Patent Application
20230384491
The present invention relates to an optical product having a minutely uneven film formed therein, and a method for manufacturing the optical product.
JP 2012-198330 A indicates that a layer that has a minutely uneven structure formed of aluminium (hereinafter also referred to as Al) or a compound thereof is formed on an outermost surface of a substrate having a curved surface, by gas-phase deposition and hydrothermal treatment at a temperature of not lower than 60° C. and not higher than a boiling temperature.
The average height of the projecting portion in the uneven structure is about 5 to 1000 nm.
The density of the film having such a minutely uneven structure (moth-eye structure) is reduced from the substrate side toward the air side. Therefore, the refractive index of the film gradually varies. Accordingly, the film acts so as to have no optical interface and acts like a thin film having a low refractive index. The film exhibits an antireflection effect through such an action and is usable as an antireflection film.
As described above, it is known that the minutely uneven structure formed of aluminium or a compound thereof is produced by aluminium or a compound thereof.
However, a minutely uneven structure formed of another material, in particular, silica (SiO2), is not known.
Therefore, a main object of the present invention is to provide an optical product having a film that has a minutely uneven structure formed by a material other than aluminium or a compound thereof.
Furthermore, another main object of the present invention is to provide an optical product manufacturing method capable of easily manufacturing an optical product having a film that has a minutely uneven structure formed by a material other than aluminium or a compound thereof.
In order to achieve the above-described object, an optical product including: a base; and an optical film formed directly or indirectly on a film-formation surface of the base is provided, and the optical film has an Al2O3 layer that is made of Al2O3 and is disposed on the base side, and an SiO2 layer that is made of SiO2 and that has a minutely uneven structure.
Furthermore, in order to achieve the above-described object, an optical product manufacturing method including: forming, on a base, an aluminum-based manufacture intermediate film made of aluminium, an aluminium alloy, or an aluminium compound; and immersing the base having the aluminum-based manufacture intermediate film in an aqueous solution of silica, is provided. In the optical product manufacturing method, the silica in the aqueous solution has a concentration of not greater than 10 mg/l.
A main effect of the present invention is to provide an optical product having a film that has a minutely uneven structure formed by a material other than aluminium or a compound thereof.
Furthermore, another main effect of the present invention is to provide an optical product manufacturing method capable of easily manufacturing an optical product having a film that has a minutely uneven structure formed by a material other than aluminium or a compound thereof.
An exemplary embodiment of the present invention will be described below with appropriate reference to the drawings.
The present invention is not limited to the following exemplary embodiment.
As shown in
The optical product 1 is used as an antireflection member having translucency. That is, in the optical product 1, the optical film 4 allows an intensity of reflected light R1 to be reduced relative to an intensity of incident light I1 (incidence angle θ) incident on the optical product 1.
The base 2 is a base for forming the optical product 1, and is plate-shaped (substrate) in the description herein. The base 2 is translucent, and the transmittance of visible light as light having a wavelength in a visible range (not less than 400 nm and not greater than 750 nm in the present invention) in the base 2 is almost 100%. The shape of the base 2 may be a flat-plate-like shape or curved-plate-like shape, or may be a non-plate-like shape such as a block-like shape.
As a material (material substance) of the base 2, plastic is used, and polycarbonate resin (hereinafter referred to as PC) as thermosetting resin is used in the description herein. The material of the base 2 is not limited to PC, and examples of the material may include polyurethane resin, thiourethane resin, episulfide resin, polyester resin, acrylic resin, polyether sulfone resin, poly(4-methylpentene-1) resin, diethylene glycol bis(allyl carbonate) resin, and a combination thereof. Furthermore, the material of the base 2 may be a material such as glass other than plastic.
The film-formation surface F of the base 2 is disposed on each of a front surface and a rear surface. The optical film 4 is disposed directly on each of the front surface and the rear surface. The optical film 4 may be disposed on one of the front surface and the rear surface, or may be disposed on three or more surfaces of the block-shaped base 2 or the like. An intermediate film such as a hard coating film may be disposed between the base 2 and at least one of the optical films 4. In a case where such an intermediate film is disposed, the optical film 4 is formed indirectly on the base 2.
The optical film 4 on the rear surface has the same structure as the optical film 4 on the front surface. Hereinafter, the optical film 4 on the front surface will be described, and description of the optical film 4 on the rear surface is omitted as appropriate.
The optical film 4 has an Al2O3 layer 12 made of alumina, on the first layer counting from the base 2 (the same counting manner is applied to the following description), and has an SiO2 layer 14 that is made of silica and that has a minutely uneven structure, on the second layer.
Alternatively, the optical film 4 has an Al2O3 layer that is a layer containing Al2O3 as a main component, on the first layer, and has an SiO2 layer 14 that is a layer containing SiO2 as a main component and that has a minutely uneven structure, on the second layer. In this case, a boundary between the first layer and the second layer may be unclear. Furthermore, typically, a component ratio of Al2O3 becomes higher in a portion closer to the base 2, and a component ratio of SiO2 to Al2O3 becomes higher in a portion farther from the base 2, in the first layer. That is, in the film thickness direction, a component ratio of SiO2 to Al2O3 in the first layer is proportional to a distance from the base 2. The first layer can be obtained as a thin-film-like layer having no minutely uneven structure regardless of distribution of the materials. Furthermore, the first layer can be obtained as a base portion (bed) of the minutely uneven structure. Moreover, the first layer can be obtained as a thin-film-like layer which has no minutely uneven structure and in which the material gradually changes in the layer. Furthermore, the second layer can contain Al2O3 in a state where the Al2O3 does not become a main component. For example, the second layer can have a core (skeleton), of the minutely uneven structure, which contains Al2O3 as a main component, and a coating which contains, as a main component, SiO2 covering a part or the entirety of the core. The second layer can be obtained as a layer having a minutely uneven structure regardless of distribution of the materials. The height of the SiO2 layer 14 is, for example, not less than about 1 nm and not greater than about 1000 nm. The minutely uneven structure in the SiO2 layer 14 is, for example, a fluff-like structure, a multiple-pyramids-shaped structure, a flower-frog-shaped structure, or a combination thereof.
The optical product 1 is manufactured from a manufacture intermediate 20 shown in
Each Al-based manufacture intermediate film 22 is formed of aluminium nitride (AlN) in the description herein. In AlN, an element ratio between Al and N may be any ratio as long as the existence thereof is stable.
A material (material substance) of at least one of the Al-based manufacture intermediate films 22 may be aluminium, an aluminium alloy, or an aluminium compound other than AlN, and may be, for example, Al, Al2O3, aluminium oxynitride (AON), or a combination of at least two selected from the group including Al, Al2O3, AlON, and AlN. In AlON, an element ratio between Al and N, an element ratio between Al and O, and an element ratio between O and N are also similar to the ratio in AlN. In a case where a plurality of the Al-based manufacture intermediate films 22 are disposed, a material of a part of the Al-based manufacture intermediate films 22 may be different from a material of the other of the Al-based manufacture intermediate films 22.
The aluminium alloy and the aluminium compound may be an alloy and a compound each containing aluminium as a main component. In the description herein, the main component may be a component having a weight ratio greater than half the entire weight ratio, a component having a volume ratio greater than half the entire volume ratio, or a component having an element ratio greater than half the entire element ratio, relative to the other components. Such a matter for the main component also applies, as appropriate, to members other than the Al-based manufacture intermediate film 22.
As shown in
A case where the Al-based manufacture intermediate film 22 made of AlN is formed through DC sputtering by a DC sputter deposition apparatus, will be described below.
That is, firstly, a plate-shaped target made of Al is set, a film forming chamber is evacuated, and cleaning of the base 2 is performed as a pretreatment by supplying oxygen (O2) gas that has become radical oxygen through application of high frequency voltage, at a predetermined flow rate (for example, 500 ccm), for a predetermined time period (for example, 30 seconds), from a radical source to the film forming chamber. More specifically, through such application of radical oxygen, even if an organic substance and the like are adhered to the base 2, the organic substance and the like are decomposed and separated by ultraviolet rays generated by the radical oxygen and plasma. Such cleaning enhances adherence of a film formed later.
Sputtering is performed for the Al-based manufacture intermediate film 22 in a predetermined process condition. In the description herein, an Al sputtering source operates in conjunction with introduction of argon (Ar) gas, and nitrogen (N2) gas is introduced as the radical source into the film forming chamber. Instead of the sputtering source or together with the sputtering source, Ar gas may be introduced for the radical source. For Ar gas, rare gas other than Ar may be used. Such change about Ar gas may be performed as appropriate for the other film forming.
The Al-based manufacture intermediate film 22 made of Al2O3 or the like may be formed through vapor deposition.
In vapor deposition for the Al-based manufacture intermediate film 22 made of Al, Al granules may be heated by electron beams (hereinafter referred to as EB) in a film forming chamber in a vacuum state.
In vapor deposition for the Al-based manufacture intermediate film 22 made of Al2O3, O2 gas may be introduced, and Al granules may be heated by EB in a film forming chamber in a vacuum state.
The base 2 having the Al-based manufacture intermediate film 22 as configured above, that is, the manufacture intermediate 20, is immersed in a solution SL in a tank T, as shown in
The solution SL is a solution in which a small amount of silica (SiO2) is dissolved in water (H2O). In other words, the solution SL is an aqueous solution of a small amount of silica. Thus, as shown in
More specifically, the Al-based manufacture intermediate film 22 gradually adsorbs a small amount of SiO2 in the solution SL on the side opposite to the base 2 side, and collects SiO2 so as to have the minutely uneven structure while changing to the Al2O3 layer 12 through reaction involving partial dissolution with water in the solution SL. The Al-based manufacture intermediate film 22 allows, for example, multiple minute fluff-like, pyramidal, conic, or needle-shaped objects which are made of SiO2, to grow in the film thickness direction in the solution SL. The orientation (direction) of the manufacture intermediate 20 in the immersed state is not limited to the horizontal orientation as shown in
The concentration of SiO2 in the solution SL is, for example, not greater than 10 mg/l and more preferably not greater than 2 mg/l, mainly from the viewpoint of advantageously forming the SiO2 layer 14.
The temperature of the solution SL is 90° C. from the viewpoint of obtaining the fluff-like structure or the like in the shortest possible time period, in the description herein. Furthermore, the temperature of the solution SL is, for example, not lower than 80° C. and not higher than 100° C., or not lower than 90° C. and not higher than 100° C. In order to obtain a temperature of not lower than 100° C., water needs to be subjected to a special treatment such as pressure application, or a substance other than water needs to be used, so that the process becomes bothersome.
A time of immersion in the solution SL is, for example, not shorter than two seconds and not longer than ten minutes, not shorter than five seconds and not longer than five minutes, or not shorter than 15 seconds and not longer than three minutes, from the viewpoint of obtaining the Al2O3 layer 12 and the SiO2 layer 14 in the shortest possible time period. If the immersion time is short, the Al2O3 layer 12 and the SiO2 layer 14 are not sufficiently formed. If the immersion time is long, the efficiency becomes low according to the treatment time becoming long.
Thereafter, as shown in
Next, preferable examples of the present invention and a comparative example which does not belong to the present invention will be described.
The present invention is not limited to the following examples. According to the interpretation of the present invention, the following examples may be substantially construed as the comparative examples or the following comparative example may be substantially construed as the example.
Examples 1 is described below.
Example 1 corresponds to the above-described embodiment.
In Example 1, the Al-based manufacture intermediate film 22 made of AlN was formed on both surfaces of the plate-shaped base 2 made of PC by DC sputtering in a process condition indicated at the top line excluding the line for column headings in the following Table 1, so as to have a physical film thickness of 72 nm.
The manufacture intermediate 20 was immersed in the solution SL having a temperature of 90° C. and containing 0.06 mg/l of silica for three minutes, and dried, to obtain the optical product 1 according to Example 1.
Particularly, the concentration of silica in the solution SL was obtained as follows. That is, the concentration of silica in the solution SL was measured by PACKTEST silica (low concentration) manufactured by KYORITSU CHEMICAL-CHECK Lab., Corp. based on a blue coloring mechanism in molybdenum blue absorption spectroscopy. The PACKTEST silica (low concentration) allows the concentration of silica in a sample to be measured within a range of 0.5 to 20 mg/l. In a case where the concentration of silica was lower than 0.5 mg/I, a solvent (H2O) in the solution SL taken as a sample was heated and evaporated to perform concentration, a reduced amount of a volume for the concentrated solution was measured, the concentration of silica in the concentrated solution was measured, and the concentration of silica in the solution SL for the sample having not been concentrated yet was obtained through calculation in which, for the measured concentration, the reduced amount of the volume for the solvent was taken into consideration.
The graphs indicate that, in Example 1, low reflection (for example, not greater than 1% over the entire visible range) was realized for visible light.
These graphs indicate that, in Example 1, low reflection (for example, not greater than 2% over the entire visible range) was realized to almost the same degree as in perpendicular incidence, up to the incidence angle θ=45°, and low reflection was realized to such a degree that the average reflectance in the visible range was not greater than 2% also at the incidence angle θ=50°. That is, the low reflection in Example 1 was realized in a wide range of incidence angles θ (characteristics of moth-eye structure), and incidence angle dependency of low reflection in Example 1 can be said to be low in a range of not less than 0° and not greater than 50°.
Furthermore, a structure and a component of the optical film 4 of Example 1 were observed in the following procedure.
That is, the optical film 4 was formed on one surface of a substrate made of PC in the same manufacturing method as in Example 1, and the optical film 4 on the substrate was cut by gallium (Ga) beams into such a size as to be stored in a sample holder made of copper (FIB (focused ion beam) process). The substrate having the optical film 4 was stored in the sample holder, and the cut substrate having the optical film 4 was covered with a carbon protective film in order to retain the structure of the optical film 4, to produce an observation target.
The observation target was observed by using a transmission electron microscope (TEM), and characteristic X-rays were applied to the observation target to analyze elements of the optical film 4.
Among them, Cu was derived from the sample holder. Ga was derived from FIB process. Furthermore, C was derived from the protective film. Therefore, the optical film 4 contained O, Al, and Si.
According to the above-described observed matters being collectively considered as appropriate, the main component of the layer on the substrate was an oxide of Al, and the main component of the minutely uneven structure was an oxide of Si. Furthermore, by taking into consideration the other observed matters such as stability thereof, it can be said that the main component of the layer on the substrate was Al2O3, and the main component of the minutely uneven structure was SiO2.
By taking into consideration the observation results of, for example, Examples 2 to 37 described below as appropriate, it can be said that the Al2O3 layer (layer on the substrate side) on the substrate and the SiO2 layer (uneven layer) having the minutely uneven structure were clearly divided into two layers in some cases, and the component was gradually changed according to the position in the film thickness direction (direction perpendicular to the film) without strictly dividing the Al2O3 layer and the SiO2 layer into two layers in other cases, according to differences in the material and film thickness of the Al-based manufacture intermediate film 22, and various manufacturing conditions such as a temperature of the solution SL.
When the component was gradually changed according to the position in the film thickness direction without strictly dividing the Al2O3 layer and the SiO2 layer into two layers, the boundary between various films may be unclear. Furthermore, in this case, typically, in the layer on the substrate side, a component ratio of Al2O3 is higher at a position closer to the substrate, and a component ratio of SiO2 to Al2O3 is higher at a position farther from the substrate. That is, in the film thickness direction, the composition ratio of SiO2 to Al2O3 is proportional to the distance from the substrate.
Furthermore, the uneven layer can contain Al2O3 in a state where the Al2O3 does not become a main component. For example, the uneven layer can have a core (skeleton), of the minutely uneven structure, which contains Al2O3 as a main component, and a coating which contains, as a main component, SiO2 covering a part or the entirety of the core.
Examples 2 to 37 and Comparative example 1 are described below.
Examples 2 to 37 and Comparative example 1 were manufactured similarly to Example 1. However, as indicated below in Table 2 to Table 9, in each of Examples 2 to 37 and Comparative example 1, at least one of the concentration of silica in the solution SL, a material of the Al-based manufacture intermediate film 22, a material of the base 2, a temperature of the solution SL, and a physical film thickness of the Al-based manufacture intermediate film 22 was different from that in Example 1.
All of the Al-based manufacture intermediate films 22 of Examples 2 to 37 and Comparative example 1 were formed by DC sputtering, and the process condition thereof was set for each material of the Al-based manufacture intermediate film 22 as indicated above in Table 1. In Table 1, process conditions for vapor deposition are also indicated as modifications.
In the lowermost lines in Table 2 to Table 9, an average reflectance in each example is indicated.
According to these graphs and tables, in comparative example 1, the average reflectance was greater than 9% and was almost 10%, and it cannot be said that reflection of visible light was sufficiently inhibited.
Meanwhile, in Examples 2 to 37, similarly to Example 1, it is indicated that low reflection of visible light was realized.
According to various observations, also in Examples 2 to 37, similarly to Example 1, it was confirmed that low reflection was realized in a state where incidence angle dependency was low, and the minutely uneven structure was made of SiO2 (the main component of the minutely uneven structure was a SiO2 layer), and, furthermore, a layer made of Al2O3 (having Al2O3 as a main component) was formed between the minutely uneven structure and the substrate.
Particularly, in a case where the Al-based manufacture intermediate film 22 was made of AlN, the optical film 4 for antireflection was formed with various physical film thicknesses of the Al-based manufacture intermediate films 22 and various temperatures of the solution SL (Examples 1 to 20).
Furthermore, also in a case where the Al-based manufacture intermediate film 22 was made of Al2O3(Examples 23 to 28, 30 to 31) or Al (Example 29), the optical film 4 for antireflection was formed.
Moreover, even when the substrate was a white sheet glass, the optical film 4 for antireflection was formed (Examples 21 to 29).
Change of characteristics according to change of temperature of the solution SL was found by comparison among the above-described Examples 2, 7, 10, 15, and 18.
Examples 2, 7, 10, 15, and 18 were the same in the concentration (0.06 mg/l) of silica, the material (AlN) of the Al-based manufacture intermediate film 22, the material (PC) of the substrate, and the physical film thickness (78.5 to 78.51 nm) of the Al-based manufacture intermediate film 22, and were different in the temperature of the solution SL, and the temperatures of the solution SL in Examples 2, 7, 10, 15, and 18 were 95, 90, 85, 80, and 75° C., respectively.
Change of characteristics according to change of concentration of silica in solution SL was found by comparison among the above-described Examples 32 to 37 and Comparative example 1.
Examples 32 to 37 and Comparative example 1 were the same in the material (AlN) of the Al-based manufacture intermediate film 22, the material (PC) of the substrate, the temperature (90° C.) of the solution SL, and the physical film thickness (78.5 nm) of the Al-based manufacture intermediate film 22, and were different in the concentration of silica in the solution SL, and the concentrations of silica in the solution SL in Examples 32 to 37 and Comparative example 1 were 0.003, 0.06, 0.5, 1, 2, 10, and 20 mg/l, respectively.
In Example 32, the concentration of silica in the solution SL was adjusted by using pure water having an extremely high purity, as it was. In Example 33, the concentration of silica in the solution SL was adjusted by using pure water having about normal purity, as it was. the concentration of silica in the solution SL was adjusted by putting an appropriate amount of silica gel into pure water having about normal purity and sufficiently stirring the mixture. In pure water having an extremely high purity and pure water having about normal purity, a small amount of silica was not completely eliminated and was left.
The concentration of silica was obtained in the manner as described in Example 1.
The above-described
Table 10 indicates a relationship between the concentration of silica in the solution SL and the average reflectance in Examples 32 to 37 and Comparative example 1.
According to these figures and tables, in a case where the concentration of silica in solution SL was not greater than 10 mg/l, one surface reflectance was further reduced as compared with a case (Comparative Example 1) where the temperature of the solution SL was greater than 10 mg/l. In a case where the concentration of silica in solution SL was not greater than 2 mg/l, one surface reflectance was further reduced as compared with a case (Example 37, Comparative example 1) where the temperature of the solution SL was greater than 2 mg/l.
In Comparative example 1, the Al-based manufacture intermediate film 22 was not changed in the solution SL, and the Al-based manufacture intermediate film 22 was left as AlN in the form of a layer.
In a reference example different from the examples and the comparative example described above, the Al-based manufacture intermediate film 22 similar to those in Examples 32 to 37 and Comparative example 1 (except for the concentration of silica in the solution SL) was immersed in tap water heated to 90° C. as the solution SL, for three minutes. In the reference example, as in Comparative example 1, an effect of reducing reflectance was not exhibited, and the Al-based manufacture intermediate film 22 did not change. The concentration of silica in the tap water was 20 mg/l.
In Examples 1 to 37, the base 2 (substrate), and the optical film 4 formed directly on the film-formation surface F of the base 2 are provided, and the optical film 4 has the Al2O3 layer 12 that is made of Al2O3 and is disposed on the base 2 side, and the SiO2 layer 14 that is made of SiO2 and that has the minutely uneven structure. Alternatively, in Examples 1 to 37, the base 2 (substrate), and the optical film 4 formed directly on the film-formation surface F of the base 2 are provided, and the optical film 4 has the Al2O3 layer 12 that contains Al2O3 as a main component and that is disposed on the base 2 side, and the SiO2 layer 14 that contains SiO2 as a main component and that has the minutely uneven structure.
Therefore, the base 2 (optical product 1) having the optical film 4 that exhibits an antireflection effect in a state where the incidence angle dependency is low, is provided.
The manufacturing method according to Examples 1 to 37 includes forming, on the base 2 (substrate), the Al-based manufacture intermediate film 22 made of aluminium, an aluminium alloy, or an aluminium compound, and immersing the base 2 having the Al-based manufacture intermediate film 22 in an aqueous solution of silica (the solution SL), and the concentration of silica in the solution SL is less than or equal to 10 mg/l unlike Comparative example 1 (20 mg/l). Accordingly, the optical product 1 including the optical film 4 that has the minutely uneven structure made of SiO2 and that exhibits an antireflection effect in a state where the incidence angle dependency is low, is obtained.
In the manufacturing method according to Examples 1 to 17, and 21 to 37, the solution SL (aqueous solution) has a temperature of not lower than 80° C. and not higher than 100° C. In the manufacturing method according to Examples 1 to 37, the Al-based manufacture intermediate film 22 is made of at least one of Al, Al2O3, AlN, and AlON. Therefore, the optical product 1 having the optical film 4 that more advantageously exhibits the antireflection effect, is obtained.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2021-018431 | Feb 2021 | JP | national |
This application is a Continuation of International Application No. PCT/JP2021/046105, filed on Dec. 14, 2021, which claims the benefit of Japanese Patent Application Number 2021-018431 filed on Feb. 8, 2021, the disclosures of which are incorporated by reference herein in their entireties.
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/JP2021/046105 | Dec 2021 | US |
| Child | 18363800 | US |
