JP5825685B2 - Method for manufacturing antireflection film - Google Patents

Description

The present invention relates to a method of manufacturing an antireflection film having a multilayer structure that prevents reflection of incident light by optical interference, and in particular, antireflection having excellent antireflection characteristics for light beams in a wide wavelength range and a wide incident angle range. The present invention relates to a film manufacturing method .

  An antireflection film is provided on the surface of an optical element substrate such as a lens or a prism constituting the optical device for the purpose of improving the light transmittance. In the antireflection film, the reflection of incident light is mainly suppressed by utilizing the interference action of light. In the case of an antireflection film composed of a single layer, part of incident light is reflected at the surface of the antireflection film and at the interface between the antireflection film and the substrate. When the optical film thickness of the antireflection film is ¼ of the incident light wavelength λ, the phase of the interface reflected light is reversed with respect to the phase of the surface reflected light, and the surface reflected light and the interface reflected light are Cancel each other. When the incident medium is air, and the refractive index of the base material is n (sub), when the refractive index of the antireflection film is (√n (sub)), the reflectance for incident light of wavelength λ is 0%. Can be. However, it is only possible to ensure a low reflectance in a narrow band (near the design center wavelength).

  Therefore, in order to produce a broadband antireflection film having a low reflectance, it is necessary to form a multilayer film in which a plurality of layers having different refractive indexes are combined. When the low refractive index layer disposed at the interface between the multilayer film and air is used as a vapor deposition film, a magnesium fluoride film having a refractive index of about 1.38 or a silica film having a refractive index of 1.49 is generally used. Is done. The performance of the antireflection film greatly depends on the refractive index of the low refractive index layer disposed at the interface, and the lower the refractive index, the higher the antireflection performance. However, there is a limit to the materials that can be used as film forming materials in the vapor deposition method, and it has been difficult to further reduce the refractive index by using the vapor deposited film. Thus, in recent years, development of wet film forming materials capable of taking air into the film has progressed, and a low refractive index layer of 1.15 to 1.35 has been realized by a wet film forming method.

  Conventionally, since many optical devices have used light incident in a specific narrow incident angle range, the antireflection film is optical so that it exhibits an excellent antireflection effect in the specific incident angle range. The design was done. In recent years, lenses having a large numerical aperture and a large lens curvature have been used with the miniaturization and high performance of lenses. When a lens having a large lens curvature is used, the light incident angle at the lens periphery increases. Therefore, there is a demand for an antireflection film having an excellent antireflection effect with respect to light rays in the entire visible light range incident in a wider incident angle range.

  From the above viewpoint, for example, Patent Document 1 discloses an antireflection film comprising a low refractive index layer having a refractive index of 1.20 to 1.50 by forming a film using hollow fine particles by a wet film forming method. Membranes have been proposed. In Patent Document 1, hollow fine particles are employed as a film forming material, and the refractive index of the layer is reduced by introducing voids into the layer. In addition, the hollow fine particles are bonded to each other with the first binder, and the voids between the hollow fine particles are filled with 40% or more of the second binder to improve the durability.

  Patent Document 2 discloses an antireflection film having a two-layer structure including a dense layer and a silica airgel porous layer in order from the single-layer base material side in order to increase the bandwidth of the antireflection film. In the antireflection film disclosed in Patent Document 2, by using the interface reflected light generated at the interface of each layer by changing the refractive index from the base material to the medium side in a smooth step shape with respect to the optical film thickness. The surface reflection light is canceled out, and even when the wavelength of the incident light is in a wide band and the incident angle of the incident light is in a wide range, an excellent antireflection effect can be exhibited.

Japanese Patent No. 4378972 JP 2006-215542 A

"The 35th Optical Symposium Proceedings", Japan Society of Applied Physics, Japan Optical Society, July 2010, P67-P70

  By the way, the low refractive index layer disclosed in Patent Document 1 and the silica airgel porous layer disclosed in Patent Document 2 are both formed by a wet film forming method. In the wet film forming method, it is difficult to accurately form an antireflection film on the curved lens surface. In particular, it is difficult to accurately form an extremely thin antireflection film on the surface of a lens having a large curvature. In addition, when there is a surface defect such as a minute protrusion such as a foreign object or a minute dent such as a scratch on the surface of the lens, the film thickness is uneven over a wide range from the surface defect. As a result, quality variation may occur, and antireflection performance and appearance may be deteriorated.

  Further, the antireflection film disclosed in Patent Document 1 employs a method of improving durability by filling voids between hollow fine particles with a second binder. The higher the porosity in the layer, the lower the refractive index, but at the same time the durability. On the other hand, when the filling rate by the second binder is increased and the porosity in the layer is decreased, the durability is increased, but the refractive index is increased. Thus, the refractive index and the durability are in a trade-off relationship, and in order to obtain a practically sufficient durability, it is difficult to obtain a higher antireflection performance because a large decrease in the refractive index cannot be expected.

  Furthermore, in the antireflection film disclosed in Patent Document 1, the adhesion of the low refractive index layer has not been sufficiently studied, and the adhesion of the low refractive index layer to the substrate may be low. Patent Document 1 also discloses a configuration in which a low refractive index layer is provided via a hard coat layer in order to improve the adhesion of the low refractive index layer to a substrate. However, since the hard coat layer itself is also formed by a wet film forming method, it is difficult to form a hard coat layer with a uniform film thickness on a lens having a large lens curvature. Further, in the antireflection film disclosed in Patent Document 1, the hard coat layer does not function as an optical interference layer. For this reason, the antireflection film is composed of a single optical interference layer, and as described above, sufficient antireflection performance is obtained when the wavelength of incident light deviates from the design wavelength or when the incident angle range is wide. There is a problem that it is not possible.

On the other hand, in the antireflection film disclosed in Patent Document 2, the refractive index and the durability are in a trade-off relationship. That is, when the silica airgel porous layer is formed on the surface of the SiO ₂ layer as the dense layer so that the refractive index is 1.15, practical durability cannot be obtained due to the inherent characteristics of the silica airgel. Silica airgel causes structural changes when moisture is adsorbed. For this reason, when silica airgel is hydrophobically treated with fluoride to prevent moisture adsorption, the refractive index of the silica airgel porous layer increases. Therefore, for example, when silica aerogels are bound together using a binder when forming a silica airgel porous layer, it is reported that the refractive index is about 1.25 in order to have practical durability. (See, for example, “Non-Patent Document 1”).

Accordingly, an object of the present invention is to provide a method for producing an antireflection film that has excellent adhesion and durability, and has excellent antireflection properties for light rays in a wide wavelength range and a wide incident angle range. .

As a result of intensive studies, the present inventors have achieved the above-mentioned problem by adopting the following method for producing an antireflection film.

Antireflection coating according to the present invention is a manufacturing method of a reflection film for producing an antireflection film having a plurality of optical interference layers that are provided on a base material, as the optical interference layer, the substrate Ri by the vacuum deposition method above, by forming a inorganic base layer made of inorganic materials, Ri by the vacuum deposition method on the inorganic undercoat layer, an inorganic oxide, or inorganic-organic composite materials, or their A surface modification layer having a wettability with respect to a coating solution used for forming the adhesion layer as the next layer ,
Using the coating liquid by a wet film formation method on the surface modification layer, an adhesion layer made of a material having adhesiveness with a binder used when forming a low refractive index layer as a next layer is formed , Ri by the wet film formation method on the adhesion layer, the hollow silica particles are deposited low refractive index layer formed by bound with the binder, the surface modification layer, SiO ₂ or SiO as the inorganic oxide Alternatively, an organic silicon oxide is used as the inorganic organic composite material, and a physical film thickness of 0.1 nm or more and 150 nm or less, and the adhesion layer is an acrylic resin as a material having adhesion to the binder. , Polymethyl methacrylate resin, epoxy resin, silicone resin, polybutylene terephthalate resin and organosilicon compound, and a physical film thickness of 0.1 nm or less. It is an upper layer of 150 nm or less, and at least a part of the hollow silica particles is embedded in the adhesion layer.

In the method for producing an antireflection film according to the present invention, the hollow silica particles have an average particle size of 5 nm to 100 nm, and the hollow silica particles are bound to each other by the binder in a state where the outside is coated with the binder. In the low refractive index layer, there are voids other than the hollow portions in the hollow silica particles, and the refractive index of the low refractive index layer is 1.15 or more and 1.24 or less. Preferably there is.

In the manufacturing method of the antireflection film according to the present invention, the inorganic base layer has a refractive index is 1.35 or more 2.35 or less, it a thin layer of a transparent inorganic material is an optical film obtained by laminating more than one layer preferable.
In the method for producing an antireflection film according to the present invention, a function having a refractive index of 1.30 or more and 2.35 or less and a physical film thickness of 0.1 nm or more and 30 nm or less on the surface of the low refractive index layer. Layers may be stacked .

In the method of manufacturing an antireflection film according to the present invention, the antireflection film has a reflectance of 0.5% or less with respect to light having a wavelength of 400 nm or more and 700 nm or less at an incident angle of 0 °, and an incident angle of 0 ° or more and 45 ° or less. The reflectance with respect to light having a wavelength of 400 nm to 700 nm is preferably 1.0% or less.

In the manufacturing method of the antireflection film according to the present invention, the base material is preferably an optical element base material.
In the method for manufacturing an antireflection film according to the present invention, the binder is preferably a resin material or a metal alkoxide.

According to the present invention, on the inorganic underlayer formed on the base material by the vacuum film forming method, the film is formed by the vacuum film forming method and applied to the coating liquid used when forming the adhesion layer. A low refractive index layer formed by binding hollow silica particles with a binder via a surface modification layer having wettability and an adhesive layer having adhesiveness with a binder used when forming the low refractive index layer. Therefore, an antireflection film having excellent adhesion to the substrate can be obtained. In addition, the adhesion layer and the low refractive index layer are each formed by a wet film formation method, but each film is formed on a surface with good wettability or a surface with good adhesion. It can be good. In addition, since the low refractive index layer is in close contact with the adhesive layer, peeling of the layer due to dropping off of the hollow silica particles is prevented. Since the hollow silica particle itself is a material having excellent durability and stability, by providing a layer of hollow silica particles on the surface side of the antireflection film, the durability and stability of the antireflection film are made excellent. be able to. Further, by setting a part of the hollow silica particles to be embedded in the adhesion layer, it is possible to increase the area where the hollow silica particles and the adhesion layer are in close contact with each other through the binder. It can be firmly adhered to the adhesion layer through the binder. Further, in the antireflection film obtained by the production method of the present invention, the inorganic underlayer, the surface modification layer, the adhesion layer, and the low refractive index layer all function as an optical interference layer. The antireflection characteristic is excellent with respect to the light having a wide wavelength range and a wide incident angle range by utilizing the interface reflected light generated in FIG.

It is a schematic diagram which shows the layer structure of the anti-reflective film manufactured by the manufacturing method of this invention. It is the schematic diagram (a) which shows the structure of the hollow silica which is a constituent material of a low refractive index layer, and the schematic diagram (b) which shows the structure of a low refractive layer. It is a schematic diagram which shows the other example of the contact | adherence structure of an adhesion layer and a low-refractive-index layer. It is a schematic diagram which shows the further another example of the contact | adherence structure of an adhesion layer and a low-refractive-index layer. It is a figure which shows the reflective characteristic of the anti-reflective film manufactured in Example 1. FIG. It is a figure which shows the reflective characteristic of the anti-reflective film manufactured in Example 2. FIG. It is a figure which shows the reflective characteristic of the anti-reflective film manufactured in Example 3. FIG. It is a figure which shows the reflective characteristic of the anti-reflective film manufactured in Example 4. FIG. In the antireflection film manufactured in Example 5, it is a figure which shows the reflection characteristic when a light ray injects with an incident angle of 0 degree. In the antireflection film produced in Example 5, it is a figure which shows the reflection characteristic when a light ray injects with an incident angle of 45 degrees. It is a figure which shows the reflective characteristic of the anti-reflective film manufactured in Example 6. FIG. It is a figure which shows the reflective characteristic of the anti-reflective film manufactured in Example 7. FIG. It is a figure which shows the reflective characteristic of the anti-reflective film manufactured in Example 8. FIG. It is a figure which shows the reflective characteristic of the anti-reflective film manufactured in Example 9. FIG. It is a figure which shows the reflective characteristic of the anti-reflective film manufactured in Example 10. FIG. It is a figure which shows the reflective characteristic of the anti-reflective film manufactured in Example 11. FIG. It is a figure which shows the reflection characteristic of the anti-reflective film manufactured in Example 12. It is a figure which shows the reflective characteristic of the anti-reflective film manufactured in Example 13. FIG. It is a figure which shows the reflective characteristic of the anti-reflective film manufactured in Example 14. FIG. It is a figure which shows the reflective characteristic of the anti-reflective film manufactured in the comparative example 1. It is a figure which shows the reflective characteristic of the anti-reflective film manufactured in the comparative example 2. It is a figure which shows the reflection characteristic of the anti-reflective film manufactured in the comparative example 3.

Hereinafter, an embodiment of a manufacturing method of an antireflection film according to the present invention will be described.

1. Antireflection film 10
First, the configuration of the antireflection film 10 manufactured by the manufacturing method of the present invention will be described with reference to FIG. The antireflection film 10 according to the present invention is an antireflection film 10 including a plurality of optical interference layers (11, 12, 13, 14) provided on a substrate 20, and the inorganic base layer 11 is used as the optical interference layer. The surface modification layer 12, the adhesion layer 13, and the low refractive index layer 14 are provided. In the present invention, the optical interference layer is such that the refractive index and the optical film thickness are set to predetermined values based on the characteristic matrix of the thin film so that the phase change of the interface reflected light with respect to the incident light is set to a predetermined value. An optical thin film that is optically designed. In the present invention, four optical interference layers of the inorganic base layer 11, the surface modification layer 12, the adhesion layer 13, and the low refractive index layer 14 are laminated on the substrate 20 in this order. As a result, even when light in a wide wavelength range is incident in a wide incident angle range, the surface reflected light can be canceled by the interference of light using the interface reflected light generated at each interface. Low reflection can be achieved in a wide wavelength range and a wide incident angle range. In the present invention, the low refractive index layer 14 has a configuration in which hollow silica particles 141 are bound by a binder 142 as shown in FIGS. 2A and 2B, and is formed by a wet film forming method. It is a filmed layer. As described below, the low refractive index layer 14 is not directly laminated on the inorganic underlayer 11, but the low refractive index layer 14 is formed on the inorganic underlayer 11 via the surface modification layer 12 and the adhesion layer 13. By laminating, the adhesion of the antireflection film 10 to the substrate 20 and the film formability are improved. Hereinafter, the base material 20 and each layer will be described.

(1) Base material 20
First, the base material 20 on which the antireflection film 10 is provided will be described. In the present invention, an optical element substrate can be used as the substrate 20 on which the antireflection film 10 is provided. The optical element substrate may be made of glass or plastic, and the material is not particularly limited. For example, various optical element substrates 20 such as lenses, prisms (color separation prisms, color synthesis prisms, etc.), polarization beam splitters (PBS), cut filters (for infrared rays, ultraviolet rays, etc.) can be used. As will be described later, the antireflection film 10 according to the present invention is excellent in film formability and adhesion, so that it can be used favorably as the substrate 20 even for a small lens having a large lens curvature.

(2) Inorganic base layer 11
Next, the inorganic base layer 11 will be described. The inorganic underlayer 11 is an optical thin film (single layer film or multilayer film (including equivalent film)) in which one or more sublayers made of an inorganic material formed by a vacuum film forming method are stacked on the surface of the base material 20. Yes, the antireflection film 10 functions as an optical interference layer. Since the inorganic underlayer 11 is formed on the surface of the substrate 20 by a vacuum film formation method, it has excellent adhesion to the surface of the substrate 20. Here, the sub layer refers to a physical layer constituting the inorganic base layer 11. In the present invention, the inorganic base layer 11 has a structure in which at least one or more sub-layers are stacked, and each sub-layer functions as an optical interference layer to realize a low reflectance of the antireflection film 10.

Here, the inorganic material is preferably a transparent inorganic material having a refractive index of 1.35 to 2.35. As such a transparent inorganic material, for example, Al ₂ O ₃ , ZrO ₂ + Al ₂ O ₃ , SiN, SiC, SiO, MgO, La ₂ O ₃ + Al ₂ O ₃ , Y ₂ O ₃ , In ₂ O ₃ + SnO ₂ , La ₂ Ti ₂ O ₇ , SnO ₂ , Ta ₂ O ₅ , HfO ₂ , ZrO ₂ , CeO ₂ , WO ₃ , ZrO ₂ + TiO ₂ , Ta ₂ O ₅ , Ta ₂ O ₅ + ZrO ₂ , Ta ₂ O ₅ + TiO ₂ , Ti ₃ O ₅ , Ti ₄ O ₇ , TiPr ₆ O ₁₁ + TiO ₂ , TiO, TiO ₂ , Nb ₂ O ₅ , TiO ₂ + La ₂ O ₃ , Pr ₆ O ₁₁ + TiO ₂ , SiO ₂ , SiO _x N _y , mention may be made of _{CeO 2, MgF 2, ZnS,} YF 3.

  In the present invention, any of a physical vapor deposition method and a chemical vapor deposition method can be suitably used as the vacuum film formation method. Examples of physical vapor deposition include vacuum vapor deposition, sputtering, ion plating, and ion beam vapor deposition. As the chemical vapor deposition method, a CVD method (including a plasma CVD method) can be given. Among these, in particular, a vacuum deposition method, a sputtering method, and a CVD method can be suitably employed.

  The inorganic underlayer 11 is a single layer film or a multilayer film in which sublayers made of an inorganic material having a refractive index in the range of 1.35 to 2.35 are stacked. From an optical point of view, the entire antireflection film 10 including the underlayer, the surface modification layer, the adhesion layer, and the low refractive index layer is considered to be a sub-layer as in the case of designing an ordinary antireflection film. The refractive index and film thickness can be designed by the matrix method. By increasing the number of sub-layers constituting the inorganic underlayer 11, the antireflection film 10 having higher antireflection performance can be obtained.

  In order to obtain the anti-reflection film 10 having a wider band and lower reflection, the optical film thickness of each sub-layer is preferably 150 nm or less. When the optical film thickness of each sub-layer exceeds 150 nm, it is not preferable because it has a design with many unnecessary ripples and the average reflectance of the antireflection film 10 cannot be kept low.

(3) Surface modified layer 12
Next, the surface modification layer 12 that functions as the second optical interference layer of the antireflection film 10 will be described. The surface modification layer 12 is formed on the inorganic underlayer 11 by a vacuum film formation method, and is made of an inorganic oxide, an inorganic-organic composite material, or a mixture containing at least one of these materials. It is a layer having wettability with respect to a coating liquid used when forming a certain adhesion layer 13. Since the surface modification layer 12 is formed by a vacuum film formation method in the same manner as the inorganic underlayer 11, the adhesion to the surface of the inorganic underlayer 11 is good. In addition, the surface modification layer 12 has wettability with respect to a coating solution used when the adhesion layer 13 is formed. Therefore, the adhesion layer 13 can be satisfactorily formed on the surface of the surface modification layer 12 by a wet film formation method, and the adhesion between the surface modification layer 12 and the adhesion layer 13 can be improved. . In addition, the vacuum film-forming method can employ | adopt the method similar to the method demonstrated in the inorganic base layer 11. FIG. For this reason, the description about the vacuum film-forming method is abbreviate | omitted here.

  Here, having wettability with respect to the coating solution means that the contact angle of the coating solution with respect to the surface modification layer 12 is less than 45 °. When the contact angle is 45 ° or more, the coating liquid hardly gets wet on the surface of the surface modification layer 12 and it is difficult to form the adhesion layer 13. On the other hand, if the contact angle is less than 45 °, the coating liquid gets wet on the surface of the surface modification layer 12, and the lower the contact angle, the better the coating liquid gets wet on the surface modification layer 12, A uniform adhesion layer 13 with no unevenness can be formed on the surface of the surface modification layer 12. At the same time, the adhesion between the surface modification layer 12 and the adhesion layer 13 can be improved. From this viewpoint, the contact angle is preferably 30 ° or less, more preferably 10 ° or less, and even more preferably 5 ° or less.

As the film forming material used when forming the surface modified layer 12, any inorganic oxide or inorganic / organic composite material having the above contact angle within the above-described range can be preferably used. Further, if surface treatment such as UV cleaning described later is performed, many materials such as Nb ₂ O ₅ , ZrO ₂ , Al ₂ O _3, and TiO ₂ can be selected as film forming materials as inorganic oxides. However, it is known that even if the surface treatment is performed, the contact angle returns to the contact angle before the surface treatment with time. Therefore, in order to maintain a good contact angle for a long time, it is preferable to use a material containing Si as a film forming material. For example, as the inorganic oxide containing Si, SiO ₂ and SiO that can be deposited by vacuum deposition can be preferably used. Moreover, as an inorganic organic composite material containing Si, for example, hexamethyldisiloxane (HMDSO) can be suitably used. By using these materials, the surface modified layer 12 excellent in wettability with the coating liquid can be obtained. When the surface modification layer 12 is formed by CVD using an organic silicon oxide such as hexamethyldisiloxane, it becomes a SiO ₂ layer (organic silicon oxide film) containing hydrocarbons.

  At this time, the surface of the surface modification layer 12 may be subjected to UV surface treatment, plasma treatment, or the like. By performing these surface treatments, the wettability of the surface modified layer 12 can be further improved. The contact angle range of the coating liquid with respect to the surface modification layer 12 may be a value when the surface treatment is not performed, or may be a value after the surface treatment is performed. In any case, when the adhesion layer 13 is formed, the contact angle with respect to the surface modification layer 12 and the coating solution is preferably within the above range. In addition, as described above, when the contact angle is lower, the film formability and the adhesion are better, and thus the contact angle of the surface modified layer 12 itself after film formation shows a value within the above range. However, it is needless to say that the contact angle of the surface modification layer 12 may be further lowered by the surface treatment.

Here, when UV surface treatment is employed as the surface treatment, wettability can be imparted to the surface of the film without roughening the surface of the film. At this time, if a so-called UV cleaning process is performed as the UV surface treatment, dirt such as organic contaminants adhering to the surface of the surface modification layer 12 can be removed. Thereby, the surface of the surface modification layer 12 can be cleaned, and the film-forming property of the adhesion layer 13 can be improved. For example, by performing UV cleaning treatment for about 180 seconds using a UV cleaner manufactured by Eye Graphics, Inc., the contact angle of the SiO ₂ layer, which was 15 ° to 30 ° during storage at normal temperature, with respect to the coating solution can be increased. It can be reduced to 10 ° or less.

Moreover, as said plasma processing, an atmospheric pressure plasma processing is preferable from a viewpoint that a decompression device etc. are not required. By performing the plasma treatment, dirt such as organic contaminants attached to the surface of the surface modification layer 12 can be removed in the same manner as in the case of performing the UV cleaning treatment. Moreover, by performing plasma treatment, the wettability of the surface of the surface modification layer 12 can be improved, and the adhesion between the surface modification layer 12 and the adhesion layer 13 can be improved. For example, by using a plasma gun manufactured by JEOL Ltd., Ar, _{O 2} atmosphere, the discharge current 25A～38A, discharge voltage 120V, vacuum degree ^{1.6 × 10 -2 Pa~2.0 × 10 -2} Pa When the plasma treatment is performed at, the contact angle of the SiO ₂ layer, which was 10 ° to 30 ° during storage at room temperature, can be reduced to 5 ° or less.

  Next, the physical film thickness of the surface modification layer 12 will be described. The physical film thickness of the surface modification layer 12 is preferably 0.1 nm or more and 150 nm or less. When the physical film thickness of the surface modified layer 12 is less than 0.1 nm, when a lens having an uneven curved surface is adopted as the substrate 20, the surface modified layer 12 is applied to such an uneven curved surface. It is difficult and undesirable to form a film uniformly and without unevenness. The physical film thickness of the surface modification layer 12 is more preferably 1 nm or more from the viewpoint of forming a uniform and non-uniform film even on the uneven curved surface. On the other hand, when the physical film thickness of the surface modification layer 12 exceeds 150 nm, it is difficult to design the film so as to satisfy the optical characteristics required for the surface modification layer 12 as an optical interference layer. That is, it is difficult to optically design the antireflection film 10 so that the phase change has an appropriate value. As a result, the antireflection performance of the antireflection film 10 may be deteriorated, which is not preferable. From this viewpoint, the physical film thickness of the surface modification layer 12 is more preferably 120 nm or less.

(4) Adhesion layer 13
Next, the adhesion layer 13 that functions as the third optical interference layer of the antireflection film 10 will be described. The adhesion layer 13 is formed on the surface modification layer 12 by the wet film formation method using the coating liquid, and has adhesion with the binder 142 used when forming the low refractive index layer 14 as the next layer. It is a layer made of material. Here, the low refractive index layer 14 is a layer in which the hollow silica particles 141 are bound by the binder 142 as described above with reference to FIGS. 2 (a) and 2 (b). By forming the adhesion layer 13 from a material having adhesion to the binder 142, the binder 142 is adhered to the adhesion layer 13, and the hollow silica particles 141 are adhered to the adhesion layer 13 through the binder 142. it can.

  Here, as the material having adhesiveness to the binder 142, the same material as the binder 142 may be used, or a material different from the binder 142 but having adhesiveness to the binder 142 may be used. From the viewpoint of making the adhesiveness to the binder 142 stronger, it is preferable to use the same material as the binder 142. Specific examples of such materials include acrylic resins, polymethyl methacrylate resins, epoxy resins, silicone resins, polybutylene terephthalate resins, cycloolefin resins (for example, ZEONEX (registered trademark, the same applies hereinafter)), and organic silicon. A compound can be mentioned. Moreover, HMDSO which is an organosilicon oxide can be used as the organosilicon compound. A silane coupling agent may also be used. These materials are preferably thermosetting, ultraviolet curable, and room temperature curable compounds, and are preferably thermosetting or ultraviolet curable compounds from the viewpoint of producing the gel layer 131 described below. . In addition, as a binder material of the hollow silica particle 141, an acrylic resin, a silicone resin, and an organic silicon compound are often used, and any of the materials listed above is excellent in adhesion to these binder materials. By making the adhesion layer 13 a layer made of these materials, the workability when forming the low refractive layer 14 can be improved.

  As described above, the adhesion layer 13 is formed by a wet film formation method. Examples of the wet film forming method include a dip coating method, a spin coating method, a spray coating method, a roll coating method, and a screen printing method. An appropriate method can be adopted as appropriate according to the shape of the substrate 20, the film thickness to be formed, and the like.

  The coating liquid used when forming the adhesion layer 13 has an appropriate concentration and viscosity with a solvent for the material itself having adhesion to the binder 142 or a monomer compound thereof (hereinafter referred to as “polymerization and curing component”). And a curing agent such as a crosslinking agent or a polymerization initiator is added as necessary. When the adhesion layer 13 is formed, the coating liquid is applied on the surface of the surface modification layer 12 so as to have an appropriate thickness. Then, the coating film is cured by applying heat treatment or ultraviolet irradiation to the coating film. Simultaneously with this curing reaction or afterwards, the adhesive layer 13 with the coated film cured can be obtained by removing the solvent.

  Here, when performing heat processing, it is preferable to carry out at 90 degreeC or more and 350 degrees C or less, and it is more preferable that it is 150 degrees C or less. For example, even when the base material 20 made of a material having a relatively high thermal expansion coefficient such as a resin base material is used, the thermal expansion deformation of the base material 20 can be prevented if the heat treatment is performed in the temperature range. The heat treatment is the same when other layers are formed. In addition, when performing heat treatment, since there are many base materials with high specific heat, in order to uniformly heat the base material, a clean oven or an inert gas oven is used rather than a method using heat conduction such as a hot plate. Such a method of heating the whole substrate is more preferable.

  When the coating film is cured by heat treatment, after pre-baking at 90 ° C. to 200 ° C. for 10 seconds to 600 seconds, then at 90 ° C. to 350 ° C. for 10 minutes to 24 hours. Post bake is preferably performed. By pre-baking the coating film, the solvent in the coating film can be slowly volatilized at a relatively low temperature. Then, by post-baking, the polymerization component in the coating film is polymerized and crosslinked, and the solvent is volatilized, whereby a dense and uniform film can be formed.

  Here, when prebaking is performed on the coating film, the coating film is in a gel state. In the present invention, before the low refractive index layer 14 is formed, the coating film is not completely cured, and the low refractive index layer 14 is formed on the surface of the gel coating film. It is also a preferred embodiment that the film is completely cured. When the low refractive index layer 14 is formed on the surface of the coating film in a gel state, for example, as shown in FIG. 3, the hollow silica particles 141 in the coating liquid for forming the low refractive index layer are coated by the own weight. It settles in (adhesion layer 13). In this state, when post-baking or ultraviolet irradiation is performed, the polymerization component in the coating film is polymerized or crosslinked, and the adhesion layer 13 is cured in a state in which a part of the hollow silica particles 141 is embedded in the adhesion layer 13. To do.

  In this way, when the hollow silica particles 141 are partially embedded in the adhesion layer 13, the low refractive index layer 14 is formed on the already cured adhesion layer 13 (see FIG. 2B). ), The area where the hollow silica particles 141 and the adhesion layer 13 are in close contact with each other through the binder 142 can be increased. Thereby, the hollow silica particles 141 can be firmly adhered to the adhesion layer 13 via the binder 142.

  When the low refractive index layer 14 is formed on the surface of the coating film in a gel state, the entire adhesion layer 13 may be configured as a gel layer 131 as shown in FIG. 3, or as shown in FIG. Even if it employs a configuration in which the adhesion layer 13 includes a gel layer 131 in a gel state and a cured layer 132 obtained by curing a polymerization component in the coating film, and the gel layer 131 is disposed on the surface side of the adhesion layer 13. Good. However, the gel layer 131 refers to a region or layer in a gel state immediately before the low refractive index layer 14 is formed, and the hardened layer 132 is completely cured immediately before the low refractive index layer 14 is formed. Refers to a region or layer that is in a closed state.

  Whether the entire adhesion layer 13 is a gel layer (131) or the adhesion layer 13 is a two-layer structure of a gel layer 131 and a hardened layer 132 immediately before the low refractive index layer 14 is formed. Depending on the physical film thickness required for 13, any configuration can be adopted as appropriate. In any case, the physical film thickness of the gel layer 131 is preferably 0.1 nm or more and 30 nm or less. When the physical film thickness of the gel layer 131 is less than 0.1 nm, it becomes difficult to form a uniform and non-uniform gel layer 131. On the other hand, when the physical film thickness of the gel layer 131 exceeds 30 nm, although depending on the particle diameter of the hollow silica particles 141, the degree to which the hollow silica particles 141 settle in the adhesion layer 13 varies, and as a result, the reflection Variations in mass production and quality of the protective film 10 may occur. On the other hand, when the physical film thickness of the gel layer 131 is 30 nm or less, the degree to which the hollow silica particles 141 settle in the adhesion layer 13 can be made almost uniform, resulting in mass production variations and quality variations. Can be prevented.

  Here, the physical film thickness of the entire adhesion layer 13 is preferably 0.1 nm or more and 150 nm or less. When the physical film thickness of the entire adhesion layer 13 is less than 0.1 nm, for example, when the substrate 20 is a lens, the surface (optical surface) of the substrate 20 that is an uneven curved surface is formed by a wet film formation method. On the other hand, it is difficult to form such a thin film uniformly and uniformly, which is not preferable. From the viewpoint of forming a uniform and non-uniform film, the physical thickness of the adhesion layer 13 is more preferably 1 nm or more. Further, from the viewpoint of improving the adhesion between the adhesion layer 13 and the low refractive index layer 14, the physical film thickness of the adhesion layer 13 is preferably thicker and is preferably thicker than 5 nm.

  On the other hand, when the physical film thickness of the adhesion layer 13 exceeds 150 nm, it becomes difficult to exhibit optical characteristics as an optical interference layer required for the adhesion layer 13. That is, as in the case of the surface modification layer 12, it is difficult to optically design the antireflection film 10 so that the phase change has an appropriate value. As a result, the antireflection performance of the antireflection film 10 may be deteriorated, which is not preferable. From this viewpoint, the physical film thickness of the adhesion layer 13 is more preferably 120 nm or less.

  Further, as described above, since the physical film thickness of the gel layer 131 is preferably 30 nm or less, the physical film thickness of the entire adhesion layer 13 is greater than 30 nm, and the gel layer 131 is provided. For this, it is preferable that the adhesion layer 13 has a two-layer structure of a gel layer 131 and a hardened layer 132. Note that the cured layer 132 need not be physically one layer, and may be a laminate of a plurality of completely cured thin films.

(5) Low refractive index layer 14
Next, the low refractive index layer 14 that is the fourth optical interference layer will be described. As already described, the low refractive index layer 14 is a layer formed on the adhesion layer 13 by a wet film forming method, and is a layer in which the hollow silica particles 141 are bound by the binder 142.

  Here, in the present invention, the hollow silica particle 141 refers to a silica particle having a balloon structure (hollow structure), and specifically, as shown schematically in FIG. 2 (a), an outer shell made of silica. It refers to a silica particle composed of a portion 141a and a hollow portion 141b whose periphery is completely surrounded by the outer shell portion 141a. In the present invention, the hollow silica particles 141 having the hollow portion 141b are adopted as the main component as a constituent component of the low refractive index layer 14, thereby changing the refractive index of the low refractive index layer 14 to the refractive index of the silica itself (1.48). ). Further, as shown in FIG. 2 (b), the outer shell 141a completely surrounds the periphery as compared with the low refractive index layer 14 or the like composed of an aggregate of porous silica having many pores in the silica particles. By forming the hollow silica particles 141 surrounded by the binder 142 with the binder 142, the low refractive index layer 14 is firmly adhered to the adhesion layer 13, and the antireflection film excellent in scratch resistance and durability. 10 can be used.

  Here, in the present invention, the hollow silica particles 141 are preferably bound to each other in a state where the outer side (outside of the outer shell portion 141 a) is covered with the binder 142. With the outside of the hollow silica particles 141 covered with the binder 142, the hollow silica particles 141 are bound to each other via the binder 142, so that the adhesion with the adhesion layer 13 is increased. Accordingly, durability and scratch resistance of the antireflection film 10 are also improved. In addition, by covering the outside of the hollow silica particles 141 with the binder 142, water and other liquids are adsorbed to the hollow portions 141 b in the hollow silica particles 141 and the void portions 143 in the low refractive index layer 14. Can be suppressed.

  Furthermore, as described with reference to FIGS. 3 and 4, it is more preferable that a part of the hollow silica particles 141 is embedded in the adhesion layer 13. Thereby, as above-mentioned, compared with the case where the hollow silica particle 141 is not embedded in the contact | adherence layer 13 (case shown in FIG.2 (b)), the adhesiveness of the contact | adherence layer 13 and the low refractive index layer 14 is. This is because it becomes even better. Here, a part of the hollow silica particles 141 is embedded in the adhesion layer 13, for example, as shown in FIGS. 3 and 4, the plurality of hollow silica particles 141 are arranged in the thickness direction of the antireflection film 10. When stacked, only a part of the hollow silica particles 141 (one particle) located at the interface between the adhesion layer 13 and the low refractive index layer 14 may be embedded, or one or more hollow silica particles 141 may be embedded. May be embedded in the adhesion layer 13. When one or more hollow silica particles 141 are embedded in the adhesion layer 13, the interface between the adhesion layer 13 and the low refractive index layer 14 is higher than the refractive index of the adhesion layer 13, and the low refractive index layer 14. An intermediate refractive index region having a refractive index lower than the refractive index is provided. The ratio of embedding the hollow silica particles 141 in the adhesion layer 13 can be appropriately designed based on the optical design of the antireflection film 10. However, when one or more hollow silica particles 141 are embedded in the adhesion layer 13, the low refractive index layer 14 in the present invention refers to a region (layer) excluding the intermediate refractive index region.

  In the low refractive index layer 14 configured as described above, the refractive index is preferably 1.15 or more and 1.24 or less. When the refractive index of the low refractive index layer 14 is less than 1.15, it is difficult to sufficiently bind the hollow silica particles 141 with the binder 142 and the hollow silica particles 141 with the binder 142. become. Therefore, when the refractive index of the low refractive index layer 14 is less than 1.15, the durability of the low refractive index layer 14 is deteriorated, which is not preferable. From this viewpoint, the refractive index of the low refractive index layer 14 is more preferably 1.17 or more. On the other hand, when the refractive index of the low refractive index layer 14 exceeds 1.24, the reflectance at the design center wavelength is increased, which is not preferable. Therefore, from this viewpoint, the refractive index of the low refractive index layer 14 is preferably lower within the above range, and more preferably 1.23 or less.

  Further, as shown in FIGS. 2B, 3, and 4, it is preferable that a void portion 143 other than the hollow portion 141 b of the hollow silica particle 141 exists in the low refractive index layer 14. The presence of the void 143 other than the hollow portion 141b in the hollow silica particle 141 in the low refractive index layer 14 can further reduce the refractive index of the low refractive index layer 14 than the refractive index of the silica itself. . In the present invention, as described above, the surface modification layer 12 formed by the vacuum film forming method and the adhesion formed by the wet film forming method are formed on the inorganic base layer 11 formed by the vacuum film forming method. By forming the low refractive index layer 14 through the layer 13 by a wet film forming method, the adhesiveness of the low refractive index layer 14 can be improved without filling the gap portion 143 with a binder material or the like. It is said. For this reason, even when the refractive index of the low refractive index layer 14 is 1.20, practically sufficient durability and scratch resistance can be maintained.

  The volume occupied by the hollow silica particles 141 in the low refractive index layer 14 is preferably 30% by volume or more and 99% by volume or less. The volume occupied by the hollow silica particles 141 as used herein refers to the entire volume of the hollow silica sphere including the outer shell portion 141a of the hollow silica particles 141 and the hollow portion 141b surrounded by the hollow portion 141b in the low refractive index layer 14. Means. When the volume occupied by the hollow silica particles 141 in the low refractive index layer 14 is less than 30% by volume, the durability and scratch resistance of the low refractive index layer 14 are lowered, which is not preferable. Further, when the volume occupied by the hollow silica particles 141 is less than 30% by volume, the volume ratio occupied by the binder 142 in the low refractive index layer 14 increases. As a result, it may be difficult to set the refractive index of the low refractive index layer 14 to a value within the above range. From these viewpoints, the volume occupied by the hollow silica particles 141 in the low refractive index layer 14 is more preferably 60% by volume or more. On the other hand, when the volume occupied by the hollow silica particles 141 in the low refractive index layer 14 exceeds 99% by volume, the volume ratio occupied by the binder 142 binding the hollow silica particles 141 is low, and the hollow silica particles 141 are sufficiently bonded together. As a result, it is difficult to form the low refractive index layer 14. From the viewpoint of sufficiently binding the hollow silica particles 141 and increasing the ratio of the voids 143 present in the low refractive index layer 14, the volume occupied by the hollow silica particles 141 in the low refractive index layer 14 is 90% by volume. The following is more preferable.

Hollow silica particles 141 as the constituent material of the low refractive index layer 14 preferably has an average particle diameter _{D 50} is 5nm or more 100nm or less. When the average particle diameter D ₅₀ of the hollow silica particles 141 is less than 5 nm, it becomes difficult to provide the void portions 143 other than the hollow portions 141 b of the hollow silica particles 141 in the low refractive index layer 14. On the other hand, when the average particle diameter of the hollow silica particles 141 exceeds 100 nm, light scattering (haze) may occur, which is not preferable. When light scattering occurs, the antireflection film 10 using the hollow silica particles 141 is not preferable because it cannot satisfy the antireflection performance required for the imaging element. Furthermore, when the average particle diameter of the hollow silica particles 141 exceeds 100 nm, it becomes extremely difficult to precisely control the physical film thickness of the low refractive index layer 14 in units of several nm.

  On the other hand, as the binder 142, a resin material or a metal alkoxide can be employed. Examples of the resin material include an epoxy resin, an acrylic resin, a fluororesin, a silicone resin, a cycloolefin resin (for example, ZEONEX (registered trademark), etc.) or a monomer compound thereof. A curable, room-temperature curable, or thermosetting compound is preferable, and an ultraviolet curable or room-temperature curable compound is particularly preferable, and a substrate 20 having a high thermal expansion coefficient such as a resin substrate is used. In this case, if the low refractive index layer 14 can be formed without heat treatment, the thermal expansion deformation of the base material 20 can be prevented. The material and the hollow silica particles 141 are mixed, a polymerization initiator or a crosslinking agent is added as necessary, and diluted to an appropriate concentration with a solvent to prepare a coating solution. Wet methods such as a dip coating method, a spin coating method, a spray method, a roll coating method, a screen printing method, etc. can be employed, so that the coating liquid can be made to have an appropriate thickness on the surface of the inorganic underlayer 11 by these methods. Then, the low refractive index layer 14 can be formed by, for example, polymerizing and crosslinking by applying ultraviolet rays or heat treatment, and volatilizing the solvent.

  Further, it is preferably a material in which a metal alkoxide is dissolved or suspended in a solvent to form a sol and a gel is generated by hydrolysis / polymerization. For example, by hydrolysis / polymerization of alkoxysilane or silsesquioxane or the like. It is preferable to use a material from which silica gel is produced. These materials and the hollow silica particles 141 are dissolved or suspended in a solvent to prepare a sol-gel agent, and the sol-gel agent is spray-coated, spin-coated, dip-coated, or flow-coated on the surface of the inorganic underlayer 11. The low refractive index layer 14 can be formed by coating by a bar coating method or the like, creating a gel containing the hollow silica particles 141 by hydrolysis, and volatilizing the solvent.

  The optical film thickness of the low refractive index layer 14 is preferably in the range of 100 nm to 180 nm. However, the optical film thickness refers to a value obtained from the refractive index of the layer × the physical film thickness (nm) (hereinafter the same). When the optical film thickness of the low refractive index layer 14 is less than 100 nm or exceeds 180 nm, it is difficult to set the phase change to an appropriate value, and the antireflection performance of the antireflection film 10 may be deteriorated. Therefore, it is not preferable.

(6) Functional layer 16
As shown in FIG. 1 , the antireflection film 10 has a refractive index of 1.30 or more and 2.35 or less and a physical film thickness of 0.1 nm or more and 30 nm or less on the surface of the low refractive index layer 14. A functional layer 16 may be provided . Reflection preventing film 10, the inorganic base layer 11 provided on the substrate 20, the surface modification layer 12, an optical four-layer structure consisting of adhesive layer 13 and the low refractive index layer 14. As a main configuration related to the antireflection Yes. The functional layer 16 is a transparent and extremely thin film that does not optically affect the antireflection effect obtained by these optical four-layer structures, and the surface of the antireflection film 10 has hardness, scratch resistance, and heat resistance. , Refers to a layer having functions such as improvement of weather resistance, solvent resistance, water repellency, oil repellency, antifogging properties, hydrophilicity, antifouling resistance, conductivity and the like.

Here, the refractive index of the functional layer 16 is not more than 1.30 2.35 or less, and, if the physical thickness of 0.1nm or more 30nm or less, optical for antireflection effect by preventing film 10 reflections Effects can be ignored. When the refractive index exceeds the above range, the antireflection characteristic of the antireflection film 10 may be optically affected. Further, if the film thickness is less than 1 nm, the function required for the functional layer 16 cannot be exhibited even if the functional layer 16 is provided. Further, when the film thickness exceeds 30 nm, even if the refractive index is within the above range, there is a possibility that the antireflection characteristic of the antireflection film 10 may be optically affected, which is not preferable.

As a material constituting the functional layer 16, a transparent material having a refractive index of 1.30 or more and 2.35 or less can be used. As long as the refractive index is within this range and is a transparent material, an appropriate material may be selected as appropriate according to the function to be imparted to the surface of the antireflection film 10. For example, as a transparent inorganic material having a refractive index within the above range, a mixture of SiO _x N _y / SiO ₂ / SiO _x / Al ₂ O ₃ / ZrO ₂ and TiO ₂ / a mixture of La ₂ O ₃ and TiO ₂ / SnO ₂ / ZrO ₂ / La ₂ O ₃ and a mixture of Al ₂ O ₃ / Pr ₂ O ₅ / ITO (indium tin oxide) / AZO (zinc aluminum oxide) and the like. Further, DLC (diamond-like carbon) / HMDSO (hexamethyldisiloxane) / epoxy resin / acrylic resin (particularly, PMMA resin (polymethyl methacrylate resin) / fluorine resin, etc. can be used. In addition, various hard coating agents containing these materials may be used In forming the functional layer 16, an appropriate film forming method can be appropriately employed depending on the material and the film thickness.

  When the functional layer 16 is provided on the surface of the low refractive index layer 14, the total optical film thickness obtained by adding the optical film thickness of the low refractive index layer 14 and the optical film thickness of the functional layer 16 is required to be 100 nm or more and 180 nm or less. It is done. Exceeding this range is not preferable because the antireflection effect of the antireflection film 10 may be reduced.

(7) Reflectance In the antireflection film 10 having the above-described configuration, the physical film thickness of each layer of the base layer 11, the surface modification layer 12, the adhesion layer 13, and the low refractive index layer 14 is within the above-described preferable range. Thus, the reflectance for light with a wavelength of 400 nm or more and 800 nm or less incident at an incident angle of 0 degrees can be reduced to 0.5% or less, and the wavelength of incident light with an incident angle of 0 degrees or more and 45 degrees or less is 400 nm or more and 700 nm or less. The reflectance with respect to light can be made 1.0% or less.

2. Optical element
Light optical element 100 is characterized in that it comprises an anti-reflection film 10 described above. Examples of the optical element 100 include a photographing optical element and a projection optical element. Specifically, a lens, a prism (color separation prism, color synthesis prism, etc.), a polarization beam splitter (PBS), a cut filter (for infrared rays) , For ultraviolet rays, etc.). Examples of the lens include various lenses such as an interchangeable lens of a single-lens reflex camera, a lens mounted on a digital camera (DSC), a lens for a digital camera mounted on a mobile phone, and the like. Note that the optical element 100 shown in FIG. 1 is merely an example, and is merely a schematic diagram of the layer configuration and the like.

  According to the embodiment described above, as already described, the adhesive layer is formed on the inorganic underlayer 11 formed on the substrate 20 by the vacuum film formation method by the vacuum film formation method. Through the surface modification layer 12 having wettability with respect to the coating liquid used when forming the layer 13 and the adhesion layer 13 having adhesion with the binder 142 used when forming the low refractive index layer 14 Since the hollow silica particles 141 are provided with the low refractive index layer 14 formed by binding with the binder 142, the antireflection film 10 having excellent adhesion to the substrate 20 can be obtained. In addition, the adhesion layer 13 and the low refractive index layer 14 are formed by a wet film formation method, respectively, but are formed on a surface with good wettability or a surface with good adhesion, and thus these film formation properties are obtained. It can also be made favorable. Furthermore, since the low refractive index layer 14 is in close contact with the adhesion layer 13, the hollow silica particles 141 are prevented from falling off. Since the hollow silica particle 141 itself is a material excellent in durability and the like, providing the layer of the hollow silica particle 141 on the surface side of the antireflection film 10 makes the antireflection film 10 excellent in durability and the like. be able to. Further, in the antireflection film 10 according to the present invention, since the inorganic underlayer 11, the surface modification layer 12, the adhesion layer 13 and the low refractive index layer 14 all function as an optical interference layer, By utilizing the interface reflected light generated at the interface, the anti-reflection property is excellent with respect to light rays in a wide wavelength range and a wide incident angle range due to the interference action of light.

The above-described embodiment is an aspect of the method for manufacturing the antireflection film 10 according to the present invention, and it is needless to say that the embodiment can be appropriately changed without departing from the gist of the present invention. Specifically, in the method of manufacturing the antireflection film 10 according to the present invention, the inorganic underlayer 11 and the surface modification layer 12 have been described as physically separate layers. The inorganic base layer 11 to be filmed and the surface modification layer 12 are partially overlapped in their configurable materials. Therefore, a material that can be used as a film-forming material for the surface modification layer 12 is used for the inorganic underlayer 11 composed of a single layer or the sublayer disposed on the outermost layer of the inorganic underlayer 11 composed of a plurality of sublayers. When the film is formed, the surface of the inorganic base layer 11 has sufficient wettability with respect to the coating solution used when forming the adhesion layer 13 by performing a surface treatment as necessary. Therefore, the labor for providing the surface modification layer 12 may be saved. Even such cases can be included in the present invention. EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not limited to the following Example.

In Example 1, a lens (refractive index n = 1.77) made of S-LAH66 optical glass manufactured by OHARA INC. Was used as the base material 20. Then, an antireflection film 10 having a laminated structure shown in Table 1 was provided on the surface of the base material 20. Specifically, the antireflection film 10 was produced as follows. First, the inorganic underlayer 11 was formed on the surface of the substrate 20 by a reactive sputtering method using a vacuum film forming apparatus (RAS1100A) manufactured by SYNCHRON Co., Ltd. As shown in Table 1, the inorganic underlayer 11 has three layers of alternating thin film SiO ₂ layers (refractive index 1.48) and extremely thin film Nb ₂ O ₅ layers (refractive index 2.35). It was set as the mixed film which consists of six laminated | stacked layers. The refractive index and physical film thickness of each layer constituting the inorganic underlayer 11 are as shown in Table 1. A SiO ₂ film having a physical thickness of 5 nm was formed as the surface modification layer 12 on the surface of the inorganic base layer 11 thus obtained by the same method as the inorganic base layer 11. In the present specification, when “SiO ₂ ” is simply described, it indicates normal silica having no hollow structure.

  Next, the surface of the surface modification layer 12 was UV cleaned. And the coating film was formed into a film by the spin coat method using MS-A150 made from Mikasa, using the solution which diluted the acrylic resin with PGMEA (propylene glycol monomethyl ether acetate) as a coating liquid. In addition, the contact angle with respect to the coating liquid of the surface modification layer 12 after UV cleaning was 5 ° or less. Thereafter, the coating film was heated (pre-baked) at 90 ° C. for 12 seconds in a clean oven, and then heated (post-baked) at 150 ° C. for 1 hour to perform polymerization crosslinking of the polymerization components in the coating film and volatilize the solvent. . As a result, the coating film was completely cured to obtain an adhesion layer 13 having a refractive index of 1.54 and a physical film thickness of 30 nm.

  Next, a low refractive index layer 14 was formed on the surface of the cured adhesion layer 13. When the low refractive index layer 14 is formed, a coating solution prepared by dissolving, suspending, and preparing hollow silica particles 141 and an acrylic resin as a binder component in a solvent is formed by spin coating as in the case of the adhesion layer 13. Filmed. And the heat processing similar to the contact | adherence layer 13 was performed, and thereby the low-refractive-index layer 14 formed by binding the hollow silica particles 141 with an acrylic resin (binder 141) was obtained. The low refractive index layer 14 had a refractive index of 1.20 and a physical film thickness of 116 nm.

  In Example 2, the anti-reflection film is the same as Example 1 except that the adhesion layer 13 adopts a two-layer structure of a cured layer and a gel layer, and the layer configuration and the thickness of each layer are as shown in Table 2. 10 was produced. Here, only differences from the film formation method of the antireflection film 10 in Example 1 will be described.

  In Example 2, the adhesion layer 13 was formed as follows. First, a cured layer 132 made of an acrylic resin was formed on the surface of the surface modified layer 12 that had been subjected to UV cleaning so as to have a film thickness of 80 nm. In forming the hardened layer 132, the same method as the method for forming the adhesion layer 13 in Example 1 was employed. Then, the gel layer 131 was formed on the surface of the cured layer 132 so that the film thickness of the cured gel layer 131 was 20 nm. For the formation of the gel layer 131, the same method as the method of forming the adhesion layer 13 in Example 1 was adopted except that post-baking was not performed. Then, the low refractive index layer 14 is formed on the surface of the gel layer 131 by the same method as in Example 1 so that the film thickness becomes 116 nm, and then post-baking is performed to form the gel layer 131 and the low refractive index layer 14. Was cured to obtain an antireflection film 10. In addition, the conditions same as Example 1 were employ | adopted for the conditions of prebaking and post-baking.

  In Example 3, as the inorganic underlayer 11, a structure composed of three sublayers shown in Table 3 was adopted, and the thickness of each layer was changed as shown in Table 3. A membrane 10 was obtained. Each sub-layer constituting the inorganic underlayer 11 was formed by a vacuum deposition method using a vacuum deposition apparatus (BMC 1300) manufactured by SYNCHRON Co., Ltd.

  In Example 4, before the low refractive index layer 14 was formed, the entire adhesion layer 13 was a gel layer 131, and the layer configuration and the thickness of each layer were as shown in Table 4. An antireflection film 10 was obtained in the same manner as in Example 2. The gel layer 131 was formed by the same method as that described in Example 2, and the gel layer 131 after curing was formed so as to have a thickness of 30 nm. However, in this embodiment, when the low refractive index layer 14 is formed, the solvent of the low refractive index layer 14 affects the film thickness of the gel layer 131, so that the physical film thickness of the gel layer 13 varies. I understood it. Since it was difficult to control the physical film thickness, unlike the other examples, three samples for reflectance measurement were prepared. As a result of measuring the physical film thickness, it was found to be in the range of 20 ± 5 nm.

Next, in Example 5, N-BK7 made by SCHOTT AG was adopted as the base material 20, the layer configuration and the thickness of each layer were as shown in Table 5, and the surface modification layer 12 was CVD using HMDSDO. An antireflection film 10 of Example 5 was produced in the same manner as in Example 1 except that the SiO ₂ layer (organosilicon oxide layer) containing hydrocarbon was formed by the method.

  In Example 6, the layer configuration and the thickness of each layer are as shown in Table 6, and the example is similar to Example 5 except that the refractive index of the low refractive index layer 14 is changed from 1.20 to 1.24. 6 was prepared. The refractive index of the low refractive index layer 14 was adjusted by increasing the amount of acrylic resin contained in the coating liquid.

In Example 7, the same base material 20 as in Example 5 was used, and the antireflection film 10 of Example 7 was obtained in the same manner as in Example 1 except that the layer configuration and the thickness of each layer were as shown in Table 7. Was made. Here, as shown in Table 7, the thickness of the SiO ₂ layer which is the surface modification layer 12 is as thick as 100 nm as compared with other examples. Further, a silicone resin layer was employed as the adhesion layer 13.

In Example 8, the same base material as in Example 5 was used, and the antireflection film 10 of Example 8 was formed in the same manner as in Example 1 except that the configuration of each layer and the thickness of each layer were as shown in Table 8. Produced. Here, as shown in Table 8, in Example 8, a TiO ₂ layer was adopted as the surface modification layer 12, and a PMMA resin layer was adopted as the adhesion layer 12. Moreover, the PMMA resin layer used what melt | dissolved PMMA resin in toluene as a coating liquid.

  In Example 9, an antireflection film 10 was produced in the same manner as in Example 1 except that the layer configuration and the thickness of each layer were as shown in Table 9. Here, as shown in Table 9, in Example 9, an extremely thin silane coupling agent layer having a physical film thickness of 1 nm was employed as the adhesion layer 13.

  In Example 10, an antireflection film 10 was produced in the same manner as in Example 1 except that the layer configuration and the thickness of each layer were as shown in Table 10. Here, as shown in Table 10, in Example 10, an extremely thin epoxy resin layer having a physical film thickness of 1 nm was employed as the adhesion layer 13.

  In Example 11, an antireflection film 10 was produced in the same manner as in Example 1 except that the layer configuration and the thickness of each layer were as shown in Table 11. Here, as shown in Table 11, in Example 11, a layer made of ZEONEX E48R (registered trademark) having an extremely thin physical thickness of 1 nm was adopted as the adhesion layer 13.

In Example 12, the antireflection film 10 having the layer configuration and the thickness of each layer shown in Table 12 was produced. As shown in Table 12, Example 12 includes an inorganic underlayer 11 composed of a single SiO ₂ layer, and the surface modification layer 12 is also used as the inorganic underlayer 11. Then, an adhesion layer 13 made of an acrylic resin was formed on the surface of the SiO ₂ layer provided on the substrate 20. On the surface of the adhesion layer 13, a low refractive index layer 14 including hollow silica particles 141 using an acrylic resin as a binder 142 was formed. In addition, the method similar to Example 1 was employ | adopted for the film-forming method of each layer.

  In Example 13, the antireflection film 10 was produced in the same manner as in Example 1 except that the layer configuration and the thickness of each layer were as shown in Table 13. Here, as shown in Table 13, in Example 13, an acrylic resin layer having a physical film thickness of 150 nm was employed as the adhesion layer 13.

In Example 14, the antireflection film 10 was produced in the same manner as in Example 1 except that the layer configuration and the thickness of each layer were as shown in Table 14. Here, as shown in Table 14, in Example 14, an SiO ₂ layer having a physical film thickness of 160 nm is employed as the surface modification layer 12, and an acrylic resin layer having a physical film thickness of 172 nm is employed as the adhesion layer 13. It was adopted.

Comparative example

[Comparative Example 1]
As the antireflection film of Comparative Example 1, the layer structure and the thickness of each layer are as shown in Table 15, and an antireflection film was produced on the substrate 20 in the same manner as in Example 1 except that the adhesion layer 13 was not provided. did.

[Comparative Example 2]
As the antireflection film of Comparative Example 2, the layer configuration and the thickness of each layer are as shown in Table 16, and the antireflection film was formed on the substrate 20 in the same manner as in Example 1 except that the surface modification layer 12 was not provided. Was made.

[Comparative Example 3]
The antireflection film of Comparative Example 3 was prepared by providing a low refractive index layer in which hollow silica particles were bound with an acryl resin via a hard coat layer on a base material (N-BK7). The specific layer configuration and the thickness of each layer are as shown in Table 16. When forming the hard coat layer, a silicone thermosetting hard coat material was formed by dipping so that the physical film thickness was 8604 nm as shown in Table 13. Moreover, in order to harden a hard-coat layer, UV irradiation was performed.

[Evaluation]
1. Evaluation Method The antireflection properties, appearance, durability and scratch resistance of each of the antireflection films 10 obtained in Examples 1 to 14 and the antireflection films of Comparative Examples 1 to 3 were evaluated. In the following description, when the antireflection film 10 produced in the example and the antireflection film produced in the comparative example are simultaneously indicated, they are referred to as an antireflection film (10).

(1) Anti-reflective properties Each anti-reflective film (10 ) Was measured. When measuring the spectral reflectance, a spectrophotometer U4000 manufactured by Hitachi High-Technologies Corporation was used.

(2) Appearance The appearance of each antireflection film (10) after film formation was evaluated visually.

(3) Durability to cleaning Ultrasonic cleaning was performed on each antireflection film (10). Specifically, as an ultrasonic cleaning machine, an 8 tank type cleaning machine (including a detergent tank, an IPA tank, and a vapor tank) manufactured by Sonic Fellow Co., Ltd. is used, and the ultrasonic output is weak and strong in two stages. The adjusted one was used.

(4) Scratch resistance In addition, the scratch resistance of each antireflection film (10) was evaluated. In this evaluation, each antireflection film (10) when the surface of each antireflection film (10) is rubbed 10 times in a reciprocating manner by applying a predetermined load using Ultiwipe manufactured by Enomoto Kogyo Co., Ltd. Each was observed for changes in appearance. However, the load when rubbing the surface of each antireflection film (10) was 20 g, 100 g, and 500 g. The load 20 g is equivalent to a load that strokes the surface of the antireflection film (10), the load 100 g is equivalent to a load that gently wipes the surface of the antireflection film (10), and the load 500 g is the antireflection film. It is equal to the load of wiping the surface of (10) strongly.

2. Evaluation Results (1) Reflection Characteristics FIGS. 5 to 19 show measurement results of the antireflection films 10 produced in Examples 1 to 14, respectively. 20 to 22 show the measurement results of the antireflection films prepared in Comparative Examples 1 to 3, respectively. Table 18 shows the maximum reflectivity at an incident angle of 0 ° and an incident angle of 45 ° when the wavelength range of incident light is 400 nm to 700 nm. In the antireflection film 10 manufactured in Examples 1 to 14, when the wavelength range of incident light is 400 nm to 700 nm and the incident angle is 0 °, the maximum value of the spectral reflectance is 0.1% to 0%. Within the 4% range. On the other hand, in the antireflection film 10 manufactured in Examples 1 to 12 in which the film thicknesses of the adhesion layer 13 and the surface modification layer 12 are in a preferable range in the wavelength range, when the incident angle is 45 °, the spectral reflectance is The maximum value of was in the range of 0.4% to 1.0%. As described above, the antireflection film 10 according to the present invention exhibits excellent reflection characteristics in a wide wavelength range, and has a reflectance of 0.5% or less with respect to light having a wavelength of 400 nm to 700 nm at an incident angle of 0 °. It was confirmed that the reflectance with respect to light having a wavelength of 45 ° to 400 nm to 700 nm was 1.0% or less.

  Next, regarding the comparative example, in the antireflection films prepared in Comparative Example 1 and Comparative Example 2, as shown in FIGS. 20, 21, and Table 18, the maximum value when the incident angle is 0 ° is 0. It was possible to achieve a low reflectance in a wide wavelength range, with a maximum value of 1% and an incident angle of 45 ° being 0.6%. On the other hand, as shown in FIG. 22, the antireflection film produced in Comparative Example 3 shows a reflectance of 0.2% or less for a light beam having a wavelength near 550 nm that is incident at an incident angle of 0 °. Yes. However, on the short wavelength side, the degree of increase in reflectivity is high, and the reflectivity for a light beam having a wavelength of 400 nm was 2.0%. Further, for example, a low reflectance of 0.2% or less is shown for a configuration near 450 nm that is incident at an incident angle of 45 °. However, the reflectance increased as the wavelength of incident light moved away from 450 nm, and the reflectance for light having a wavelength of 700 nm was 2.0%.

  Here, the antireflection film (10) produced in each of Examples 1 to 14, Comparative Example 1 and Comparative Example 2 includes the surface modification layer 12 and / or the inorganic underlayer 11 and the low refractive index layer 14. Alternatively, the adhesive layer 13 is provided and a plurality of optical interference layers are provided. As a result, as described above, it is considered that low reflectance can be achieved in a wide wavelength range. On the other hand, the antireflection film produced in Comparative Example 3 is obtained by providing a low refractive index layer 14 composed of hollow silica particles 141 and a binder 142 on a base material 20 via a hard coat layer. The hard coat layer is a layer that is used only for securing the adhesion between the base material and the low refractive index layer and improving the durability of the low refractive index layer 14. As shown in Table 17 and Table 18, the physical thickness of the hard coat layer is as thick as 8604 nm, and the hard coat layer has no function as an optical interference layer. Therefore, the antireflection film of Comparative Example 3 is composed of an optical interference layer having 14 low refractive index layers, and has a low reflectance of 0.5% or less or 1.0% or less only within a narrow wavelength range. Can't show. From the above, it has been confirmed that it is effective to provide a plurality of optical interference layers together with the low refractive index layer 14 in order to achieve a low reflectance over a wider wavelength range.

  The physical thickness of the adhesion layer 13 of the antireflection film 10 produced in Example 13 is 150 nm. This film thickness is the upper limit value of the preferable range of the physical film thickness of the adhesion layer 13 described in the embodiment. Referring to FIG. 18, in the antireflection film 10 of Example 13, when the incident angle of the light beam is 0 °, a low reflectance of 0.3% or less can be achieved in the wavelength range of 400 nm to 700 nm. is made of. On the other hand, when a light beam is incident at an incident angle of 45 °, the maximum reflectance of the antireflection film 10 is 1.03%. As described above, when the physical film thickness of the adhesion layer 13 exceeds 150 nm, it is difficult to design the film so as to satisfy the optical characteristics required for the adhesion layer 13, and the antireflection performance is lowered. Accordingly, the upper limit value of the physical film thickness of the adhesion layer 13 is preferably 150 nm as described above.

Moreover, in the antireflection film 10 produced in Example 14, the physical film thickness of the surface modification layer 12 is 160 nm, and the physical film thickness of the adhesion layer 13 is 172 nm. Any of these physical film thicknesses exceeds the upper limit (150 nm) of the preferred range described above. If the physical film thickness of these layers exceeds the upper limit, and a light beam is incident at an incident angle of 0 °, a low reflectance of 0.4% or less can be maintained throughout the entire area. However, when incident at an incident angle of 45 °, the reflectivity exceeds 1.0% depending on the wavelength of the incident light, and the maximum value in the wavelength range is 1.6%. Therefore, in the manufacturing method of the antireflection film 10 according to the present invention, the physical film thicknesses of the surface modification layer 12 and the adhesion layer 13 are preferably within the above-described preferable range from the viewpoint of improving the antireflection characteristics. .

(2) Appearance Table 18 shows the results of evaluating the appearance of the antireflection film (10) produced in each Example and each Comparative Example. In Table 18, “◯” indicates that the appearance of the antireflection film (10) is good, and “x” indicates that the appearance of the antireflection film is not good. As shown in Table 18, it was confirmed that the appearance of the other antireflection film (10) was good except for the antireflection film of Comparative Example 2 in which the surface modification layer 12 was not provided. Many foreign substances were observed on the surface of the antireflection film prepared in Comparative Example 2. Thus, by providing the surface modification layer 12 on the inorganic underlayer 11, the film-forming property of the adhesion layer 13 and / or the low-refractive index layer 14 formed by the wet film-forming method is improved, and the appearance is improved. It was confirmed that a uniform antireflection film 10 without unevenness was obtained. On the other hand, when the surface modification layer 12 is not provided, the wettability of the coating liquid of the adhesion layer 13 formed by the wet film formation method is poor with respect to the inorganic underlayer 11, and the adhesion layer 13 could not be formed excellently. As a result, the film forming property of the low refractive index layer 14 was lowered, and the appearance of the antireflection film was also deteriorated.

(3) Durability with respect to cleaning Table 18 shows the results of evaluating the durability with respect to cleaning of the antireflection film (10) prepared in each Example and each Comparative Example. In Table 18, “◯” indicates that there was no change in appearance before and after the evaluation test. That is, “◯” indicates that the durability against washing is good. “X” indicates that the appearance deteriorates after the evaluation test and the durability against washing is not good. As shown in Table 18, when the output of the ultrasonic wave was weakened, no change was observed in the appearance of any antireflection film (10). On the other hand, when the output of the ultrasonic wave was increased, the appearance of the antireflection film produced in Comparative Example 1 deteriorated. Specifically, scratches associated with peeling of the antireflection film were observed. The antireflection film of Comparative Example 1 includes the inorganic base layer 11 and the surface modification layer 12 on the base material 20, and the low refractive index layer 14 is directly provided on the surface modification layer 12 without providing the adhesion layer 13. It is a thing. In many cases, the optical element passes through a cleaning line in an assembly process. For this reason, when the adhesion layer 13 is not provided, the durability of the antireflection film 10 is weak, and the antireflection film may be damaged in the cleaning line. Moreover, there is a possibility that it cannot be used practically.

(4) Scratch resistance Table 18 shows the results of evaluating the scratch resistance of the antireflection film (10) prepared in each Example and each Comparative Example. In Table 18, “◯” indicates that there was no change in appearance before and after the evaluation test. That is, “◯” indicates that the scratch resistance is good. In addition, “x” indicates that the appearance deteriorates after the evaluation test and the scratch resistance is not good. Furthermore, “Δ” indicates that minute scratches were observed only in some areas. As shown in Table 18, when the load was 20 g, there was no change in the appearance of any antireflection film (10), and scratches or the like did not adhere to the surface of the antireflection film (10). I understand. When the scratch resistance evaluation test was performed with a load of 100 g, many scratches were observed on the surface of the antireflection film of Comparative Example 1 after the evaluation test. Further, when an evaluation test of scratch resistance was performed with a load of 500 g, after the evaluation test, the low refractive index layer as a surface layer peeled off in the antireflection film of Comparative Example 1. Therefore, by providing the low refractive index layer 14 via the adhesion layer 13, the adhesion of the low refractive index layer 14 is improved, and the durability and scratch resistance of the antireflection film 10 are also improved. I understand that. On the other hand, when the load is 500 g, the thickness of the adhesion layer 13 is 5 nm, 1 nm, and the thickness of the antireflection film 10 of Examples 3, 9, 10, and 11 is relatively small. Minute scratches were observed only in some areas. Accordingly, it can be seen that a thick physical layer of the adhesion layer 13 is preferable from the viewpoint of improving the scratch resistance, and is preferably thicker than 5 nm.

The antireflection film obtained by the production method of the present invention is excellent in adhesion, durability and scratch resistance, and has an excellent antireflection effect for light beams in a wide wavelength range and a wide incident angle range. Therefore, it can be suitably used for an optical device having a wide wavelength range of light rays, an optical device using a lens having a high curvature, or the like.

DESCRIPTION OF SYMBOLS 10 ... Antireflective film 11 ... Inorganic base layer 12 ... Surface modification layer 13 ... Adhesion layer 14 ... Low refractive index layer 15 ... Functional layer 20 ... Base material 100 * ..Optical elements

Claims (7)

A method of manufacturing a reflective film for producing an antireflection film having a plurality of optical interference layers that are provided on a substrate,
As the optical interference layer,
Ri by the vacuum deposition method on the substrate, an inorganic undercoat layer made of inorganic materials deposited,
Ri by the vacuum deposition method on the inorganic underlayer, an inorganic oxide, or inorganic-organic composite material, or consist a mixture thereof, with respect to the coating solution used in forming the adhesion layer is the next layer Form a surface modification layer with wettability ,
Using the coating liquid by a wet film formation method on the surface modification layer, an adhesion layer made of a material having adhesiveness with a binder used when forming a low refractive index layer as a next layer is formed ,
Ri by the wet film formation method on the adhesion layer, the hollow silica particles are deposited low refractive index layer formed by bound with the binder,
The surface modification layer is a layer having a physical film thickness of 0.1 nm or more and 150 nm or less, using SiO ₂ or SiO as the inorganic oxide, or an organic silicon oxide as the inorganic organic composite material,
The adhesion layer uses at least one of acrylic resin, polymethyl methacrylate resin, epoxy resin, silicone resin, polybutylene terephthalate resin, and organosilicon compound as a material having adhesion to the binder, and It is a layer having a physical film thickness of 0.1 nm to 150 nm,
A method for producing an antireflection film , wherein at least a part of the hollow silica particles are embedded in the adhesion layer. The hollow silica particles have an average particle size of 5 nm to 100 nm,
The hollow silica particles are bound to each other by the binder in a state where the outside is coated with the binder,
2. The low refractive index layer includes voids other than hollow portions in the hollow silica particles, and the low refractive index layer has a refractive index of 1.15 to 1.24. The manufacturing method of antireflection film of description. The inorganic base layer has a refractive index is 1.35 or more 2.35 or less, the antireflection film according to claim 1 or claim 2 thin layer of transparent inorganic material is an optical film laminated one or more layers Manufacturing method . The functional layer having a refractive index of 1.30 or more and 2.35 or less and a physical film thickness of 1 nm or more and 30 nm or less is laminated on the surface of the low refractive index layer. The method for producing an antireflection film according to one item. The antireflection film has a reflectance of 0.5% or less for light having a wavelength of 400 nm or more and 700 nm or less incident at an incident angle of 0 °, and is incident at a wavelength of 400 nm or more and 700 nm or less at an incident angle of 0 ° or more and 45 ° or less. The manufacturing method of the anti-reflective film as described in any one of Claims 1-4 whose reflectance with respect to is 1.0% or less. The said base material is an optical element base material, The manufacturing method of the antireflection film as described in any one of Claims 1-5. The method for manufacturing an antireflection film according to any one of claims 1 to 6, wherein the binder is a resin material or a metal alkoxide.

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