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

Abstract

The present invention provides a component comprising an aluminum oxide layer containing crystalline aluminum oxide with an uneven structure, which is easy to restore by solvent wiping. [Solution] A member 10 comprising a base material 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 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 102 contains 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

Technical Field

[0001] The present disclosure relates to a member having a concavo-convex structure and a method for manufacturing the same. The present disclosure also relates to an optical member using the member for optical applications, an optical device using the optical member, and an imaging device.

Background Art

[0002] A member using an aluminum oxide layer containing aluminum oxide of a crystal having a concavo-convex structure is known. In Patent Document 1, in order to achieve both productivity and antireflection characteristics by using the member as an optical member, an organic resin layer containing polyimide and a porous layer mainly composed of aluminum oxide are provided as an intermediate layer on a substrate.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] When this member needs to be repaired for some reason during manufacturing, a regeneration operation may be performed, but it has been desired to be able to perform this regeneration operation more simply.

Means for Solving the Problems

[0005] A first aspect for solving the above problems is a member including a substrate, an organic resin layer, a porous layer, and an aluminum oxide layer in this order, wherein the organic resin layer 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 includes at least a first porous layer containing a material different from amorphous aluminum oxide, and the aluminum oxide layer includes aluminum oxide of a crystal having a concavo-convex 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. [Effects of the Invention]

[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. [Brief explanation of the drawing]

[0008] [Figure 1] A schematic cross-sectional view of the member according to the first embodiment, cut from the stacking direction. [Figure 2] A magnified view of the area enclosed by rectangle AA in Figure 1. [Figure 3] A schematic diagram showing an example of the refractive index of an aluminum oxide layer. [Figure 4] A schematic cross-sectional view of the member according to the second embodiment, cut from the stacking direction. [Figure 5] A schematic cross-sectional view of the member according to the third embodiment, cut from the stacking direction. [Figure 6] (a) is a schematic cross-sectional view of the member according to the fourth embodiment, cut from the stacking direction, and (b) is a schematic cross-sectional view of the member according to a modified example of the fourth embodiment, cut from the stacking direction. [Figure 7] A schematic diagram of the imaging device, which is the fifth embodiment. [Figure 8] A flowchart illustrating one embodiment of a method for manufacturing a component. [Modes for carrying out the invention]

[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 components] The components disclosed herein have at least one of the following functions: optical properties, antifouling properties, hydrophilicity, antibacterial properties, antiviral properties, and decorative properties. First, we will describe the optical components.

[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 base material 100 is not particularly limited, and any material such as glass, ceramics, resin, metal, semiconductor, etc. can be used. Also, its shape is not limited, and a flat plate, a curved surface shape having a concave surface or a convex surface, a film, or a sheet can be used. The base material 100 is preferably a transparent base material. As the transparent base material, resin or glass can be used. In this specification, transparent means that the transmittance of light in the wavelength range of 400 nm or more and 780 nm or less is 10% or more. As the transparent base material, glass is preferably used. For example, general optical glasses typified by silicate glass, borosilicate glass, and phosphate glass, quartz glass, and glass ceramics can be used.

[0015] Glass and ceramics are so-called complex oxides, and for example, 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 are contained. The manufacturing method of the base material 100 is not particularly limited, and it can be manufactured, for example, by grinding and polishing, mold molding, or float molding.

[0016] As the resin, a thermoplastic resin or a thermosetting resin is preferably used. Examples of the thermoplastic resin include polyethylene terephthalate, PET (polyethylene naphthalate), PP (polypropylene), triacetyl cellulose, PC (polycarbonate), cycloolefin polymer, and polyvinyl alcohol. Examples of the thermosetting resin include urethane resin.

[0017] As the metal, one composed of a single metal element or an alloy containing two or more metal elements can be used.

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

[0019] The refractive index ns of the d-line of the base material 100 is, for example, greater than 1.43 and less than 2.20. When a base material with a refractive index ns within this range is used, it becomes possible to meet a wide range of optical application needs. Preferably, it is in the range of 1.45 or more and 2.05 or less.

[0020] The base material 100 also includes an undercoat layer provided on the main surface 100A of the above-described base material such as glass. The undercoat layer preferably has a thickness of less than 15 nm so as not to be affected by peeling during the regeneration operation by solvent wiping or light interference. When there is an undercoat layer, an organic resin layer 101 is provided on the undercoat layer. The undercoat layer is composed of, for example, at least one of an adhesive layer, a primer layer, an oxide, a nitride, and a fluoride that prevent the diffusion of impurities from the base material, a polymer having no aromatic ring in the main chain, and a polymer having no imide ring in the main chain.

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

[0022] [Chemical formula]

[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 between 5 nm and 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 freedom of 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 polymer. 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 placing 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 particles of an inorganic compound 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 composition of the particles 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 with voids inside the particle, but cocoon-shaped particles or chain-like particles that can contain many voids in the layer are preferred. Note that 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 is preferably determined by the refractive index n2, the wavelength of light to prevent reflection, and 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. However, if it is in the range of 5 nm or more and 100 nm or less, a high antireflection effect can be expected. 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] [[ID= <Second Porous Layer>]]<Second Porous Layer> The second porous layer 113 containing amorphous aluminum oxide is preferably a porous layer formed from amorphous material mainly composed of aluminum oxide, for example. 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 ridged structure 114a. The ridged structure 114a of the aluminum oxide layer 104 is cone-shaped, tapering towards the atmosphere where the refractive index is 1.0. In other words, the aluminum oxide layer 104 is a ridged structure (ridged film) having a substantially continuously changing region. Here, "substantially continuously changing" does not mean that the refractive index of the film material itself changes continuously, but rather that the effective refractive index changes due to a continuous change in the space-filling ratio of the fine ridged structure with an average pitch of 400 nm or less. This is due to the property that light does not recognize ridged shapes below its own wavelength, but recognizes the ridged structure as a medium for the effective refractive index.

[0040] The uneven 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, using a transmission electron microscope.

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

[0042] The aluminum oxide layer 104 is preferably formed from crystals 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." The aluminum oxide layer 104 consists of crystals of various sizes arranged randomly, with their upper ends forming protrusions. Therefore, it is necessary to control the precipitation and growth of 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 containing 30 mol% or less of any of ZrO2, SiO2, TiO2, ZnO, or MgO. Alternatively, this 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 regeneration work difficult, but with the configuration in which the porous layer 112 is provided on top of the organic resin layer 101 described above, regeneration work can be carried out without problems even if the aluminum oxide layer contains phosphoric acid.

[0045] As described above, according to the optical member 10 of the first embodiment, the member 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 work 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 to the organic resin layer 101, the dissolution of the organic resin layer is promoted and it is easy to peel off. Therefore, the regeneration work using a solvent can be easily performed. Furthermore, with the optical member 10, the refractive index and thickness of each layer can be easily adjusted by the coating liquid or application conditions for forming 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 explained 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 facilitating the design of optical properties, it is preferable that the thickness of the third porous layer 202 be thinner than the thickness of the first porous layer 112. Similarly, it is preferable that the thickness of the third porous layer 202 be 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 as a single unit 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 lamination direction. The member 10B of the third embodiment differs from that of the first embodiment in that it includes 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 contains a material different from amorphous aluminum oxide and 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. A larger number of layers increases the number of interfaces between the laminated layers, which increases the likelihood of solvent clogging. If clogging occurs, the solvent may have difficulty reaching the organic resin layer 101. However, because member 10B has fewer intermediate layers, the solvent can reach the organic resin layer 101 more easily. Therefore, member 10B can be regenerated more easily than member 10.

[0051] [Fourth Embodiment] Figure 6(a) is a schematic cross-sectional view of a member according to the fourth embodiment, cut from the lamination direction. Figure 6(b) 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 explained 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 6(a), or it may have a shape that follows the uneven structure 114a, as shown by part number 105D in Figure 6(b).

[0053] Preferred functional layers with antifouling properties (antifouling layers) include, for example, layers containing fluoropolymers, fluorosilane monolayers, and layers containing titanium dioxide particles. Furthermore, water-repellent layers 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 protective functional 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 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 Instruments and Imaging Devices] The following explanation uses interchangeable lenses and a single-lens reflex digital camera as examples, but the device is not limited to these; a smartphone or compact digital camera may also be used.

[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 within 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, an example of a component inside the camera body housing 621, passes through the prism 611, and is then projected onto the photographer's 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 by the main mirror holder 640 by adhesive or other means. 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, we will explain the manufacturing method of component 10, and along the way, we will also mention the manufacturing methods of components 10A and 10B. Note that the manufacturing method of component 10 is not limited to the methods exemplified below.

[0065] (Method of manufacturing component) Figure 8 is a flowchart showing one embodiment of the manufacturing method for component 10, and the manufacturing method for component may include the following steps. (S01) Process of preparing the substrate (S02) A step of forming an organic resin layer by 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 a substrate. (S03) A process of forming a porous layer by applying a second coating liquid containing a material different from amorphous aluminum oxide onto an organic resin layer. (S04) A third coating solution of aluminum oxide precursor sol is applied to the porous layer, and the third coating solution is cured to obtain a coating film. (S05) A process of immersing the coating film in hot water to form an aluminum oxide layer containing aluminum oxide crystals having an uneven structure. (S06) After forming the aluminum oxide layer, if a manufacturing defect occurs, the component is wiped with a solvent to remove the multilayer film and regenerate it. The following describes each step.

[0066] [(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.

[0067] [(S02) A step of forming an organic resin layer by 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 a substrate.] Polymers having an imide ring used in the formation of the organic resin layer 101, with the exception of polyimides, can be produced by the following methods. For example, they can be synthesized by polyaddition or polycondensation reactions of a monomer having an aromatic ring alone or a bifunctional monomer having an aromatic ring with a bifunctional monomer having a different functional group. The type of polymer varies depending on the type of functional group. For example, aromatic polycarbonates are synthesized by polycondensation reactions of aromatic monomers such as bisphenol A and phosgene. Aromatic polyurethanes are synthesized by polyaddition reactions of diphenylmethane diisocyanate and diols. Although polyimides can also be synthesized from monomers having an imide ring by polyaddition or polycondensation reactions, they are generally synthesized by polyaddition and dehydration condensation reactions of acid dianhydrides and diamines. A key feature is that combinations can be selected from various monomers to satisfy the required properties. For example, by introducing aliphatic chains, alicyclic structures, or fluoroalkyl groups to diamines and / or acid dianhydrides, thermoplastic polyimides that are transparent in the visible light region and soluble in solvents can be obtained. In particular, by using an acid dianhydride having an alicyclic structure, and by introducing various structures such as a siloxane structure, aliphatic chain, alicyclic structure, or aromatic ring into the diamine, either individually or in combination, the refractive index can be arbitrarily changed from 1.50 to 1.90.

[0068] 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 dianhydride, bicyclo[2.2.2]octo-7-ene-2,3,5,6-tetracarboxylic 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. 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.

[0069] 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 -Si-O-Si- groups 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.

[0070] 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.

[0071] 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.

[0072] 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% to 100% by mass of the total solvent.

[0073] 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.

[0074] A polymer solution containing a polymer having an imide ring in its main chain, which is an example of a first coating liquid, can be mixed with components other than the polymer having an imide ring in its main chain. 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.

[0075] 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 matter including the polymer; if it exceeds 40% by mass, 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.

[0076] The polymer solution, which is the first coating liquid, can contain components other than the polymer. However, it is preferable that the amount of non-volatile 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.

[0077] 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.

[0078] Furthermore, the process of applying a coating liquid containing a material different from amorphous aluminum oxide onto the (S03) organic resin layer 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.

[0079] [(S03) A 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, we will describe a coating solution for forming the first porous layer by applying a second coating solution containing a material different from amorphous aluminum oxide.

[0080] The second coating solution for forming the first porous layer 112 includes 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, potentially resulting in radial unevenness in the coating or liquid accumulating at the edges of the substrate, making it difficult to form a uniform coating film.

[0081] 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.

[0082] 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.

[0083] 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 oligomer, resulting in a film with high mechanical strength.

[0084] 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. A range of 1 part by mass to 15 parts by mass is more preferable, and a range of 3.0 parts by mass to 15 parts by mass is even more preferable. 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, which would worsen the visible light scattering of the resulting film.

[0085] 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.

[0086] 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.

[0087] 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.

[0088] 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 components, changes in optical performance in high-humidity environments 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 hexadecafluorosebacic 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 and having 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 and having two or more acidic groups on its surface is more than 10 parts by mass, the acidity of the acidic groups is not equal, so if it is included in excess, the reaction of the first acidic group may be prioritized, making it difficult to bond between particles. Therefore, it may be more susceptible to adsorption of moisture and chemical contaminants.Furthermore, the strength of the membrane may decrease.

[0089] 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.

[0090] [(S04) A step in which a third coating solution of aluminum oxide precursor sol is applied to a porous layer, and the third coating solution is cured to obtain a coating film.] In the step of forming the second porous layer 113 containing amorphous aluminum oxide, the aluminum oxide precursor sol (third coating liquid) placed on the first porous layer 112 is dried and / or fired at a temperature in the range of 50°C to 250°C. This allows for the formation of the second porous layer 113 containing amorphous aluminum oxide. Higher heat treatment temperatures make it easier to achieve high density in the film, but temperatures exceeding 250°C can cause damage such as deformation to the substrate. More preferably, the temperature is between 100°C and 200°C. The heating time depends on the heating temperature, but 10 minutes or more is preferred. The layer mainly composed of aluminum oxide can be formed on the first porous layer 112 by known vapor phase methods such as CVD and PVD, liquid phase methods such as the sol-gel method, or hydrothermal synthesis using inorganic salts. A method is preferred that allows for the formation of a uniform anti-reflective layer over a large area or on a non-planar substrate, 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 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, as in member 10B, in which the components contained in the second porous layer 113 are included in the first porous layer 112.

[0091] 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. For Al2O3, ZrO2, SiO2, TiO2, ZnO, and MgO, metal alkoxides, chlorides, nitrates, and other salt compounds can be used as raw materials. From the viewpoint of film formation, it is particularly preferable to use metal alkoxides as raw materials for ZrO2, SiO2, and TiO2.

[0092] Examples of aluminum compounds include aluminum ethoxide, aluminum isopropoxide, aluminum-n-butoxide, aluminum-sec-butoxide, aluminum-tert-butoxide, and aluminum acetylacetonate. Also included are their oligomers, aluminum nitrate, aluminum chloride, aluminum acetate, aluminum phosphate, aluminum sulfate, and aluminum hydroxide.

[0093] Specific examples of zirconium alkoxides include: zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetra-n-propoxide, zirconium tetraisopropoxide, zirconium tetra-n-butoxide, and zirconium tetra-t-butoxide.

[0094] Various types of silicon alkoxides represented by the general formula Si(OR)4 can be used. R can be the same or different lower alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, and isobutyl groups.

[0095] Examples of titanium alkoxides include tetramethoxytitanium, tetraethoxytitanium, tetra-n-propoxytitanium, tetraisopropoxytitanium, tetra-n-butoxytitanium, and tetraisobutoxytitanium.

[0096] Examples of zinc compounds include zinc acetate, zinc chloride, zinc nitrate, zinc stearate, zinc oleate, and zinc salicylate, with zinc acetate and zinc chloride being particularly preferred.

[0097] Examples of magnesium compounds include magnesium alkoxides such as dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, and dibutoxymagnesium, as well as magnesium acetylacetonate and magnesium chloride.

[0098] 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.

[0099] 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.

[0100] 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.

[0101] 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.

[0102] 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.

[0103] [(S05) A step of immersing the coating film in hot water to form an aluminum oxide layer containing aluminum oxide crystals having an uneven structure.] The coating film, mainly composed of aluminum oxide, formed on a porous layer by the above method, precipitates aluminum oxide crystals when immersed in hot water or exposed to steam, forming a surface with protrusions or uneven structures 114a. In this method, an amorphous aluminum oxide layer may remain beneath the protrusions in the layer containing the protrusions. By immersing the aluminum oxide-based layer in hot water, the surface of the aluminum oxide-based layer undergoes papillosis, etc., and some components dissolve. Due to differences 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 approximately 5 minutes to 24 hours.

[0104] In layers primarily composed of aluminum oxide with added oxides such as TiO2, ZrO2, SiO2, ZnO, and MgO as heterogeneous components, crystallization is achieved by utilizing the differences 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.

[0105] [(S06) After forming the aluminum oxide layer, if a manufacturing defect occurs, the component is wiped with a solvent to remove the multilayer film and regenerate it.] This process is performed only if manufacturing defects such as cracks or stains occur after the above processes (S01) to (S05). This process involves wiping the fabricated component with a solvent to remove 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 remove 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 to use a solvent that 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.

[0106] 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. [Examples]

[0107] 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.

[0108] <Fabrication of components> The following flat glass plates and spherical lenses with concave surfaces were prepared as substrates. In the following examples and comparative examples, an organic resin layer, a porous layer, and an aluminum oxide layer were provided on each substrate to produce optically functional components. Table 1 shows the glass type and refractive index of the substrates used in each example or comparative example. Flat glass 1: φ30mm, 1mm thick, polished on one side. Spherical lens 1: φ30mm, radius of curvature 18.4mm, center thickness 2mm The components were fabricated by forming layers on the polished surface of a flat glass plate 1 and on a spherical lens 1. The coating liquid for forming each layer was applied using the spin coating method.

[0109] The fabricated components were evaluated using the following method.

[0110] <Evaluation of film thickness of components> The refractive index and film thickness of each layer of the material were evaluated using a high-speed spectroscopic ellipsometer (M-2000 JAWoollam 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.

[0111] <Evaluation of reflectivity of materials> The reflectance of perpendicularly incident light at the center of the flat glass plate 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 plate 1 and the spherical lens 1, and evaluated according to the following criteria. A: Average reflectance is between 0% and 0.2%. B: Average reflectance greater than 0.2% and less than or equal to 0.6% C: Average reflectance is greater than 0.6% Components with an evaluation of A or B were judged to have good anti-reflective properties.

[0112] <Evaluation of wipeability with solvents (regeneration process)> The evaluation of the wipeability (regeneration process) with solvent 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 while pressing cleaning paper (Nikon's Silbon paper) soaked in a solvent (a mixture of isohexane and ethanol in a 7:3 ratio) against the surface and wiping away all layers. The evaluation criteria are as follows: A: All layers have been cleanly peeled off and wiped away, and it is in a condition where it can be immediately restored and used. B: Except for a small portion, the entire layer has peeled off and been wiped away, but it can be restored and used again if the solvent is wiped again. C: Except for a small portion, the entire layer has peeled off and been wiped away. It can be restored and used again by wiping it with a solvent again using cleaning paper soaked in abrasive. D: The entire layer did not peel off cleanly, and even after wiping with a cleaning paper soaked in abrasive and wiping with solvent again, some parts remained, making it unusable for restoration. <Evaluation of appearance> A spherical lens 1 with a film applied was visually observed and its appearance was evaluated. Particular attention was paid to evaluating cracks in the peripheral area. Here, the peripheral area refers to a 2 mm wide region along the outer edge of the concave surface. The appearance was evaluated according to the following criteria. A: Reflections in the peripheral areas are barely noticeable. B: Reflections can be felt in the peripheral areas. C: Reflections are quite noticeable in the peripheral areas. Products rated A show almost no visible change in appearance from the center to the periphery of the lens, indicating a good anti-reflective effect. Products rated B are inferior to those rated A, but still provide a sufficient anti-reflective effect. Products rated C have an insufficient anti-reflective effect.

[0113] <Reliability evaluation under high temperature and high humidity conditions> A flat glass plate 1 with a film applied and a spherical lens 1 were exposed to high temperature and high humidity conditions of 60°C and 90% for 1000 hours, and the change in reflectivity and appearance were evaluated. The change in reflectivity was evaluated according to the following criteria: The change in average reflectivity after exposure to high temperature and high humidity conditions was calculated relative to the average reflectivity in the visible light region (400-700 nm) of the flat glass plate 1 before exposure to high temperature and high humidity conditions. A: There is almost no fluctuation in reflectance (the rate of change in average reflectance is less than 20%). B: Slight fluctuations in reflectivity are observed (the percentage change in average reflectivity is between 20% and 50%). C: Large fluctuations in reflectance (average reflectance fluctuation rate is 20% or more but less than 50%) The appearance was evaluated according to the following criteria. Spherical lens 1 was visually observed after exposure to high temperature and high humidity, and changes in appearance were evaluated. A: There is almost no change in appearance. B: There are slight changes in the appearance, including minor scratches. C: The appearance has changed significantly, with scratches, peeling of the film, clouding, etc. For lenses rated A, there is almost no change in optical properties or appearance from the center to the periphery, indicating good reliability. For lenses rated B, while inferior to those rated A, sufficient reliability is still considered to be achieved. For lenses rated C, reliability is considered insufficient. The following provides a detailed explanation of the examples and comparative examples.

[0114] [Example 1] (Coating liquid 1a, which is the first coating liquid 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 dissolved completely by gradually 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 a white solid alicyclic diamine DADCM was obtained.

[0115] 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 volume of 12 mmol.

[0116] 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.

[0117] The solution was stirred at room temperature for 15 hours to carry out the polymerization reaction. Further dilution with DMAc to an 8% by weight concentration was performed, followed by the addition of 7.4 ml of pyridine and 3.8 ml of acetic anhydride. The mixture was then 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 powdery polyimide was obtained.

[0118] The obtained polyimide was dissolved in cyclohexanone to a solid content concentration of 2.5% by mass to obtain coating solution 1a.

[0119] (Coating liquid 2a, which is the second coating liquid 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.

[0120] In a separate container, 12.48 g of ethyl silicate was added to 13.82 g of ethanol and a 3% aqueous nitric acid solution. 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.

[0121] Silica sol 1 was added so that the silica particle:silica sol component was in a mass ratio of 100:21. Furthermore, by mixing and stirring at room temperature for 2 hours, a coating solution 2a containing cocoon-shaped silica particles was obtained.

[0122] (Preparation of aluminum oxide precursor sol for forming the second porous layer and aluminum oxide layer, which are the third coating liquid) 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 as 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 was used to prepare aluminum oxide precursor sol 3a. The average particle size measured by dynamic light scattering was 10 nm.

[0123] (Fabrication of components) 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 cured by heating at 140°C for 60 minutes, and then the substrate was immersed in 80°C hot water for 20 minutes, followed by drying at 60°C for 15 minutes. FE-SEM observation of the surface and cross-section of the obtained substrate revealed a protruding structure with a fine uneven surface, where plate-like crystals mainly composed of aluminum oxide grew randomly, resulting in the member of Example 1. The thicknesses of each layer of the member of Example 1 were 27.3 nm, 19.5 nm, 15.5 nm, and 226.4 nm, respectively, from the substrate.

[0124] [Example 2] (Coating liquid 1b, which is the first coating liquid 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 volume of 12 mmol.

[0125] 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.

[0126] The solution was stirred at room temperature for 15 hours to carry out the polymerization reaction. Further dilution with DMAc to an 8% by weight concentration was performed, followed by the addition of 7.4 ml of pyridine and 3.8 ml of acetic anhydride. The mixture was then 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 powdery polyimide was obtained.

[0127] The obtained polyimide was dissolved in cyclohexanone to a solid content concentration of 1.8% by mass to obtain coating solution 1b.

[0128] (Coating liquid 2b, which is the second coating liquid 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 1.5% 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.

[0129] In a separate container, 12.48 g of ethyl silicate was added to 13.82 g of ethanol and a 3% aqueous nitric acid solution. 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.

[0130] Silica sol 1 was added so that the silica particle:silica sol component was in a mass ratio of 100:21. Furthermore, by mixing and stirring at room temperature for 2 hours, a coating solution 2a containing cocoon-shaped silica particles was obtained.

[0131] (Preparation of aluminum oxide precursor sol for forming the second porous layer and aluminum oxide layer, which are the third coating liquid) An aluminum oxide precursor sol 3a obtained in the same manner as the coating solution 3a was used.

[0132] (Fabrication of components) After forming a coating film of coating liquid 1b on a substrate made of S-TIL26 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 cured by heating at 140°C for 60 minutes, 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 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.

[0133] [Example 3] (Coating liquid 1c, which is the first coating liquid for forming an organic resin layer) The polyimide obtained in the same manner as coating solution 1a was dissolved in cyclohexanone to obtain coating solution 1c, with a solid content concentration of 2.2% by mass.

[0134] (Coating liquid 2c, which is the second coating liquid for forming the first porous layer) As a dispersion of spherical solid silica (silicon dioxide) particles in propylene glycol monomethyl ether, Nissan Chemical Corporation's PGM-ST (particle size 10 nm, solid content concentration 30% by mass) was used. 1-Propoxy-2-propanol was added to 100 g of the dispersion of solid silica particles in propylene glycol monomethyl ether to achieve a solid content concentration of 2.0% by mass.

[0135] 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.

[0136] Silica sol 2 was added to a dispersion of solid silica particles so that the silica particle:silica sol ratio was 25:3. Furthermore, by stirring and mixing at room temperature for 2 hours, a coating solution 2c containing solid silica particles was obtained.

[0137] (Preparation of aluminum oxide precursor sol for forming the second porous layer and aluminum oxide layer, which are the third coating liquid) An aluminum oxide precursor sol 3a obtained in the same manner as the coating solution 3a was used.

[0138] (Fabrication of components) After forming a coating film of coating liquid 1c on an L-BSL7 substrate 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 cured by heating at 140°C for 60 minutes, 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 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.

[0139] [Example 4] (Coating liquid 1d, which is the first coating liquid for forming an organic resin layer) The polyimide obtained in the same manner as coating solution 1b was dissolved in cyclohexanone to obtain coating solution 1d, with a solid content concentration of 2.1% by mass.

[0140] (Coating liquid 2d, which is the second coating liquid 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 1.4% 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.

[0141] Silica sol 1 was added so that the mass ratio of silica particles to silica sol components 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.

[0142] (Preparation of aluminum oxide precursor sol for forming the second porous layer and aluminum oxide layer, which are the third coating liquid) An aluminum oxide precursor sol 3a obtained in the same manner as the coating solution 3a was used.

[0143] (Fabrication 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 cured by heating at 140°C for 60 minutes, 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 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.

[0144] [Example 5] (Coating liquid 1e, which is the first coating liquid for forming an organic resin layer) The polyimide obtained in the same manner as coating solution 1a was dissolved in cyclohexanone to obtain coating solution 1e, with a solid content concentration of 2.0% by mass.

[0145] (Coating liquid 2e, which is the second coating liquid 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. 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.

[0146] Silica sol 1 was added so that the mass ratio of silica particles to silica sol components 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.

[0147] (Preparation of aluminum oxide precursor sol for forming the second porous layer and aluminum oxide layer, which are the third coating liquid) An aluminum oxide precursor sol 3a obtained in the same manner as the coating solution 3a was used.

[0148] (Fabrication 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 cured by heating at 140°C for 60 minutes, 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 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.

[0149] [Example 6] (Coating liquid 1f, which is the first coating liquid for forming an organic resin layer) A branched melamine polymer photocuring 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 solution 1b prepared in Example 2 were stirred and mixed at room temperature to prepare a blended polymer coating solution 1f of branched melamine polymer and polyimide.

[0150] (Coating liquid 2f, which is the second coating liquid 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 1.4% 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.

[0151] In a separate container, 12.48 g of ethyl silicate was added to 13.82 g of ethanol and a 3% aqueous nitric acid solution. 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.

[0152] 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.

[0153] (Preparation of aluminum oxide precursor sol for forming the second porous layer and aluminum oxide layer, which are the third coating liquid) An aluminum oxide precursor sol 3a obtained in the same manner as the coating solution 3a was used.

[0154] (Fabrication 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 of coating liquid 2f was subsequently formed without curing the coating film of coating liquid 1f. Furthermore, a coating film of coating liquid 3a was subsequently formed without curing the coating film of coating liquid 2f. The coating films made of coating liquids 1f, 2f, and 3a were cured by heating at 140°C for 60 minutes, 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 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.

[0155] [Example 7] (1 g of coating liquid, which is the first coating liquid for forming the organic resin layer) A branched melamine polymer photocuring 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 mixed at room temperature while stirring to prepare 1 g of a blended polymer coating solution of branched melamine polymer and polyimide.

[0156] (2g of coating liquid, which is the second coating liquid 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. 1-Ethoxy-2-propanol was added to 100 g of the aqueous dispersion of cocoon-shaped silica particles to achieve a solid content concentration of 2.4% by mass. Dibenzenesulfonimide was added to prepare a dispersion of cocoon-shaped silica particles by adjusting the mass ratio of cocoon-shaped silica particles to acidic component to 100:2.

[0157] Silica sol 1 was added so that the mass ratio of silica particles to silica sol 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.

[0158] (Preparation of aluminum oxide precursor sol for forming the second porous layer and aluminum oxide layer, which are the third coating liquid) An aluminum oxide precursor sol 3a obtained in the same manner as the coating solution 3a was used.

[0159] (Fabrication of components) A coating film of 1 g of coating solution was formed on a synthetic quartz substrate using 1 g of coating solution. Without curing the 1 g coating film, a coating film of 2 g of coating solution was subsequently formed. Furthermore, without curing the 2 g coating film, a coating film of 3 a was subsequently formed. The coating films made of 1 g, 2 g, and 3 a were cured by heating at 140°C for 60 minutes. 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 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.

[0160] [Example 8] (Coating liquid 1h, which is the first coating liquid for forming the organic resin layer) A branched melamine polymer photocuring 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.

[0161] (Coating liquid 2h, which is the second coating liquid for forming the first porous layer) As the isopropyl alcohol dispersion of chain-like silica (silicon dioxide) 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.

[0162] 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.

[0163] 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.

[0164] (Preparation of aluminum oxide precursor sol for forming the second porous layer and aluminum oxide layer, which are the third coating liquid) An aluminum oxide precursor sol 3a obtained in the same manner as the coating solution 3a was used.

[0165] (Fabrication of components) After forming a coating film of coating liquid 1h on a substrate made of S-LAH79 using coating liquid 1h, a coating film of coating liquid 2h was formed without curing the coating film of coating liquid 1h. Furthermore, a coating film 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, and then the substrate was immersed in 80°C hot water for 20 minutes, 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 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.

[0166] [Example 9] (Coating liquid 1i, which is the first coating liquid 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-purged 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 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 the polymaleimide powder and 0.5 g of the polyimide powder obtained in Example 2 in 97.0 g of 1-acetoxy-2-methoxypropane.

[0167] (Coating liquid 2i, which is the second coating liquid 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 the mixture was stirred at room temperature for 240 minutes to obtain coating solution 2i consisting of silica sol.

[0168] (Preparation of aluminum oxide precursor sol for forming the second porous layer and aluminum oxide layer, which are the third coating liquid) Coating solution 3b was prepared by mixing 0.001 g of aluminum oxide particles (manufactured by Sigma-Aldrich: particle size 50 nm or less) with 10.0 g of aluminum oxide precursor sol 3a prepared in Example 1, and this mixture was used.

[0169] (Fabrication 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 of coating liquid 2i was subsequently formed without curing the coating film of coating liquid 1i. Furthermore, a coating film of coating liquid 3b was subsequently formed without curing the coating film of coating liquid 2i. The coating films made of coating liquids 1i, 2i, and 3b were cured by heating at 140°C for 60 minutes, 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 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.

[0170] [Example 10] (Coating liquid 1j, which is the first coating liquid for forming an organic resin layer) The 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.

[0171] (Coating liquid 2j, which is the second coating liquid 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 a coating solution 2 j consisting of silica sol.

[0172] (Preparation of aluminum oxide precursor sol for forming the second porous layer and aluminum oxide layer, which are the third coating liquid) An aluminum oxide precursor sol 3a obtained in the same manner as the coating solution 3a was used.

[0173] (Fabrication 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.

[0174] [Example 11] (Coating liquid 1k, which is the first coating liquid for forming the organic resin layer) A branched melamine polymer photocuring 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 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.

[0175] (Coating liquid 2k, which is the second coating liquid 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 1.2% 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.

[0176] Silica sol 1 was added so that the mass ratio of silica particles to silica sol components 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.

[0177] (Preparation of aluminum oxide precursor sol for forming the second porous layer and aluminum oxide layer, which are the third coating liquid) An aluminum oxide precursor sol 3a obtained in the same manner as the coating solution 3a was used.

[0178] (Fabrication 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 of coating liquid 2k was subsequently formed without curing the coating film of coating liquid 1k. Furthermore, a coating film of coating liquid 3a was subsequently formed without curing the coating film of coating liquid 2k. The coating films made of coating liquids 1k, 2k, and 3a were cured by heating at 140°C for 60 minutes, 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 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.

[0179] [Example 12] (1 liter of coating liquid, which is the first coating liquid for forming the organic resin layer) Coating solution 1a and coating solution 1b were mixed in a ratio of 40:60 to obtain coating solution 1L.

[0180] (Coating liquid 2l, which is the second coating liquid 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.

[0181] 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, 2 liters of coating solution containing cocoon-shaped silica particles was obtained.

[0182] (Preparation of aluminum oxide precursor sol for forming the second porous layer and aluminum oxide layer, which are the third coating liquid) An aluminum oxide precursor sol 3a obtained in the same manner as the coating solution 3a was used.

[0183] (Fabrication of components) A coating film of 1 liter of coating solution was formed on a polycarbonate resin (AD-5503) substrate using 1 liter of coating solution. Without curing the coating film of 1 liter of coating solution, a coating film of 2 liters of coating solution was subsequently formed. Furthermore, without curing the coating film of 2 liters of coating solution, a coating film of 3a was subsequently formed. The coating films made of 1 liter, 2 liters, and 3a were cured by heating at 140°C for 60 minutes. 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.

[0184] [Example 13] (Coating liquid 1n, which is the first coating liquid for forming an organic resin layer) A branched melamine polymer photocuring 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 mixed at room temperature while stirring to prepare a blended polymer coating solution 1n of branched melamine polymer and polyimide.

[0185] (Coating liquid 2n, which is the second coating liquid 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 1.1% 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.

[0186] Silica sol 2 was added so that the mass ratio of silica particles to silica sol components was 100:22. Furthermore, by mixing and stirring at room temperature for 2 hours, a coating solution 2n containing cocoon-shaped silica particles was obtained.

[0187] (Preparation of aluminum oxide precursor sol for forming the second porous layer and aluminum oxide layer, which are the third coating liquid) An aluminum oxide precursor sol 3a obtained in the same manner as the coating solution 3a was used.

[0188] (Fabrication 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 of coating liquid 2n was subsequently formed without curing the coating film of coating liquid 1n. Furthermore, a coating film of coating liquid 3a was subsequently formed without curing the coating film of coating liquid 2n. The coating films made of coating liquids 1n, 2n, and 3a were cured by heating at 140°C for 60 minutes, 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 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.

[0189] [Comparative Example 1] (1 m of coating liquid, which is the first coating liquid for forming the organic resin layer) The white to pale yellow powdered polyimide obtained in Example 1 was dissolved in cyclohexanone to a solid content concentration of 4.5% by mass to obtain 1 m of coating solution.

[0190] (Coating liquid 2m, which is the second coating liquid for forming the first porous layer) In Comparative Example 1, the coating solution 2m for forming the first porous layer, which contains a material different from amorphous aluminum oxide, was not used.

[0191] (Preparation of aluminum oxide precursor sol for forming the second porous layer and aluminum oxide layer, which are the third coating liquid) An aluminum oxide precursor sol 3a obtained in the same manner as the coating solution 3a was used.

[0192] (Fabrication 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 of coating liquid 1 m and 3a were cured by heating at 140°C for 60 minutes, 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 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.

[0193] [Comparative Example 2] The process was carried out without forming the organic resin layer and the first porous layer.

[0194] (Fabrication of components) A coating film made of coating liquid 3a was formed on a substrate made of S-LAH79 using coating liquid 3a, and then cured by heating at 140°C for 60 minutes. Next, the substrate was immersed in 80°C hot water for 20 minutes, 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 thicknesses of each layer of the component of Comparative Example 2 were 19.9 nm and 226.4 nm from the substrate, respectively.

[0195] [Comparative Example 3] The white to pale yellow powdered polyimide obtained in Example 2 was dissolved in cyclohexanone to a solid content concentration of 2.5% by mass to obtain coating solution 1p.

[0196] (Fabrication of components) A coating film of coating liquid 1p was formed on a methacrylic resin (HR-S) substrate using coating liquid 1p, and cured by heating at 140°C for 30 minutes. 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 cured by heating at 140°C for 60 minutes, 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 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.

[0197] 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.

[0198] [Table 1]

[0199] 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.

[0200] 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.

[0201] This disclosure includes the following:

[0202] (Section 1) A component comprising a base material, an organic resin layer, a porous layer, and an aluminum oxide layer in this order, The organic resin layer contains 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 includes a first porous layer containing a material different from amorphous aluminum oxide, The aluminum oxide layer contains crystalline aluminum oxide having a concavo-convex structure, A member characterized by this.

[0203] (Item 2) The member according to item 1, wherein the porous layer further includes a second porous layer containing amorphous aluminum oxide provided between the first porous layer and the aluminum oxide layer.

[0204] (Item 3) The member according to item 2, wherein the porous layer further includes a third porous layer composed of a component contained in the first porous layer and a component contained in the second porous layer provided between the first porous layer and the second porous layer.

[0205] (Item 4) The member according to item 1, wherein the first porous layer contains amorphous aluminum oxide.

[0206] (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.

[0207] (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.

[0208] (Item 7) The thickness ta of the organic resin layer and the thickness tb of the first porous layer are The member according to any one of items 1 to 6, satisfying the relationship of 0.2 < ta / tb < 1.0 and 20 nm < ta + tb < 58 nm.

[0209] (Item 8) The member according to any one of claims 1 to 7, wherein the aluminum oxide layer contains phosphorus.

[0210] (Section 9) The member according to any one of claims 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.

[0211] (Section 10) The member according to any one of items 1 to 9, wherein the first porous layer consists of a plurality of inorganic particles.

[0212] (Section 11) The member according to item 10, wherein the inorganic particles are silica particles.

[0213] (Section 12) The member according to claim 10 or 11, wherein the first porous layer comprises a plurality of inorganic particles bound together by an inorganic compound binder.

[0214] (Section 13) The member according to any one of claims 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.

[0215] (Section 14) The member according to any one of claims 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.

[0216] (Section 15) An optical component comprising the member described in any one of items 1 to 13.

[0217] (Section 16) An optical instrument comprising a housing and an optical system having at least one lens disposed within the housing, An optical instrument characterized in that at least one of the lenses is an optical component as described in item 15.

[0218] (Section 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, An imaging device characterized in that at least one of the lenses is an optical element as described in item 15.

[0219] (Section 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, A step of forming an organic resin layer by 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 a substrate, A 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, The process involves 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. The process involves immersing the aforementioned coating film in hot water to form an aluminum oxide layer containing aluminum oxide crystals having an uneven structure, A method for manufacturing a component, characterized by comprising the above.

[0220] (Section 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 the first porous layer containing a material different from the amorphous aluminum oxide and the aluminum oxide layer.

[0221] (Section 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.

[0222] (Section 21) In the step of forming the aluminum oxide layer, the coating film is immersed in warm water to form a first porous layer including a material different from the amorphous aluminum oxide and the amorphous aluminum oxide, according to the method for manufacturing the member described in item 18.

Explanation of symbols

[0223] 10 member 100 base material 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 concavo-convex structure 131 particle 132 binder 133 void 202 third porous layer 600 single-lens reflex digital camera (imaging device) 601 lens barrel (optical instrument) 603 lens (optical member) 605 lens (optical member)

Claims

1. A component comprising a base material, an organic resin layer, a porous layer, and an aluminum oxide layer in this order, The organic resin layer comprises 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 includes a first porous layer containing a material different from amorphous aluminum oxide, The aluminum oxide layer contains aluminum oxide crystals having an uneven structure. A component characterized by the following features.

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 comprising 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 contains 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 thickness ta of the organic resin layer and the thickness tb of the first porous layer are, The component according to claim 1, satisfying the relationships 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 comprises 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 properties, antiviral properties, 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 instrument comprising a housing and an optical system having at least one lens disposed within the housing, An optical device characterized in that 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 that has passed through the optical system, An imaging device characterized in that at least one of the lenses is the optical member 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, A step of forming an organic resin layer by 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 a substrate, A step of forming a porous layer by applying a second coating liquid containing a material different from amorphous aluminum oxide onto the aforementioned organic resin layer, The process involves 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. The process involves immersing the aforementioned coating film in hot water to form an aluminum oxide layer containing aluminum oxide crystals having an uneven structure, A method for manufacturing a component, characterized by comprising the above.

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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