooling it with water. The dianhydride used was 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride (product name TDA-100: manufactured by Shin Nippon Rika). The amount of DMAc was adjusted so that the total mass of the diamine and dianhydride was 20% by weight.

[0118] The solution was stirred at room temperature for 15 hours to carry out the polymerization reaction. Further dilution with DMAc was adjusted to 8% by weight, and then 7.4 ml of pyridine and 3.8 ml of acetic anhydride were added. The mixture was stirred at room temperature for 1 hour. The mixture was then stirred in an oil bath at 60-70°C for 4 hours. The polymerization solution was reprecipitation in methanol to remove the polymer, which was then washed several times in methanol. After drying at 60°C for 24 hours, a white to pale yellow powdered polyimide was obtained.

[0119] The obtained polyimide was dissolved in cyclohexanone to a solid content concentration of 2.5% by mass to obtain coating solution 1a.

[0120] (Coating liquid 2a, which is the second coating liquid for forming the first porous layer) PL-1 (particle size 15 nm, solid content concentration 12% by mass) manufactured by Fuso Chemical Co., Ltd. was used as an aqueous dispersion of cocoon-shaped silica particles. Ethyl lactate was added to 100 g of the aqueous dispersion of cocoon-shaped silica particles so that the solid content concentration was 1.3% by mass. Dodecafluorosuberic acid was added so that the mass ratio of cocoon-shaped silica particles to acid component was 100:1 to prepare a dispersion of cocoon-shaped silica particles.

[0121] In a separate container, 12.48 g of ethyl silicate was added to 13.82 g of ethanol and an aqueous nitric acid solution (3% concentration). The mixture was stirred at room temperature for 10 hours to prepare silica sol 1 (solid content concentration 11.5% by mass). Gas chromatography confirmed that no components of the starting material ethyl silicate remained.

[0122] Silica sol 1 was added so that the mass ratio of silica particles to silica sol component was 100:21. Furthermore, by mixing and stirring at room temperature for 2 hours, a coating solution 2a containing cocoon-shaped silica particles was obtained.

[0123] (Preparation of aluminum oxide precursor sol for forming the second porous layer and aluminum oxide layer, which are the third coating solution) 14.8 g of aluminum-sec-butoxide (ASBD, manufactured by Kawaken Fine Chemicals), 3.42 g of 3-methyl-2,4-pentanedione, and 2-ethylbutanol were mixed and stirred until homogeneous. 1.94 g of 0.01 M dilute hydrochloric acid was dissolved in a mixed solvent of 2-ethylbutanol / 1-ethoxy-2-propanol, and then slowly added to the aluminum-sec-butoxide solution and stirred for a while. The solvent was ultimately prepared to be a mixed solvent of 36.9 g of 2-ethylbutanol and 15.8 g of 1-ethoxy-2-propanol. Further stirring in an oil bath at 120°C for 2 to 3 hours or more prepared aluminum oxide precursor sol 3a. The average particle size measured by dynamic light scattering was 10 nm.

[0124] (Preparation of the component) After forming a coating film of coating liquid 1a on a substrate made of S-BSM14 using coating liquid 1a, a coating film made of coating liquid 2a was formed without curing the coating film of coating liquid 1a. Furthermore, a coating film made of coating liquid 3a was formed without curing the coating film of coating liquid 2a. The coating films made of coating liquids 1a, 2a, and 3a were heated at 140°C for 60 minutes to cure, and then the substrate was immersed in 80°C hot water for 20 minutes, and then dried at 60°C for 15 minutes. FE-SEM observation of the surface and cross-section of the obtained substrate revealed a component of Example 1 in which a fine, uneven structure with protruding structures formed by randomly grown plate-like crystals mainly composed of aluminum oxide was observed. The thicknesses of each layer of the component of Example 1 were 27.3 nm, 19.5 nm, 15.5 nm, and 226.4 nm, respectively, from the substrate.

[0125] [Example 2] (Coating solution 1b, which is the first coating solution for forming an organic resin layer) Two types of diamines, the aromatic diamine 4,4'-bis(4-aminophenoxy)biphenyl (product name BODA: manufactured by Wakayama Seika Kogyo) and the siloxane-containing diamine 1,3-bis(3-aminopropyl)tetramethyldisiloxane (product name PAM-E: manufactured by Shin-Etsu Chemical Co., Ltd.), were dissolved in N,N-dimethylacetamide (hereinafter referred to as DMAc) to a total of 12 mmol.

[0126] Approximately 12 mmol of dianhydride was added to this diamine solution while cooling it with water. The dianhydride used was 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride (product name TDA-100: manufactured by Shin Nippon Rika). The amount of DMAc was adjusted so that the total mass of the diamine and dianhydride was 20% by weight.

[0127] The solution was stirred at room temperature for 15 hours to carry out the polymerization reaction. Further dilution with DMAc was adjusted to 8% by weight, and then 7.4 ml of pyridine and 3.8 ml of acetic anhydride were added. The mixture was stirred at room temperature for 1 hour. The mixture was then stirred in an oil bath at 60-70°C for 4 hours. The polymerization solution was reprecipitation in methanol to remove the polymer, which was then washed several times in methanol. After drying at 60°C for 24 hours, a white to pale yellow powdered polyimide was obtained.

[0128] The obtained polyimide was dissolved in cyclohexanone to obtain coating solution 1b, with a solid content concentration of 1.8% by mass.

[0129] (Coating liquid 2b, which is the second coating liquid for forming the first porous layer) PL-1 (particle size 15 nm, solid content concentration 12% by mass) manufactured by Fuso Chemical Co., Ltd. was used as an aqueous dispersion of cocoon-shaped silica particles. Ethyl lactate was added to 100 g of the aqueous dispersion of cocoon-shaped silica particles so that the solid content concentration was 1.5% by mass. Dodecafluorosuberic acid was added so that the mass ratio of cocoon-shaped silica particles to acid component was 100:1 to prepare a dispersion of cocoon-shaped silica particles.

[0130] In a separate container, 12.48 g of ethyl silicate was added to 13.82 g of ethanol and an aqueous nitric acid solution (3% concentration). The mixture was stirred at room temperature for 10 hours to prepare silica sol 1 (solid content concentration 11.5% by mass). Gas chromatography confirmed that no components of the starting material ethyl silicate remained.

[0131] Silica sol 1 was added so that the mass ratio of silica particles to silica sol component was 100:21. Furthermore, by mixing and stirring at room temperature for 2 hours, a coating solution 2a containing cocoon-shaped silica particles was obtained.

[0132] (Preparation of aluminum oxide precursor sol for forming the second porous layer and aluminum oxide layer, which are the third coating solution) Aluminum oxide precursor sol 3a obtained in the same manner as coating solution 3a was used.

[0133] (Preparation of components) After forming a coating film of coating liquid 1b on a substrate made of S-TIL 26 using coating liquid 1b, a coating film made of coating liquid 2b was formed without curing the coating film of coating liquid 1b. Furthermore, a coating film made of coating liquid 3a was formed without curing the coating film of coating liquid 2b. The coating films made of coating liquids 1b, 2b, and 3a were heated at 140°C for 60 minutes to cure them, and then the substrate was immersed in 80°C hot water for 20 minutes, and then dried at 60°C for 15 minutes to obtain the component of Example 2. The thicknesses of each layer of the component of Example 2 were 18.8 nm, 26.0 nm, 15.5 nm, and 226.4 nm, respectively, from the substrate.

[0134] [Example 3] (Coating solution 1c, which is the first coating solution for forming an organic resin layer) Polyimide obtained in the same manner as coating solution 1a was dissolved in cyclohexanone to obtain coating solution 1c so that the solid content concentration was 2.2% by mass.

[0135] (Coating solution 2c, which is the second coating solution for forming the first porous layer) As a propylene glycol monomethyl ether dispersion of spherical solid silica (silicon oxide) particles, PGM-ST (particle size 10 nm, solid content concentration 30% by mass) manufactured by Nissan Chemical Corporation was used. 1-propoxy-2-propanol was added to 100 g of the propylene glycol monomethyl ether dispersion of solid silica particles so that the solid content concentration was 2.0% by mass.

[0136] In a separate container, 12.48 g of ethyl silicate was added to 13.82 g of ethanol and an aqueous nitric acid solution (3% concentration). The mixture was stirred at room temperature for 10 hours to prepare silica sol 2 (solid content concentration 11.5% by mass). Gas chromatography confirmed that no components of the starting material ethyl silicate remained.

[0137] Silica sol 2 was added to a dispersion of solid silica particles so that the silica particle:silica sol ratio was 25:3. Furthermore, the mixture was stirred at room temperature for 2 hours to obtain a coating solution 2c containing solid silica particles.

[0138] (Preparation of aluminum oxide precursor sol for forming the second porous layer and aluminum oxide layer, which are the third coating solution) Aluminum oxide precursor sol 3a obtained in the same manner as coating solution 3a was used.

[0139] (Preparation of components) After forming a coating film of coating liquid 1c on a substrate made of L-BSL7 using coating liquid 1c, a coating film made of coating liquid 2c was formed without curing the coating film of coating liquid 1c. Furthermore, a coating film made of coating liquid 3a was formed without curing the coating film of coating liquid 2c. The coating films made of coating liquids 1c, 2c, and 3a were heated at 140°C for 60 minutes to cure them, and then the substrate was immersed in 80°C hot water for 20 minutes, and then dried at 60°C for 15 minutes to obtain the component of Example 3. The thicknesses of each layer of the component of Example 3 were 32.8 nm, 28.5 nm, 15.5 nm, and 226.4 nm, respectively, from the substrate.

[0140] [Example 4] (Coating solution 1d, which is the first coating solution for forming an organic resin layer) Polyimide obtained in the same manner as coating solution 1b was dissolved in cyclohexanone to obtain coating solution 1d so that the solid content concentration was 2.1% by mass.

[0141] (Coating liquid 2d, which is the second coating liquid for forming the first porous layer) PL-1 (particle size 15 nm, solid content concentration 12% by mass) manufactured by Fuso Chemical Co., Ltd. was used as an aqueous dispersion of cocoon-shaped silica particles. Ethyl lactate was added to 100 g of the aqueous dispersion of cocoon-shaped silica particles so that the solid content concentration was 1.4% by mass. Dibenzenesulfonimide was added so that the mass ratio of cocoon-shaped silica particles to acid component was 100:1 to prepare a dispersion of cocoon-shaped silica particles.

[0142] Silica sol 1 was added so that the mass ratio of silica particles to silica sol component was 100:21. Furthermore, by mixing and stirring at room temperature for 2 hours, a coating solution 2d containing cocoon-shaped silica particles was obtained.

[0143] (Preparation of aluminum oxide precursor sol for forming the second porous layer and aluminum oxide layer, which are the third coating solution) Aluminum oxide precursor sol 3a obtained in the same manner as coating solution 3a was used.

[0144] (Preparation of components) After forming a coating film of coating liquid 1d on a substrate made of L-BAL42 using coating liquid 1d, a coating film made of coating liquid 2d was formed without curing the coating film of coating liquid 1d. Furthermore, a coating film made of coating liquid 3a was formed without curing the coating film of coating liquid 2d. The coating films made of coating liquids 1d, 2d, and 3a were heated at 140°C for 60 minutes to cure them, and then the substrate was immersed in 80°C hot water for 20 minutes, and then dried at 60°C for 15 minutes to obtain the component of Example 4. The thicknesses of each layer of the component of Example 4 were 17.9 nm, 24.2 nm, 15.5 nm, and 226.4 nm, respectively, from the substrate.

[0145] [Example 5] (Coating solution 1e, which is the first coating solution for forming an organic resin layer) Polyimide obtained in the same manner as coating solution 1a was dissolved in cyclohexanone to obtain coating solution 1e so that the solid content concentration was 2.0% by mass.

[0146] (Coating liquid 2e, which is the second coating liquid for forming the first porous layer) PL-1 (particle size 15 nm, solid content concentration 12% by mass) manufactured by Fuso Chemical Co., Ltd. was used as an aqueous dispersion of cocoon-shaped silica particles. 1-ethoxy-2-propanol was added to 100 g of the aqueous dispersion of cocoon-shaped silica particles so that the solid content concentration was 1.4% by mass. Dibenzenesulfonimide was added so that the mass ratio of cocoon-shaped silica particles to acid component was 100:4 to prepare a dispersion of cocoon-shaped silica particles.

[0147] Silica sol 1 was added so that the mass ratio of silica particles to silica sol component was 100:19. Furthermore, by mixing and stirring at room temperature for 2 hours, a coating solution 2e containing cocoon-shaped silica particles was obtained.

[0148] (Preparation of aluminum oxide precursor sol for forming the second porous layer and aluminum oxide layer, which are the third coating solution) Aluminum oxide precursor sol 3a obtained in the same manner as coating solution 3a was used.

[0149] (Preparation of components) After forming a coating film of coating liquid 1e on a substrate made of L-BAL42 using coating liquid 1e, a coating film made of coating liquid 2e was formed without curing the coating film of coating liquid 1e. Furthermore, a coating film made of coating liquid 3a was formed without curing the coating film of coating liquid 2e. The coating films made of coating liquids 1e, 2e, and 3a were heated at 140°C for 60 minutes to cure them, and then the substrate was immersed in 80°C hot water for 20 minutes, and then dried at 60°C for 15 minutes to obtain the component of Example 5. The thicknesses of each layer of the component of Example 5 were 30.5 nm, 20.9 nm, 15.5 nm, and 226.4 nm, respectively, from the substrate.

[0150] [Example 6] (Coating liquid 1f, which is the first coating liquid for forming an organic resin layer) A branched melamine polymer photocurable coating (product name: Hypertech UR101, manufactured by Nissan Chemical Corporation) was diluted to a concentration of 1.0% by mass with a cyclopentanone / cyclohexanone mixed solvent to prepare a branched melamine polymer solution. 30.0 g of the branched melamine polymer solution and 15.0 g of coating liquid 1b prepared in Example 2 were stirred and mixed at room temperature to prepare a blended polymer coating liquid 1f of branched melamine polymer and polyimide.

[0151] (Coating liquid 2f, which is the second coating liquid for forming the first porous layer) PL-1 (particle size 15 nm, solid content concentration 12% by mass) manufactured by Fuso Chemical Co., Ltd. was used as an aqueous dispersion of cocoon-shaped silica particles. Ethyl lactate was added to 100 g of the aqueous dispersion of cocoon-shaped silica particles so that the solid content concentration was 1.4% by mass. Dodecafluorosuberic acid was added so that the mass ratio of cocoon-shaped silica particles to acid component was 100:2 to prepare a dispersion of cocoon-shaped silica particles.

[0152] In a separate container, 12.48 g of ethyl silicate was added to 13.82 g of ethanol and an aqueous nitric acid solution (3% concentration). The mixture was stirred at room temperature for 10 hours to prepare silica sol 1 (solid content concentration 11.5% by mass). Gas chromatography confirmed that no components of the starting material ethyl silicate remained.

[0153] Silica sol 1 was added so that the mass ratio of silica particles to silica sol components was 100:20. Furthermore, by mixing and stirring at room temperature for 2 hours, a coating solution 2f containing cocoon-shaped silica particles was obtained.

[0154] (Preparation of aluminum oxide precursor sol for forming the second porous layer and aluminum oxide layer, which are the third coating solution) Aluminum oxide precursor sol 3a obtained in the same manner as coating solution 3a was used.

[0155] (Preparation of components) After forming a coating film of coating liquid 1f on a substrate made of S-BSM14 using coating liquid 1f, a coating film made of coating liquid 2f was formed without curing the coating film of coating liquid 1f. Furthermore, a coating film made of coating liquid 3a was formed without curing the coating film of coating liquid 2f. The coating films made of coating liquids 1f, 2f, and 3a were heated at 140°C for 60 minutes to cure them, and then the substrate was immersed in 80°C hot water for 20 minutes, and then dried at 60°C for 15 minutes to obtain the component of Example 6. The thicknesses of each layer of the component of Example 6 were 6.0 nm, 23.3 nm, 15.5 nm, and 226.4 nm, respectively, from the substrate.

[0156] [Example 7] (1 g of coating solution, which is the first coating solution for forming an organic resin layer) A branched melamine polymer photocurable coating (product name: Hypertech UR101, manufactured by Nissan Chemical Corporation) was diluted to a concentration of 2.5% by mass with a cyclopentanone / cyclohexanone mixed solvent to prepare a branched melamine polymer solution. 30.0 g of the branched melamine polymer solution and 25.0 g of the coating solution 1a prepared in Example 1 were stirred and mixed at room temperature to prepare 1 g of a blended polymer coating solution of branched melamine polymer and polyimide.

[0157] (2 g of coating solution, which is the second coating solution for forming the first porous layer) PL-1 (particle size 15 nm, solid content concentration 12% by mass) manufactured by Fuso Chemical Co., Ltd. was used as an aqueous dispersion of cocoon-shaped silica particles. 1-ethoxy-2-propanol was added to 100 g of the aqueous dispersion of cocoon-shaped silica particles so that the solid content concentration was 2.4% by mass. Dibenzenesulfonimide was added so that the mass ratio of cocoon-shaped silica particles to acid component was 100:2 to prepare a dispersion of cocoon-shaped silica particles.

[0158] Silica sol 1 was added so that the mass ratio of silica particles to silica sol component was 100:19. Furthermore, by mixing and stirring at room temperature for 2 hours, 2 g of coating solution containing cocoon-shaped silica particles was obtained.

[0159] (Preparation of aluminum oxide precursor sol for forming the second porous layer and aluminum oxide layer, which are the third coating solution) Aluminum oxide precursor sol 3a obtained in the same manner as coating solution 3a was used.

[0160] (Preparation of the component) Using 1 g of coating solution, a coating film of 1 g of coating solution was formed on a synthetic quartz substrate. Without curing the coating film of 1 g of coating solution, a coating film of 2 g of coating solution was subsequently formed. Furthermore, without curing the coating film of 2 g of coating solution, a coating film of 3 a was subsequently formed. The coating films made of 1 g, 2 g, and 3 a were heated at 140°C for 60 minutes to cure, and then the substrate was immersed in 80°C hot water for 20 minutes, followed by drying at 60°C for 15 minutes to obtain the component of Example 7. The thicknesses of each layer of the component of Example 7 were 25.4 nm, 40.6 nm, 15.5 nm, and 226.4 nm, respectively, from the substrate.

[0161] [Example 8] (Coating solution 1h, which is the first coating solution for forming an organic resin layer) A branched melamine polymer photocurable coating (product name: Hypertech UR101, manufactured by Nissan Chemical Corporation) was diluted to a concentration of 3.0% by mass with a cyclopentanone / cyclohexanone mixed solvent to prepare a branched melamine polymer solution. 30.0 g of the branched melamine polymer solution and 25.0 g of the coating solution 1a prepared in Example 1 were stirred and mixed at room temperature to prepare a blended polymer coating solution 1h of branched melamine polymer and polyimide.

[0162] (Coating solution 2h, which is the second coating solution for forming the first porous layer) As an isopropyl alcohol dispersion of chain-like silica (silicon oxide) particles, IPA-ST-UP (particle size 40-100 nm, solid content concentration 15% by mass) manufactured by Nissan Chemical Corporation was used. 1-propoxy-2-propanol was added to 100 g of the isopropyl alcohol dispersion of chain-like silica particles so that the solid content concentration was 1.0% by mass.

[0163] In a separate container, 10 g of 0.1% dilute hydrochloric acid, 30 g of isopropyl alcohol, and 12 g of methyl polysilicate (methyl silicate 53A manufactured by Colcoat Co., Ltd.) were slowly added, and the mixture was stirred at room temperature for 240 minutes to prepare silica sol 3.

[0164] Silica sol 3 was added to a dispersion of chain-like silica particles so that the silica particle:silica sol ratio was 25:8. Furthermore, the mixture was stirred and mixed at room temperature for 2 hours to obtain a coating solution 2h containing chain-like silica particles.

[0165] (Preparation of aluminum oxide precursor sol for forming the second porous layer and aluminum oxide layer, which are the third coating solution) Aluminum oxide precursor sol 3a obtained in the same manner as coating solution 3a was used.

[0166] (Preparation of the component) After forming a coating film of coating liquid 1h on a substrate made of S-LAH79 using coating liquid 1h, a coating film made of coating liquid 2h was formed without curing the coating film of coating liquid 1h. Furthermore, a coating film made of coating liquid 3a was formed without curing the coating film of coating liquid 2h. The coating films made of coating liquids 1h, 2h, and 3a were heated at 140°C for 60 minutes to cure, then the substrate was immersed in 80°C hot water for 20 minutes, dried at 60°C for 15 minutes, and then phosphoric acid solution was applied and heated at 150°C for 30 minutes to obtain the component of Example 8. The thicknesses of each layer of the component of Example 8 were 49.7 nm, 15.4 nm, 15.5 nm, and 226.4 nm, respectively, from the substrate.

[0167] [Example 9] (Coating solution 1i, which is the first coating solution for forming an organic resin layer) 6.00 g of N-benzylmaleimide (hereinafter abbreviated as BzMI), 4.30 g of N-cyclohexylmaleimide, and 0.07 g of 2,2'-azobis(isobutyronitrile) (hereinafter abbreviated as AIBN) were dissolved in 25.8 g of toluene with stirring. This solution was repeatedly degassed and nitrogen replaced while being cooled with ice water, and then stirred at 60-70°C for 7 hours with nitrogen flow. The polymerization solution was slowly added to strongly stirred methanol, and the precipitated polymer was filtered off and then washed several times with stirring in methanol. The filtered polymer was vacuum dried at 80-90°C. A white powdery polymaleimide was obtained. Coating solution 1i was prepared by dissolving 2.5 g of polymaleimide powder and 0.5 g of the polyimide powder obtained in Example 2 in 97.0 g of 1-acetoxy-2-methoxypropane.

[0168] (Coating solution 2i, which is the second coating solution for forming the first porous layer) 10 g of 0.1% dilute hydrochloric acid, 100 g of 1-propoxy-2-propanol, and 2 g of methyl polysilicate (methyl silicate 51 manufactured by Colcoat Co., Ltd.) were slowly added and stirred at room temperature for 240 minutes to obtain coating solution 2i consisting of silica sol.

[0169] (Preparation of aluminum oxide precursor sol for forming the second porous layer and aluminum oxide layer, which are the third coating solution) 0.001 g of aluminum oxide particles (manufactured by Sigma-Aldrich: particle size 50 nm or less) and 10.0 g of the aluminum oxide precursor sol 3a prepared in Example 1 were mixed to prepare coating solution 3b, which was then used.

[0170] (Preparation of components) After forming a coating film of coating liquid 1h on a substrate made of S-NPH3 using coating liquid 1i, a coating film made of coating liquid 2i was formed without curing the coating film of coating liquid 1i. Furthermore, a coating film made of coating liquid 3b was formed without curing the coating film of coating liquid 2i. The coating films made of coating liquids 1i, 2i, and 3b were heated at 140°C for 60 minutes to cure them, and then the substrate was immersed in 80°C hot water for 20 minutes, and then dried at 60°C for 15 minutes to obtain the component of Example 9. The thicknesses of each layer of the component of Example 9 were 46.8 nm, 5.1 nm, 56.4 nm, and 185.5 nm, respectively, from the substrate.

[0171] [Example 10] (Coating solution 1j, which is the first coating solution for forming an organic resin layer) Polyimide obtained in the same manner as coating solution 1a was dissolved in cyclohexanone to obtain coating solution 1j with a solid content concentration of 3.2% by mass.

[0172] (Coating solution 2j, which is the second coating solution for forming the first porous layer) 1 g of dodecafluorosuberic acid diluted to 0.1% with 1-propoxy-2-propanol, 100 g of 1-propoxy-2-propanol, and 2 g of methyl polysilicate (methyl silicate 51 manufactured by Colcoat Co., Ltd.) were slowly added, and the mixture was stirred at room temperature for 240 minutes to obtain coating solution 2j consisting of silica sol.

[0173] (Preparation of aluminum oxide precursor sol for forming the second porous layer and aluminum oxide layer, which are the third coating solution) Aluminum oxide precursor sol 3a obtained in the same manner as coating solution 3a was used.

[0174] (Preparation of components) After forming a coating film of coating liquid 1j on a substrate made of S-BAH28 using coating liquid 1j, a coating film made of coating liquid 2j was formed without curing the coating film of coating liquid 1j. After drying at 140°C for 30 minutes, a coating film made of coating liquid 3a was formed. The coating films made of coating liquids 1j, 2j, and 3a were heated at 140°C for 60 minutes to cure them, and then the substrate was immersed in 80°C hot water for 20 minutes, and then dried at 60°C for 15 minutes to obtain the component of Example 10. The thicknesses of each layer of the component of Example 10 were 46.7 nm, 5.6 nm, 19.9 nm, and 226.4 nm, respectively, from the substrate.

[0175] [Example 11] (Coating solution 1k, which is the first coating solution for forming an organic resin layer) A branched melamine polymer photocurable coating (product name: Hypertech UR101, manufactured by Nissan Chemical Corporation) was diluted to a concentration of 0.9% by mass with a cyclopentanone / cyclohexanone mixed solvent to prepare a branched melamine polymer solution. 30.0 g of the branched melamine polymer solution and 15.0 g of the coating solution 1b prepared in Example 2 were stirred and mixed at room temperature to prepare a blended polymer coating solution 1k of branched melamine polymer and polyimide.

[0176] (Coating solution 2k, which is the second coating solution for forming the first porous layer) PL-1 (particle size 15 nm, solid content concentration 12% by mass) manufactured by Fuso Chemical Co., Ltd. was used as an aqueous dispersion of cocoon-shaped silica particles. Ethyl lactate was added to 100 g of the aqueous dispersion of cocoon-shaped silica particles so that the solid content concentration was 1.2% by mass. Dodecafluorosuberic acid was added so that the mass ratio of cocoon-shaped silica particles to acid component was 100:2 to prepare a dispersion of cocoon-shaped silica particles.

[0177] Silica sol 1 was added so that the mass ratio of silica particles to silica sol component was 100:21. Furthermore, by mixing and stirring at room temperature for 2 hours, a coating solution 2k containing cocoon-shaped silica particles was obtained.

[0178] (Preparation of aluminum oxide precursor sol for forming the second porous layer and aluminum oxide layer, which are the third coating solution) Aluminum oxide precursor sol 3a obtained in the same manner as coating solution 3a was used.

[0179] (Preparation of components) After forming a coating film of coating liquid 1k on a substrate made of S-BAH28 using coating liquid 1k, a coating film made of coating liquid 2k was formed without curing the coating film of coating liquid 1k. Furthermore, a coating film made of coating liquid 3a was formed without curing the coating film of coating liquid 2k. The coating films made of coating liquids 1k, 2k, and 3a were heated at 140°C for 60 minutes to cure them, and then the substrate was immersed in 80°C hot water for 20 minutes, and then dried at 60°C for 15 minutes to obtain the component of Example 11. The thicknesses of each layer of the component of Example 11 were 4.8 nm, 17.1 nm, 15.5 nm, and 226.4 nm, respectively, from the substrate.

[0180] [Example 12] (Coating liquid 1l, which is the first coating liquid for forming an organic resin layer) Coating liquid 1a and coating liquid 1b were mixed in a ratio of 40:60 to obtain coating liquid 1l.

[0181] (Coating solution 2L, which is the second coating solution for forming the first porous layer) As an aqueous dispersion of cocoon-shaped silica particles, PL-1 (particle size 15 nm, solid content concentration 12% by mass) manufactured by Fuso Chemical Co., Ltd. was used. Ethyl lactate was added to 100 g of the aqueous dispersion of cocoon-shaped silica particles so that the solid content concentration was 1.3% by mass. Dodecafluorosuberic acid was added so that the mass ratio of cocoon-shaped silica particles to acid component was 100:1 to prepare a dispersion of cocoon-shaped silica particles.

[0182] Silica sol 1 was added so that the mass ratio of silica particles to silica sol components was 100:20. Furthermore, by mixing and stirring at room temperature for 2 hours, a coating solution 2L containing cocoon-shaped silica particles was obtained.

[0183] (Preparation of aluminum oxide precursor sol for forming the second porous layer and aluminum oxide layer, which are the third coating solution) Aluminum oxide precursor sol 3a obtained in the same manner as coating solution 3a was used.

[0184] (Preparation of component) Using 1 liter of coating solution, a coating film of 1 liter of coating solution was formed on a polycarbonate resin (AD-5503) substrate. Without curing the coating film of 1 liter of coating solution, a coating film made of 2 liters of coating solution was subsequently formed. Furthermore, without curing the coating film of 2 liters of coating solution, a coating film made of 3 a was subsequently formed. The coating films made of 1 liter, 2 liters, and 3 a were heated at 140°C for 60 minutes to cure them. Next, the substrate was immersed in 80°C hot water for 20 minutes, and then dried at 60°C for 15 minutes to obtain the component of Example 12. The thicknesses of each layer of the component of Example 12 were 12.9 nm, 28.6 nm, 15.5 nm, and 226.4 nm, respectively, from the substrate.

[0185] [Example 13] (Coating solution 1n, which is the first coating solution for forming an organic resin layer) A branched melamine polymer photocurable coating (product name: Hypertech UR101, manufactured by Nissan Chemical Corporation) was diluted to a concentration of 4.5% by mass with a cyclopentanone / cyclohexanone mixed solvent to prepare a branched melamine polymer solution. 30.0 g of the branched melamine polymer solution and 25.0 g of coating solution 1a prepared in Example 1 were stirred and mixed at room temperature to prepare a blended polymer coating solution 1n of branched melamine polymer and polyimide.

[0186] (Coating solution 2n, which is the second coating solution for forming the first porous layer) PL-1 (particle size 15 nm, solid content concentration 12% by mass) manufactured by Fuso Chemical Co., Ltd. was used as an aqueous dispersion of cocoon-shaped silica particles. Ethyl lactate was added to 100 g of the aqueous dispersion of cocoon-shaped silica particles so that the solid content concentration was 1.1% by mass. Dodecafluorosuberic acid was added so that the mass ratio of cocoon-shaped silica particles to acid component was 100:1 to prepare a dispersion of cocoon-shaped silica particles.

[0187] Silica sol 2 was added so that the silica particle:silica sol component was in a mass ratio of 100:22. Furthermore, by mixing and stirring at room temperature for 2 hours, a coating solution 2n containing cocoon-shaped silica particles was obtained.

[0188] (Preparation of aluminum oxide precursor sol for forming the second porous layer and aluminum oxide layer, which are the third coating solution) Aluminum oxide precursor sol 3a obtained in the same manner as coating solution 3a was used.

[0189] (Preparation of components) After forming a coating film of coating liquid 1n on a substrate made of S-NPH3 using coating liquid 1n, a coating film made of coating liquid 2n was formed without curing the coating film of coating liquid 1n. Furthermore, a coating film made of coating liquid 3a was formed without curing the coating film of coating liquid 2n. The coating films made of coating liquids 1n, 2n, and 3a were heated at 140°C for 60 minutes to cure them, and then the substrate was immersed in 80°C hot water for 20 minutes, and then dried at 60°C for 15 minutes to obtain the component of Example 14. The thicknesses of each layer of the component of Example 14 were 73.1 nm, 16.3 nm, 15.5 nm, and 226.4 nm, respectively, from the substrate.

[0190] [Comparative Example 1] (Coating solution 1 m, which is the first coating solution for forming an organic resin layer) The white to pale yellow powdered polyimide obtained in Example 1 was dissolved in cyclohexanone to obtain a coating solution 1 m with a solid content concentration of 4.5% by mass.

[0191] (Coating liquid 2m, which is the second coating liquid for forming the first porous layer) In Comparative Example 1, the coating liquid 2m for forming the first porous layer, which contains a material different from amorphous aluminum oxide, was not used.

[0192] (Preparation of aluminum oxide precursor sol for forming the second porous layer and aluminum oxide layer, which are the third coating solution) Aluminum oxide precursor sol 3a obtained in the same manner as coating solution 3a was used.

[0193] (Preparation of components) After forming a coating film of coating liquid 1 m on a synthetic quartz substrate using coating liquid 1 m, a coating film of coating liquid 3a was subsequently formed without curing the coating film of coating liquid 1 m. The coating films made of coating liquid 1 m and 3a were heated at 140°C for 60 minutes to cure, and then the substrate was immersed in 80°C hot water for 20 minutes, and then dried at 60°C for 15 minutes to obtain the component of Comparative Example 1. The thicknesses of each layer of the component of Comparative Example 1 were 94.6 nm, 19.9 nm, and 226.4 nm, respectively, from the substrate.

[0194] [Comparative Example 2] The experiment was carried out without forming the organic resin layer and the first porous layer.

[0195] (Preparation of the component) A coating film made of coating liquid 3a was formed on a substrate made of S-LAH79 using coating liquid 3a, and then heated at 140°C for 60 minutes to cure it. Next, the substrate was immersed in 80°C hot water for 20 minutes, then dried at 60°C for 15 minutes, and then coated with phosphoric acid solution and heated at 150°C for 30 minutes to obtain the component of Comparative Example 2. The thickness of each layer of the component of Comparative Example 2 was 19.9 nm and 226.4 nm from the substrate, respectively.

[0196] [Comparative Example 3] The white to pale yellow powdered polyimide obtained in Example 2 was dissolved in cyclohexanone to obtain coating solution 1p, with a solid content concentration of 2.5% by mass.

[0197] (Preparation of components) A coating film of coating liquid 1p was formed on a methacrylic resin (HR-S) substrate using coating liquid 1p, and it was heated at 140°C for 30 minutes to cure. Subsequently, a coating film made of the same coating liquid 1p was formed, and without curing the coating film of coating liquid 1p, a coating film made of coating liquid 3a was subsequently formed. The coating films made of coating liquids 1p, 1p, and 3a were heated at 140°C for 60 minutes to cure, and then the substrate was immersed in 80°C hot water for 20 minutes, and then dried at 60°C for 15 minutes to obtain the component of Comparative Example 3. The thicknesses of each layer of the component of Comparative Example 3 were 45.0 nm, 43.1 nm, 19.9 nm, and 226.4 nm, respectively, from the substrate.

[0198] Table 1 summarizes the materials, refractive index, and film thickness of the organic resin layer containing an imide ring polymer, the first porous layer containing a material different from amorphous aluminum oxide, the second porous layer containing amorphous aluminum oxide, and the aluminum oxide layer containing crystalline aluminum oxide with an uneven structure, along with the evaluation results for Examples 1 to 12 and Comparative Examples 1 to 4.

[0199]

[0200] The results in Table 1 show that the components of Examples 1 to 13 exhibit excellent solvent-based wipeability and provide good anti-reflective performance across the entire surface, regardless of the type of substrate or the shape of the main surface on which the layer is applied. Furthermore, they were confirmed to have excellent appearance and reliability.

[0201] On the other hand, it was found that the materials in Comparative Examples 1 to 3 all had poor wiping properties with solvents, making regeneration work difficult.

[0202] This disclosure includes the following:

[0203] (Item 1) A member comprising a base material, an organic resin layer, a porous layer, and an aluminum oxide layer in this order, wherein the organic resin layer contains a polymer having an aromatic ring in its main chain and / or a polymer having an imide ring in its main chain, the porous layer contains a first porous layer containing a material different from amorphous aluminum oxide, and the aluminum oxide layer contains crystalline aluminum oxide having an uneven structure.

[0204] (Item 2) The member according to item 1, wherein the porous layer further comprises a second porous layer containing amorphous aluminum oxide, provided between the first porous layer and the aluminum oxide layer.

[0205] (Item 3) The member according to item 2, wherein the porous layer further comprises a third porous layer provided between the first porous layer and the second porous layer, the third porous layer comprising the components contained in the first porous layer and the components contained in the second porous layer.

[0206] (Item 4) The member according to item 1, wherein the first porous layer comprises amorphous aluminum oxide.

[0207] (Item 5) The member according to any one of items 1 to 4, wherein the thickness ta of the organic resin layer is in the range of 5 nm or more and 50 nm or less.

[0208] (Item 6) The member according to any one of items 1 to 5, wherein the thickness tb of the first porous layer is in the range of 5 nm or more and 50 nm or less.

[0209] (Item 7) The member according to any one of items 1 to 6, wherein the thickness ta of the organic resin layer and the thickness tb of the first porous layer satisfy the relationship 0.2 < ta / tb < 1.0 and 20 nm < ta + tb < 58 nm.

[0210] (Item 8) The member according to any one of items 1 to 7, wherein the aluminum oxide layer contains phosphorus.

[0211] (Clause 9) The member according to any one of Clauses 1 to 8, wherein the refractive index ns of the d line of the substrate is greater than 1.43 and less than 2.20.

[0212] (Item 10) The member according to any one of items 1 to 9, wherein the first porous layer is made up of a plurality of inorganic particles.

[0213] (Item 11) The member according to item 10, wherein the inorganic particles are silica particles.

[0214] (Clause 12) The member according to Clause 10 or 11, wherein the first porous layer comprises a plurality of inorganic particles bound together by an inorganic compound binder.

[0215] (Item 13) The member according to any one of items 1 to 12, wherein the refractive index n1 of the d line of the organic resin layer is in the range of 1.50 or more and 1.90 or less.

[0216] (Item 14) The member according to any one of items 1 to 13, further comprising a functional layer having one of the functions selected from the group consisting of antifouling, hydrophilicity, antibacterial, antiviral, and decorative properties, on the aluminum oxide layer.

[0217] (Item 15) An optical component comprising the member described in any one of items 1 to 13.

[0218] (Item 16) An optical instrument comprising a housing and an optical system having at least one lens disposed within the housing, wherein at least one of the lenses is the optical component described in Item 15.

[0219] (Item 17) An imaging device comprising a housing, an optical system having at least one lens disposed within the housing, and an image sensor that receives light passing through the optical system, wherein at least one of the lenses is the optical element described in Item 15.

[0220] (Item 18) A method for manufacturing a member comprising a base material, an organic resin layer, a porous layer, and an aluminum oxide layer in this order, comprising: a step of applying a first coating solution of a polymer having an aromatic ring in its main chain and / or an imide ring in its main chain onto the base material to form an organic resin layer; a step of applying a second coating solution containing a material different from amorphous aluminum oxide onto the organic resin layer to form a porous layer; a step of applying a third coating solution of an aluminum oxide precursor sol onto the porous layer and curing the third coating solution to obtain a coating film; and a step of immersing the coating film in hot water to form an aluminum oxide layer containing crystalline aluminum oxide having an uneven structure.

[0221] (Item 19) The method for manufacturing a member according to Item 18, wherein in the step of forming the aluminum oxide layer, the coating film is immersed in hot water, and a second porous layer containing amorphous aluminum oxide is formed between a first porous layer containing a material different from amorphous aluminum oxide and the aluminum oxide layer.

[0222] (Item 20) The method for manufacturing a member according to Item 19, wherein in the step of forming the aluminum oxide layer, the coating film is immersed in hot water to form a third porous layer between the first porous layer and the second porous layer, the third porous layer being composed of the components contained in the first porous layer and the components contained in the second porous layer.

[0223] (Item 21) The method for manufacturing a member according to Item 18, wherein in the step of forming the aluminum oxide layer, the coating film is immersed in hot water to form a first porous layer comprising a material different from the amorphous aluminum oxide and the amorphous aluminum oxide.

[0224] The present invention is not limited to the embodiments described above, and various modifications and variations are possible without departing from the spirit and scope of the invention. Accordingly, the following claims are attached to make the scope of the invention public.

[0225] This application claims priority based on Japanese Patent Application No. 2024-194940, filed on November 7, 2024, and all of its contents are incorporated herein by reference.

[0226] 10 Components 100 Substrate 101 Organic resin layer 102 Porous layer 112 First porous layer 113 Second porous layer 104 Aluminum oxide layer 105C Functional layer 105D Functional layer 114 Uneven structure 131 Particles 132 Binder 133 Void 202 Third porous layer 600 Single-lens reflex digital camera (imaging device) 601 Lens barrel (optical instrument) 603 Lens (optical component) 605 Lens (optical component)

Claims

1. A component comprising a base material, an organic resin layer, a porous layer, and an aluminum oxide layer in this order, wherein the organic resin layer contains a polymer having an aromatic ring in its main chain and / or a polymer having an imide ring in its main chain, the porous layer contains a first porous layer containing a material different from amorphous aluminum oxide, and the aluminum oxide layer contains crystalline aluminum oxide having an uneven structure.

2. The member according to claim 1, wherein the porous layer further comprises a second porous layer containing amorphous aluminum oxide, provided between the first porous layer and the aluminum oxide layer.

3. The member according to claim 2, wherein the porous layer further comprises a third porous layer provided between the first porous layer and the second porous layer, the third porous layer being composed of the components contained in the first porous layer and the components contained in the second porous layer.

4. The member according to claim 1, wherein the first porous layer comprises amorphous aluminum oxide.

5. The member according to claim 1, wherein the thickness ta of the organic resin layer is in the range of 5 nm or more and 50 nm or less.

6. The member according to claim 1, wherein the thickness tb of the first porous layer is in the range of 5 nm or more and 50 nm or less.

7. The member according to claim 1, wherein the thickness ta of the organic resin layer and the thickness tb of the first porous layer satisfy the relationship 0.2 < ta / tb < 1.0 and 20 nm < ta + tb < 58 nm.

8. The member according to claim 1, wherein the aluminum oxide layer contains phosphorus.

9. The member according to claim 1, wherein the refractive index ns of the d line of the substrate is greater than 1.43 and less than 2.

20.

10. The member according to claim 1, wherein the first porous layer is made up of a plurality of inorganic particles.

11. The member according to claim 10, wherein the inorganic particles are silica particles.

12. The member according to claim 10, wherein the first porous layer is made up of a plurality of inorganic particles bound together by an inorganic compound binder.

13. The member according to claim 1, wherein the refractive index n1 of the d line in the organic resin layer is in the range of 1.50 or more and 1.90 or less.

14. The member according to claim 1, further comprising a functional layer having one of the functions selected from the group consisting of antifouling, hydrophilicity, antibacterial, antiviral, and decorative properties, on the aluminum oxide layer.

15. An optical member comprising the member described in any one of claims 1 to 13.

16. An optical device comprising a housing and an optical system having at least one lens disposed within the housing, wherein at least one of the lenses is the optical component described in claim 15.

17. An imaging device comprising a housing, an optical system having at least one lens disposed within the housing, and an image sensor that receives light passing through the optical system, wherein at least one of the lenses is the optical element described in claim 15.

18. A method for manufacturing a component comprising a base material, an organic resin layer, a porous layer, and an aluminum oxide layer in this order, comprising: a step of applying a first coating solution, a solution of a polymer having an aromatic ring in its main chain and / or an imide ring in its main chain, onto the base material to form an organic resin layer; a step of applying a second coating solution, containing a material different from amorphous aluminum oxide, onto the organic resin layer to form a porous layer; a step of applying a third coating solution, containing an aluminum oxide precursor sol, onto the porous layer and curing the third coating solution to obtain a coating film; and a step of immersing the coating film in hot water to form an aluminum oxide layer containing crystalline aluminum oxide having an uneven structure.

19. The method for manufacturing a member according to claim 18, wherein, in the step of forming the aluminum oxide layer, the coating film is immersed in hot water, and a second porous layer containing amorphous aluminum oxide is formed between the first porous layer containing a material different from the amorphous aluminum oxide and the aluminum oxide layer.

20. The method for manufacturing a member according to claim 19, wherein in the step of forming the aluminum oxide layer, the coating film is immersed in hot water to form a third porous between the first porous layer and the second porous layer, the third porous being composed of the components contained in the first porous layer and the components contained in the second porous layer.

21. The method for manufacturing a member according to claim 18, wherein, in the step of forming the aluminum oxide layer, the coating film is immersed in hot water to form a first porous layer containing a material different from the amorphous aluminum oxide and the amorphous aluminum oxide.

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