JP2020067518A - Reflection prevention film and optical component having the same - Google Patents

Abstract

To provide a reflection prevention film that has improved appearance, low reflection in a wide wavelength range of visible light, and a high reflection prevention effect for wide incident rays, and can reduce occurrence of ghost and flare for substrates having various refractive indexes, and to provide an optical component having the reflection prevention film.SOLUTION: In a reflection prevention film in which a first layer 1, a second layer 2, a third layer 3, a fourth layer, a fifth layer, a sixth layer, a seventh layer, an eighth layer, a ninth layer, a tenth layer, an eleventh layer, and a twelfth layer are laminated in this order on a substrate 6 from the substrate side, a refractive index of the substrate ranges from 1.40 to 2.10 at a reference wavelength λ=520nm, the first, third, fifth, seventh, ninth, and eleventh layers are made of a material having a high refractive index of 1.9 or larger and 2.5 or smaller, the second, fourth, sixth, eighth, and tenth layers are made of a material having a low refractive index of 1.35 or larger and 1.55 or smaller, the twelfth layer is made of a material having an ultra-low refractive index of 1.15 or larger and 1.3 or smaller, and an optical film thickness of the first layer to the twelfth layer is within a predetermined range.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an antireflection film in the visible light band, which is suitable for a taking lens used in a digital camera, a video camera or the like, and an optical component having the antireflection film.

  An antireflection film is formed on a lens surface typified by a digital camera or a video camera in order to prevent a ghost generated due to surface reflection from affecting a captured image to a minimum. Further, in recent years, the number of lens components has tended to increase as the performance and size of image pickup devices have increased, and many zoom lenses and the like are composed of 20 to 30 lenses. However, as the number of lenses to be configured increases, the combination of ghosts caused by the lens surface increases exponentially, so it is difficult to take measures against all of them, and a higher-performance antireflection film is required. There is.

  In order to enhance the antireflection effect on the substrate surface, it is generally known that the antireflection film is formed into a multi-layer film. However, a low refractive index material generally used in the vacuum deposition method is about 1.46 silicon oxide. The amount of magnesium fluoride was about 1.38, and reflection at the interface between air and the low refractive index material could not be completely removed.

  Therefore, in order to improve the performance of the antireflection film, the applicant has developed an antireflection film which has achieved a low reflectance by using a low refractive index material having a refractive index of about 1.2 to 1.25 for the uppermost layer. We are developing.

JP, 2018-101132, A

  Patent Document 1 discloses a six-layer antireflection film applicable within the range of a refractive index of 1.4 to 2.1 of the substrate. Of these, the most air-side layer has a refractive index of 1.2 to 1.2. By using the material made of 1.25 silicon oxide, the reflectance in the wavelength band of 400 to 700 nm has been successfully suppressed to 0.15% or less. However, the antireflection film of Patent Document 1 achieves the maximum effect when the ghost ray incident on the surface to which it is applied is substantially parallel to the surface normal or has a small incident angle, while it is large relative to the surface normal. The effect was insufficient for a ghost that is incident at an angle (so-called oblique incidence). Therefore, when a film is formed on a surface having a relatively small radius of curvature, the spectral reflectance characteristics of the central portion and the peripheral portion change, and there arises a problem that the reflectance of the peripheral portion rises.

  In addition, the unevenness of the reflectance that occurs is reddish toward the outside of the lens, which is not preferable from the viewpoint of not only the ghost but also the appearance. Such a surface is often seen in an object-side lens such as a large-diameter wide-angle lens, and is directly connected to the appearance, and in addition, a high-intensity ghost is often generated due to oblique incidence. Therefore, there is a demand for an antireflection film that has a good appearance and that can obtain good low-reflectivity characteristics even at oblique incidence.

  From the above problems, the present invention has a good appearance with respect to substrates having various refractive indices, has low reflection in a wide wavelength range of visible light, and has a high antireflection effect with respect to a wide incident light ray, and ghost and flare. It is an object of the present invention to provide an antireflection film that can reduce the occurrence of light and an optical component having the antireflection film.

The invention described in claim 1 is, on the substrate, from the substrate side, a first layer, a second layer, a third layer, a fourth layer, a fifth layer, a sixth layer, a seventh layer, an eighth layer, and a ninth layer. A layer, a tenth layer, an eleventh layer, and a twelfth layer in this order, wherein the substrate has a refractive index of 1.40 to 2.10 at a reference wavelength λ of 520 nm. The 1st, 3rd, 5th, 7th, 9th, and 11th layers are high-refractive index materials having a refractive index of 1.9 or more and 2.5 or less. Is a low refractive index material having a refractive index of 1.35 or more and 1.55 or less, and the twelfth layer is an ultra low refractive index material having a refractive index of 1.15 or more and 1.3 or less. The optical film thickness of is within the following range.
First layer: 0.022λ or more and 0.074λ or less Second layer: 0.065λ or more, 0.237λ or less Third layer: 0.043λ or more, 0.136 or less Fourth layer: 0.134λ or more, 0. 295λ or less 5th layer: 0.022λ or more, 0.165λ or less 6th layer: 0.097λ or more, 0.379λ or less 7th layer: 0.057λ or more, 0.228λ or less 8th layer: 0.063λ or more, 0.184λ or less 9th layer: 0.111λ or more, 0.253λ or less 10th layer: 0.111λ or more, 0.188λ or less 11th layer: 0.064λ or more, 0.094λ or less 12th layer: 0.288λ Above, 0.359λ or less

According to a second aspect of the present invention, a first layer, a second layer, a third layer, a fourth layer, a fifth layer, a sixth layer, a seventh layer, an eighth layer and a ninth layer are provided on the substrate from the substrate side. A layer, a tenth layer, an eleventh layer, a twelfth layer, and a thirteenth layer are laminated in this order, and the refractive index of the substrate is 1.40 to 2.10 at a reference wavelength λ = 520 nm. And the first, third, fifth, seventh, ninth, and eleventh layers are low-refractive-index materials having a refractive index of 1.35 or more and 1.55 or less. The 12th layer is a high refractive index material having a refractive index of 1.9 or more and 2.5 or less, and the 13th layer is an ultra low refractive index material having a refractive index of 1.15 or more and 1.3 or less, The optical film thickness of the 1st to 13th layers is in the following range, which is an antireflection film.
First layer: 0.024λ or more and 0.705λ or less Second layer: 0.03λ or more, 0.108λ or less Third layer: 0.072λ or more, 0.756λ or less Fourth layer: 0.022λ or more, 0. 106λ or less Fifth layer: 0.056λ or more, 0.58λ or less Sixth layer: 0.021λ or more, 0.072λ or less Seventh layer: 0.029λ or more, 0.654λ or less Eightth layer: 0.019λ or more, 0.134λ or less 9th layer: 0.087λ or more, 0.205λ or less 10th layer: 0.024λ or more, 0.175λ or less 11th layer: 0.066λ or more, 0.215λ or less 12th layer: 0.05λ Above, 0.087λ or less 13th layer: 0.281λ or more, 0.357λ or less

According to a third aspect of the present invention, the first layer, the second layer, the third layer, the fourth layer, the fifth layer, the sixth layer, the seventh layer, the eighth layer, the ninth layer are arranged on the substrate from the substrate side. A layer, an 10th layer, an 11th layer, a 12th layer, a 13th layer, and a 14th layer are laminated in this order, and the refractive index of the substrate is 1.40 at a reference wavelength λ = 520 nm. 2.10, the first, third, fifth, fifth, seventh, ninth, eleventh, and thirteenth layers are high-refractive index materials having a refractive index of 1.9 or more and 2.5 or less. The 6/8/10/12 layer is a low refractive index material having a refractive index of 1.35 or more and 1.55 or less, and the 14th layer is an ultra low refractive index material of 1.15 or more and 1.3 or less. The antireflection film is made of a refractive index material and has an optical film thickness of the 1st to 14th layers within the following range.
First layer: 0.018λ or more and 0.115λ or less Second layer: 0.03λ or more, 0.233λ or less Third layer: 0.08λ or more, 0.3λ or less Fourth layer: 0.037λ or more, 0. 173λ or less Fifth layer: 0.097λ or more, 0.676λ or less Sixth layer: 0.101λ or more, 0.22λ or less Seventh layer: 0.046λ or more, 0.085λ or less Eightth layer: 0.274λ or more, 0.631λ or less 9th layer: 0.027λ or more, 0.076λ or less 10th layer: 0.124λ or more, 0.226λ or less 11th layer: 0.08λ or more, 0.16λ or less 12th layer: 0.14λ Above, 0.208λ or less 13th layer: 0.054λ or more, 0.088λ or less 14th layer: 0.281λ or more, 0.357λ or less

  In the invention according to claim 4, the high refractive index material is any one of cerium oxide, hafnium oxide, indium oxide, niobium oxide, tin oxide, tantalum oxide, titanium oxide, yttrium oxide, zirconium oxide, and zinc oxide, or The low refractive index material is made of a mixture of the oxides, and the low refractive index material is made of aluminum oxide, magnesium fluoride, or silicon oxide, or a mixture, and the ultra low refractive index material is magnesium fluoride, silicon oxide, or aluminum oxide. The antireflection film according to any one of claims 1 to 3, wherein the antireflection film is a porous material made of a mixture or a mixture thereof.

  According to a fifth aspect of the present invention, the outermost layer from the substrate side is formed by a wet film forming method, and the other layers are formed by a vacuum vapor deposition method, a sputtering method, a CVD method, or an ALD method. The antireflection film according to any one of claims 1 to 4.

  The invention according to claim 6 has an average reflectance of 0.2% or less at a wavelength of 400 nm to 700 nm at an incident angle of 0 to 30 degrees, and an average reflectance of 2.4 at a wavelength of 400 nm to 700 nm at an incident angle of 60 degrees. % Or less, It is an antireflection film in any one of Claim 1 thru | or 5 characterized by the above-mentioned.

  A seventh aspect of the present invention is an optical component including the antireflection film according to any one of the first to sixth aspects.

  ADVANTAGE OF THE INVENTION According to this invention, the external appearance is favorable with respect to the board | substrate of various refractive indexes, it has low reflection in a wide wavelength range of visible light, and also has high antireflection effect with respect to a wide incident light ray, and it has a ghost and a flare. It is possible to provide an antireflection film capable of reducing the occurrence and an optical component having the antireflection film.

3 is a schematic view of an antireflection film formed on a substrate surface according to an embodiment of the present invention. 5 is a graph showing the spectral reflectance of the antireflection film of Example 1. 5 is a graph showing the spectral reflectance of the antireflection film of Example 2. 9 is a graph showing the spectral reflectance of the antireflection film of Example 3. 9 is a graph showing the spectral reflectance of the antireflection film of Example 4. 9 is a graph showing the spectral reflectance of the antireflection film of Example 5. 9 is a graph showing the spectral reflectance of the antireflection film of Example 6. 9 is a graph showing the spectral reflectance of the antireflection film of Example 7. 9 is a graph showing the spectral reflectance of the antireflection film of Example 8. 9 is a graph showing the spectral reflectance of the antireflection film of Example 9. 13 is a graph showing the spectral reflectance of the antireflection film of Example 10. 13 is a graph showing the spectral reflectance of the antireflection film of Example 11. 13 is a graph showing the spectral reflectance of the antireflection film of Example 12. 16 is a graph showing the spectral reflectance of the antireflection film of Example 13. 16 is a graph showing the spectral reflectance of the antireflection film of Example 14. 20 is a graph showing the spectral reflectance of the antireflection film of Example 15. 17 is a graph showing the spectral reflectance of the antireflection film of Example 16. 20 is a graph showing the spectral reflectance of the antireflection film of Example 17. 20 is a graph showing the spectral reflectance of the antireflection film of Example 18. 20 is a graph showing the spectral reflectance of the antireflection film of Example 19. 20 is a graph showing the spectral reflectance of the antireflection film of Example 20. 20 is a graph showing the spectral reflectance of the antireflection film of Example 21. 17 is a graph showing the spectral reflectance of the antireflection film of Example 22. It is a graph which shows the spectral reflectance of the antireflection film of a comparative example. 6 is a graph showing a refractive index dispersion of a film material used for an antireflection film.

The antireflection film according to the first embodiment of the present invention comprises a first layer (1), a second layer (2), and a third layer (3) in order from the substrate (6) side, as shown in the schematic view of FIG. The eleventh layer (4) and the twelfth layer (5) are laminated in this order, and the refractive index of the substrate is 1.40 to 2.10 when the reference wavelength λ is 520 nm. , The 1st, 3rd, 5th, 7th, 9th, and 11th layers are high-refractive index materials having a refractive index of 1.9 or more and 2.5 or less, and the 2nd, 4th, 6th, 8th, and 10th layers are refracted. The low refractive index material having a refractive index of 1.35 or more and 1.55 or less, and the twelfth layer is an ultra low refractive index material having a refractive index of 1.15 or more and 1.3 or less. The optical film thickness of
First layer: 0.022λ or more and 0.074λ or less Second layer: 0.065λ or more, 0.237λ or less Third layer: 0.043λ or more, 0.136 or less Fourth layer: 0.134λ or more, 0. 295λ or less 5th layer: 0.022λ or more, 0.165λ or less 6th layer: 0.097λ or more, 0.379λ or less 7th layer: 0.057λ or more, 0.228λ or less 8th layer: 0.063λ or more, 0.184λ or less 9th layer: 0.111λ or more, 0.253λ or less 10th layer: 0.111λ or more, 0.188λ or less 11th layer: 0.064λ or more, 0.094λ or less 12th layer: 0.288λ As described above, the range is 0.359λ or less.

  According to the present invention, visible light (especially 400 to 700 nm) is formed by stacking alternating layers of high refractive index layers and low refractive index layers from the substrate side and forming an ultra-low refractive index layer on the uppermost layer. It is possible to provide an antireflection film having excellent low reflection performance regardless of the incident angle in the band (1). Furthermore, by using this antireflection film for an optical component, an optical device having high optical performance can be realized.

  If the difference in refractive index between the high-refractive index material and the low-refractive index material is too small, a good reflectance cannot be obtained from a low incident angle to a high incident angle. Therefore, the first layer, the third layer, and the fifth layer The refractive index of the high refractive index material of the seventh layer, the ninth layer, and the eleventh layer is preferably 2.0 or more and 2.4 or less, and the second layer, the fourth layer, the sixth layer, and the eighth layer. The refractive index of the low refractive index material of the layer and the tenth layer is preferably 1.38 or more and 1.5 or less.

  The uppermost twelfth layer is preferably an ultra-low refractive index material having a refractive index of 1.18 or more and 1.29 or less. In order to secure good adhesion strength and environment resistance to the ultra-low refractive index material, it is effective to mix a resin material and a silane agent, and the lower limit of the refractive index should be 1.2 or more. More preferably, in order to maintain low reflection performance, it is more preferable to limit the upper limit of the refractive index to 1.28 or less.

  In order to achieve low reflectance in a wide range of visible light at a wider incident angle, the film thickness of each layer is 0.023λ or more and 0.071λ or less in the first layer, and 0.069λ in the second layer. As described above, 0.226λ or less, the third layer is 0.045λ or more, 0,13λ or less, the fourth layer is 0.141λ or more, 0.281λ or less, and the fifth layer is 0.023λ or more, 0.158λ. Hereinafter, the sixth layer is 0.103λ or more and 0.361λ or less, the seventh layer is 0.06λ or more and 0.218λ or less, the eighth layer is 0.066λ or more, 0.176λ or less, and the ninth layer The eye is 0.117λ or more and 0.241λ or less, the 10th layer is 0.117λ or more and 0.18λ or less, the 11th layer is 0.067λ or more and 0.09λ or less, and the 12th layer is 0.304λ As described above, it is preferably 0.342λ or less.

  Further, the high refractive index material is any one of cerium oxide, hafnium oxide, indium oxide, niobium oxide, tin oxide, tantalum oxide, titanium oxide, yttrium oxide, zirconium oxide, zinc oxide, or a mixture of the above oxides. Preferably, the low refractive index material is any one of aluminum oxide, magnesium fluoride, silicon oxide, or a mixture, and the ultra low refractive index material is any one of magnesium fluoride, silicon oxide, aluminum oxide, or a mixture. It is preferable that the porous material is composed of

  The first to eleventh layers are preferably formed by a vacuum film forming method. In particular, as the vacuum film forming method, it is more preferable to form by a vacuum vapor deposition method of a physical vapor deposition method, a sputtering method, a CVD method of a chemical vapor deposition method, or an ALD method. Further, the twelfth layer of the final layer is preferably formed by a wet film forming method. In particular, it is more preferably formed by a dipping method, a spin coating method, a spray coating method, or a slit coating method.

The antireflection film according to the second embodiment of the present invention comprises a first layer (1), a second layer (2) and a third layer (3) in order from the substrate (6) side as shown in the schematic view of FIG. In this order, thin films are laminated up to a twelfth layer (4) and a thirteenth layer (5), and when the reference wavelength λ is 520 nm, the refractive index of the substrate is 1.40 to 2.10. , The first layer, the third layer, the fifth layer, the seventh layer, the ninth layer, and the eleventh layer are low refractive index materials having a refractive index of 1.35 or more and 1.55 or less, and the second layer, The fourth layer, the sixth layer, the eighth layer, the tenth layer, and the twelfth layer are high refractive index materials having a refractive index of 1.9 or more and 2.5 or less, and the thirteenth layer has a refractive index of 1 or less. It is an ultra-low refractive index material of 15 or more and 1.3 or less, and the optical film thickness of the 1 to 13 layers is
First layer: 0.024λ or more and 0.705λ or less Second layer: 0.03λ or more, 0.108λ or less Third layer: 0.072λ or more, 0.756λ or less Fourth layer: 0.022λ or more, 0. 106λ or less Fifth layer: 0.056λ or more, 0.58λ or less Sixth layer: 0.021λ or more, 0.072λ or less Seventh layer: 0.029λ or more, 0.654λ or less Eightth layer: 0.019λ or more, 0.134λ or less 9th layer: 0.087λ or more, 0.205λ or less 10th layer: 0.024λ or more, 0.175λ or less 11th layer: 0.066λ or more, 0.215λ or less 12th layer: 0.05λ As described above, the 13th layer having a thickness of 0.087λ or less: a range of 0.281λ or more and 0.357λ or less is characterized.

  If the difference in refractive index between the high-refractive index material and the low-refractive index material is too small, a good reflectance cannot be obtained from a low incident angle to a high incident angle. Therefore, the first layer, the third layer, and the fifth layer The refractive index of the high refractive index material of the seventh layer, the ninth layer, and the eleventh layer is preferably 2.0 or more and 2.4 or less, and the second layer, the fourth layer, the sixth layer, and the eighth layer. The low refractive index materials of the layers, the tenth layer and the twelfth layer preferably have a refractive index of 1.38 or more and 1.5 or less.

  The thirteenth layer, which is the uppermost layer, is preferably an ultralow refractive index material having a refractive index of 1.18 or more and 1.29 or less. In order to secure good adhesion strength and environment resistance to the ultra-low refractive index material, it is effective to mix a resin material and a silane agent, and the lower limit of the refractive index should be 1.2 or more. More preferably, in order to maintain low reflection performance, it is more preferable to limit the upper limit of the refractive index to 1.28 or less.

  The thickness of each layer is 0.025λ or more and 0.673λ or less for the first layer, and 0.032λ or more for the second layer in order to achieve low reflectance in a wide range of visible light at a wider incident angle. , 0.103λ or less, the third layer is 0.076λ or more, 0,722λ or less, the fourth layer is 0.023λ or more, 0.101λ or less, and the fifth layer is 0.059λ or more, 0.554λ or less. , The sixth layer is 0.022λ or more and 0.069λ or less, the seventh layer is 0.031λ or more and 0.624λ or less, the eighth layer is 0.02λ or more and 0.128λ or less, and the ninth layer Is 0.092λ or more and 0.196λ or less, the 10th layer is 0.025λ or more and 0.167λ or less, the 11th layer is 0.07λ or more and 0.205λ or less, and the 12th layer is 0.053λ or more , 0.083λ or less, the 13th layer is 0.296λ or more, 0.341λ or less It is preferably below.

  Further, the high refractive index material is any one of cerium oxide, hafnium oxide, indium oxide, niobium oxide, tin oxide, tantalum oxide, titanium oxide, yttrium oxide, zirconium oxide, zinc oxide, or a mixture of the above oxides. Preferably, the low refractive index material is any one of aluminum oxide, magnesium fluoride, silicon oxide, or a mixture, and the ultra low refractive index material is any one of magnesium fluoride, silicon oxide, aluminum oxide, or a mixture. It is preferable that the porous material is composed of

  The first to twelfth layers are preferably formed by a vacuum film forming method. In particular, as the vacuum film forming method, it is more preferable to form by a vacuum vapor deposition method of a physical vapor deposition method, a sputtering method, a CVD method of a chemical vapor deposition method, or an ALD method. Further, the thirteenth layer of the final layer is preferably formed by a wet film forming method. In particular, it is more preferably formed by a dipping method, a spin coating method, a spray coating method, or a slit coating method.

The antireflection film according to the third embodiment of the present invention comprises a first layer (1), a second layer (2) and a third layer (3) in order from the substrate (6) side, as shown in the schematic view of FIG. In this order, thin films are laminated up to the thirteenth layer (4) and the fourteenth layer (5), and the refractive index of the substrate is 1.40 to 2.10 when the reference wavelength λ is 520 nm. , The first layer, the third layer, the fifth layer, the seventh layer, the ninth layer, the eleventh layer, and the thirteenth layer are high refractive index materials having a refractive index of 1.9 or more and 2.5 or less, The second layer, the fourth layer, the sixth layer, the eighth layer, the tenth layer, and the twelfth layer are low refractive index materials having a refractive index of 1.35 or more and 1.55 or less, and the fourteenth layer is It is an ultra-low refractive index material having a refractive index of 1.15 or more and 1.3 or less, and the optical film thickness of the 1st to 14th layers is
First layer: 0.018λ or more and 0.115λ or less Second layer: 0.03λ or more, 0.233λ or less Third layer: 0.08λ or more, 0.3λ or less Fourth layer: 0.037λ or more, 0. 173λ or less Fifth layer: 0.097λ or more, 0.676λ or less Sixth layer: 0.101λ or more, 0.22λ or less Seventh layer: 0.046λ or more, 0.085λ or less Eightth layer: 0.274λ or more, 0.631λ or less 9th layer: 0.027λ or more, 0.076λ or less 10th layer: 0.124λ or more, 0.266λ or less 11th layer: 0.08λ or more, 0.16λ or less 12th layer: 0.14λ As described above, the thirteenth layer of 0.208λ or less: 0.054λ or more and 0.088λ or less, the fourteenth layer: 0.281λ or more, or 0.357λ or less are characterized.

  If the difference in refractive index between the high-refractive index material and the low-refractive index material is too small, a good reflectance cannot be obtained from a low incident angle to a high incident angle. Therefore, the first layer, the third layer, and the fifth layer , The seventh layer, the ninth layer, the eleventh layer, and the thirteenth layer, the high refractive index material preferably has a refractive index of 2.0 or more and 2.4 or less, and the second layer, the fourth layer, and the sixth layer. The low refractive index material of the layers, the eighth layer, the tenth layer, and the twelfth layer preferably has a refractive index of 1.38 or more and 1.5 or less.

  The 14th layer, which is the uppermost layer, is preferably an ultra-low refractive index material having a refractive index of 1.18 or more and 1.29 or less. In order to secure good adhesion strength and environment resistance to the ultra-low refractive index material, it is effective to mix a resin material and a silane agent, and the lower limit of the refractive index should be 1.2 or more. More preferably, in order to maintain low reflection performance, it is more preferable to limit the upper limit of the refractive index to 1.28 or less.

  The thickness of each layer is 0.019 λ or more and 0.11 λ or less for the first layer and 0.032 λ or more for the second layer in order to achieve low reflectance in a wide range of visible light at a wider incident angle. , 0.223λ or less, the third layer is 0.084λ or more and 0.286λ or less, the fourth layer is 0.039λ or more and 0.165λ or less, and the fifth layer is 0.102λ or more and 0.646λ or less. , The sixth layer is 0.107λ or more and 0.21λ or less, the seventh layer is 0.048λ or more and 0.082λ or less, the eighth layer is 0.289λ or more and 0.602λ or less, the ninth layer Is 0.029λ or more and 0.073λ or less, the 10th layer is 0.131λ or more and 0.216λ or less, the 11th layer is 0.085λ or more and 0.153λ or less, and the 12th layer is 0.147λ or more , 0.198λ or less, the 13th layer is 0.057λ or more, 0.084λ or less It is preferable that the 14th layer has a thickness of 0.296λ or more and 0.341λ or less.

  Further, the high refractive index material is any one of cerium oxide, hafnium oxide, indium oxide, niobium oxide, tin oxide, tantalum oxide, titanium oxide, yttrium oxide, zirconium oxide, zinc oxide, or a mixture of the above oxides. Preferably, the low refractive index material is any one of aluminum oxide, magnesium fluoride, silicon oxide, or a mixture, and the ultra low refractive index material is any one of magnesium fluoride, silicon oxide, aluminum oxide, or a mixture. It is preferable that the porous material is composed of

  The first to thirteenth layers are preferably formed by a vacuum film forming method. In particular, as the vacuum film forming method, it is more preferable to form by a vacuum vapor deposition method of a physical vapor deposition method, a sputtering method, a CVD method of a chemical vapor deposition method, or an ALD method. Furthermore, the 14th layer of the final layer is preferably formed by a wet film forming method. In particular, it is more preferably formed by a dipping method, a spin coating method, a spray coating method, or a slit coating method.

  It is preferable that the average reflectance at a wavelength of 400 nm to 700 nm at an incident angle of 0 to 30 degrees is 0.2% or less, and the average reflectance at a wavelength of 400 nm to 700 nm at an incident angle of 60 degrees is 2.4% or less. This not only reduces ghosting and flare due to general lens surfaces, but also keeps the reflectance low even when ghosting occurs at a relatively large incident angle, so even on the front surface of the wide-angle lens. It can have good performance.

  Hereinafter, an example of an example of the antireflection film of the invention will be described. However, the embodiments of the present invention are not limited to the following.

  The respective layers of the base material (6) and the antireflection film (1-5) were simulated in consideration of the refractive index dispersion, and the refractive index dispersion of the film substance used for the antireflection film is shown in FIG.

  Example 1 is an antireflection film having a film configuration of 12 layers shown in Table 1 according to the first embodiment. An FCD100 (manufactured by HOYA) substrate is used, and the first layer and the second layer are sequentially formed from the substrate side up to the eleventh layer by a vacuum film formation method (for example, a vacuum evaporation method or a sputtering method), and the first layer, the second layer 3rd, 5th, 7th, 9th and 11th layers are high refractive index layers made of niobium oxide, 2nd, 4th, 6th, 8th and 10th layers are silicon oxides. The low refractive index layer is composed of The twelfth layer, which is the uppermost layer, is an ultra-low refractive index layer having a refractive index of 1.25 and made of porous silica formed by a wet film forming method (for example, spin coating method, dipping method, etc.).

  FIG. 2 shows the spectral reflectance data of the antireflection film according to Example 1 at incident angles of 0 °, 30 °, and 60 ° at wavelengths of 400 nm to 700 nm. As shown in FIG. 2 and Table 24, the highest reflectance is 0.23%, the average reflectance is 0.13% or less in the incident angle range of 0 to 30 degrees, and the maximum of the incidence angle of 60 degrees. The reflectance was 2.36% and the average reflectance was 1.97%, indicating that a film having a low reflectance was obtained regardless of the incident angle. Further, also in the coat reflection color, it was possible to prevent a rapid hue change due to the incident angle, and the appearance was good.

  Example 2 is an antireflection film having a film configuration of 12 layers shown in Table 2 according to the first embodiment. Using an FCD1 (manufactured by HOYA) substrate, the first layer, the second layer, and the eleventh layer are sequentially formed from the substrate side by a vacuum film forming method to form the first layer, the third layer, the fifth layer, and the seventh layer. The ninth layer and the eleventh layer are high refractive index layers made of niobium oxide, and the second layer, the fourth layer, the sixth layer, the eighth layer, and the tenth layer are low refractive index layers made of silicon oxide. ing. The twelfth layer, which is the uppermost layer, is an ultra-low refractive index layer having a refractive index of 1.25 and made of porous silica formed by a wet film forming method.

  FIG. 3 shows the spectral reflectance data of the antireflection film according to Example 2 at incident angles of 0 °, 30 °, and 60 ° at wavelengths of 400 nm to 700 nm. As shown in FIG. 3 and Table 24, the highest reflectance is 0.23%, the average reflectance is 0.12% or less in the incident angle range of 0 to 30 degrees, and the maximum of the incidence angle of 60 degrees. The reflectance was 2.34% and the average reflectance was 1.97%, indicating that a film having a low reflectance was obtained regardless of the incident angle. Further, also in the coat reflection color, it was possible to prevent a rapid hue change due to the incident angle, and the appearance was good.

  Example 3 is an antireflection film having a film configuration of 12 layers shown in Table 3 according to the first embodiment. An FCD515 (manufactured by HOYA) substrate is used, and the first layer, the second layer, and the eleventh layer are sequentially formed from the substrate side by a vacuum film forming method, and the first layer, the third layer, the fifth layer, and the seventh layer. The ninth layer and the eleventh layer are high refractive index layers made of niobium oxide, and the second layer, the fourth layer, the sixth layer, the eighth layer, and the tenth layer are low refractive index layers made of silicon oxide. ing. The twelfth layer, which is the uppermost layer, is an ultra-low refractive index layer having a refractive index of 1.25 and made of porous silica formed by a wet film forming method.

  FIG. 4 shows spectral reflectance data of the antireflection film according to Example 3 at incident angles of 0 °, 30 °, and 60 ° at wavelengths of 400 nm to 700 nm. As shown in FIG. 4 and Table 24, the highest reflectance is 0.21% and the average reflectance is 0.11% or less in the incident angle range of 0 to 30 degrees. The reflectance was 2.31% and the average reflectance was 2.02%, indicating that a film having a low reflectance was obtained regardless of the incident angle. Further, also in the coat reflection color, it was possible to prevent a rapid hue change due to the incident angle, and the appearance was good.

  Example 4 is an antireflection film having a film configuration of 12 layers shown in Table 4 according to the first embodiment. Using a LAC14 (manufactured by HOYA) substrate, the first layer, the second layer, and the eleventh layer are sequentially formed from the substrate side by a vacuum deposition method to form the first layer, the third layer, the fifth layer, and the seventh layer. The ninth layer and the eleventh layer are high refractive index layers made of niobium oxide, and the second layer, the fourth layer, the sixth layer, the eighth layer, and the tenth layer are low refractive index layers made of silicon oxide. ing. The twelfth layer, which is the uppermost layer, is an ultra-low refractive index layer having a refractive index of 1.25 and made of porous silica formed by a wet film forming method.

  FIG. 5 shows the spectral reflectance data of the antireflection film according to Example 4 at incident angles of 0 °, 30 °, and 60 ° at wavelengths of 400 nm to 700 nm. As shown in FIG. 5 and Table 24, the highest reflectance is 0.22%, the average reflectance is 0.11% or less in the range of the incident angle of 0 to 30 degrees, and the maximum of the incident angle of 60 degrees. It was found that the reflectance was 2.31% and the average reflectance was 2.04%, and a film having a low reflectance was obtained regardless of the incident angle. Further, also in the coat reflection color, it was possible to prevent a rapid hue change due to the incident angle, and the appearance was good.

  Example 5 is an antireflection film having a film structure of 12 layers shown in Table 5 according to the first embodiment. Using an FDS90 (manufactured by HOYA) substrate, the first layer, the second layer, and the eleventh layer are sequentially formed from the substrate side by a vacuum film forming method to form the first layer, the third layer, the fifth layer, and the seventh layer. The ninth layer and the eleventh layer are high refractive index layers made of niobium oxide, and the second layer, the fourth layer, the sixth layer, the eighth layer, and the tenth layer are low refractive index layers made of silicon oxide. ing. The twelfth layer, which is the uppermost layer, is an ultra-low refractive index layer having a refractive index of 1.25 and made of porous silica formed by a wet film forming method.

  FIG. 6 shows the spectral reflectance data of the antireflection film according to Example 5 at incident angles of 0 °, 30 °, and 60 ° at wavelengths of 400 nm to 700 nm. As shown in FIG. 6 and Table 24, the highest reflectance is 0.21% and the average reflectance is 0.11% or less in the range of the incident angle of 0 to 30 degrees, and the maximum of the incident angle of 60 degrees. The reflectance was 2.36% and the average reflectance was 2.05%, indicating that a film having a low reflectance was obtained regardless of the incident angle. Further, also in the coat reflection color, it was possible to prevent a rapid hue change due to the incident angle, and the appearance was good.

  Example 6 is an antireflection film having a film configuration of 12 layers shown in Table 6 according to the first embodiment. Using a TAFD55 (manufactured by HOYA) substrate, the first layer, the second layer, and the eleventh layer are sequentially formed from the substrate side by a vacuum film-forming method to form the first layer, the third layer, the fifth layer, and the seventh layer. The ninth layer and the eleventh layer are high refractive index layers made of niobium oxide, and the second layer, the fourth layer, the sixth layer, the eighth layer, and the tenth layer are low refractive index layers made of silicon oxide. ing. The twelfth layer, which is the uppermost layer, is an ultra-low refractive index layer having a refractive index of 1.25 and made of porous silica formed by a wet film forming method.

  FIG. 7 shows spectral reflectance data of the antireflection film according to Example 6 at incident angles of 0 °, 30 °, and 60 ° at wavelengths of 400 nm to 700 nm. As shown in FIG. 7 and Table 24, the highest reflectance is 0.21% and the average reflectance is 0.10% or less in the range of the incident angle of 0 to 30 degrees, and the maximum of the incident angle of 60 degrees is. The reflectance was 2.27% and the average reflectance was 2.05%, indicating that a film having a low reflectance was obtained regardless of the incident angle. Further, also in the coat reflection color, it was possible to prevent a rapid hue change due to the incident angle, and the appearance was good.

  Example 7 is an antireflection film having a film configuration of 12 layers shown in Table 7 according to the first embodiment. Using a TAFD65 (manufactured by HOYA) substrate, the first layer, the second layer, and the eleventh layer are sequentially formed from the substrate side by a vacuum film forming method to form the first layer, the third layer, the fifth layer, and the seventh layer. The ninth layer and the eleventh layer are high refractive index layers made of niobium oxide, and the second layer, the fourth layer, the sixth layer, the eighth layer, and the tenth layer are low refractive index layers made of silicon oxide. ing. The twelfth layer, which is the uppermost layer, is an ultra-low refractive index layer having a refractive index of 1.25 and made of porous silica formed by a wet film forming method.

  FIG. 8 shows the spectral reflectance data of the antireflection film according to Example 7 at incident angles of 0 °, 30 °, and 60 ° at wavelengths of 400 nm to 700 nm. As shown in FIG. 8 and Table 24, the highest reflectance is 0.21% and the average reflectance is 0.10% or less in the range of the incident angle of 0 to 30 degrees, and the maximum of the incident angle of 60 degrees. The reflectance was 2.26% and the average reflectance was 2.05%, indicating that a film having a low reflectance was obtained regardless of the incident angle. Further, also in the coat reflection color, it was possible to prevent a rapid hue change due to the incident angle, and the appearance was good.

  Example 8 is an antireflection film having a film configuration of 13 layers shown in Table 8 according to the second embodiment. An FCD1 (manufactured by HOYA) substrate is used, and the first layer, the second layer, and the twelfth layer are formed by vacuum deposition from the substrate side, and the first layer, the third layer, the fifth layer, and the seventh layer are formed. The ninth and eleventh layers are low refractive index layers made of silicon oxide, and the second, fourth, sixth, eighth, tenth and twelfth layers are high refractive index layers made of niobium oxide. It has a structure of. The thirteenth layer, which is the uppermost layer, is an ultra-low refractive index layer having a refractive index of 1.25 and made of porous silica formed by a wet film forming method.

  FIG. 9 shows the spectral reflectance data of the antireflection film according to Example 8 at incident angles of 0 °, 30 °, and 60 ° at wavelengths of 400 nm to 700 nm. As shown in FIG. 9 and Table 24, the highest reflectance is 0.29% and the average reflectance is 0.09% or less in the range of the incident angle of 0 to 30 degrees, and the maximum of the incident angle of 60 degrees. The reflectance was 2.25% and the average reflectance was 2.10%, indicating that a film having a low reflectance was obtained regardless of the incident angle. Further, also in the coat reflection color, it was possible to prevent a rapid hue change due to the incident angle, and the appearance was good.

  Example 9 is an antireflection film having a film configuration of 13 layers shown in Table 9 according to the second embodiment. Using the E-FD2 (manufactured by HOYA) substrate, the first layer, the second layer, and the twelfth layer are deposited by a vacuum deposition method from the substrate side to the first layer, the third layer, the fifth layer, and the second layer. 7th layer, 9th layer and 11th layer are low refractive index layers made of silicon oxide, 2nd layer, 4th layer, 6th layer, 8th layer, 10th layer and 12th layer are high refractive index made of niobium oxide It has a stratified structure. The thirteenth layer, which is the uppermost layer, is an ultra-low refractive index layer having a refractive index of 1.25 and made of porous silica formed by a wet film forming method.

  FIG. 10 shows the spectral reflectance data of the antireflection film according to Example 9 at incident angles of 0 °, 30 °, and 60 ° at wavelengths of 400 nm to 700 nm. As shown in FIG. 10 and Table 24, the highest reflectance is 0.29% and the average reflectance is 0.12% or less in the range of the incident angle of 0 to 30 degrees, and the maximum of the incident angle of 60 degrees. The reflectance was 2.45% and the average reflectance was 2.07%, indicating that a film having a low reflectance was obtained regardless of the incident angle. Further, also in the coat reflection color, it was possible to prevent a rapid hue change due to the incident angle, and the appearance was good.

  Example 10 is an antireflection film having a film configuration of 13 layers shown in Table 10 according to the second embodiment. Using a FF8 (manufactured by HOYA) substrate, the first layer, the second layer, and the twelfth layer from the substrate side are formed by a vacuum film formation method, and the first layer, the third layer, the fifth layer, and the seventh layer are formed. The ninth and eleventh layers are low refractive index layers made of silicon oxide, and the second, fourth, sixth, eighth, tenth and twelfth layers are high refractive index layers made of niobium oxide. It has a structure of. The thirteenth layer, which is the uppermost layer, is an ultra-low refractive index layer having a refractive index of 1.25 and made of porous silica formed by a wet film forming method.

  FIG. 11 shows the spectral reflectance data of the antireflection film according to Example 10 at incident angles of 0 °, 30 °, and 60 ° at wavelengths of 400 nm to 700 nm. As shown in FIG. 11 and Table 24, the highest reflectance is 0.37% and the average reflectance is 0.12% or less in the range of the incident angle of 0 to 30 degrees, and the maximum of the incident angle of 60 degrees. The reflectance was 2.36% and the average reflectance was 2.03%, indicating that a film having a low reflectance was obtained regardless of the incident angle. Further, also in the coat reflection color, it was possible to prevent a rapid hue change due to the incident angle, and the appearance was good.

  Example 11 is an antireflection film having a film structure of 13 layers shown in Table 11 according to the second embodiment. Using a TAF3D (manufactured by HOYA) substrate, a first layer, a second layer, and a twelfth layer are sequentially formed from the substrate side by a vacuum film forming method to form a first layer, a third layer, a fifth layer, and a seventh layer. The ninth and eleventh layers are low refractive index layers made of silicon oxide, and the second, fourth, sixth, eighth, tenth and twelfth layers are high refractive index layers made of niobium oxide. It has a structure of. The thirteenth layer, which is the uppermost layer, is an ultra-low refractive index layer having a refractive index of 1.25 and made of porous silica formed by a wet film forming method.

  FIG. 12 shows the spectral reflectance data of the antireflection film according to Example 11 at incident angles of 0 °, 30 °, and 60 ° at wavelengths of 400 nm to 700 nm. As shown in FIG. 12 and Table 24, the highest reflectance is 0.22%, the average reflectance is 0.11% or less in the range of the incident angle of 0 to 30 degrees, and the maximum of the incident angle of 60 degrees. The reflectance was 2.33% and the average reflectance was 2.01%, indicating that a film having a low reflectance was obtained regardless of the incident angle. Further, also in the coat reflection color, it was possible to prevent a rapid hue change due to the incident angle, and the appearance was good.

  Example 12 is an antireflection film having a film configuration of 13 layers shown in Table 12 according to the second embodiment. Using an FDS90 (manufactured by HOYA) substrate, the first layer, the second layer, and the twelfth layer are sequentially formed from the substrate side by a vacuum film forming method to form the first layer, the third layer, the fifth layer, and the seventh layer. The ninth and eleventh layers are low refractive index layers made of silicon oxide, and the second, fourth, sixth, eighth, tenth and twelfth layers are high refractive index layers made of niobium oxide. It has a structure of. The thirteenth layer, which is the uppermost layer, is an ultra-low refractive index layer having a refractive index of 1.25 and made of porous silica formed by a wet film forming method.

  FIG. 13 shows the spectral reflectance data of the antireflection film according to Example 12 at incident angles of 0 °, 30 °, and 60 ° at wavelengths of 400 nm to 700 nm. As shown in FIG. 13 and Table 24, the highest reflectance is 0.18% and the average reflectance is 0.11% or less in the range of the incident angle of 0 to 30 degrees, and the maximum of the incident angle of 60 degrees. The reflectance was 2.36% and the average reflectance was 2.03%, indicating that a film having a low reflectance was obtained regardless of the incident angle. Further, also in the coat reflection color, it was possible to prevent a rapid hue change due to the incident angle, and the appearance was good.

  Example 13 is an antireflection film having a film configuration of 13 layers shown in Table 13 according to the second embodiment. Using a TAFD37A (manufactured by HOYA) substrate, a first layer, a second layer, and a twelfth layer are formed by a vacuum film forming method from the substrate side to form a first layer, a third layer, a fifth layer, and a seventh layer. The ninth and eleventh layers are low refractive index layers made of silicon oxide, and the second, fourth, sixth, eighth, tenth and twelfth layers are high refractive index layers made of niobium oxide. It has a structure of. The thirteenth layer, which is the uppermost layer, is an ultra-low refractive index layer having a refractive index of 1.25 and made of porous silica formed by a wet film forming method.

  FIG. 14 shows the spectral reflectance data of the antireflection film according to Example 13 at incident angles of 0 °, 30 °, and 60 ° at wavelengths of 400 nm to 700 nm. As shown in FIG. 14 and Table 24, the highest reflectance is 0.21% and the average reflectance is 0.12% or less in the range of the incident angle of 0 to 30 degrees, and the maximum of the incident angle of 60 degrees. The reflectance was 2.35% and the average reflectance was 2.03%, indicating that a film having a low reflectance was obtained regardless of the incident angle. Further, also in the coat reflection color, it was possible to prevent a rapid hue change due to the incident angle, and the appearance was good.

  Example 14 is an antireflection film having a film structure of 13 layers shown in Table 14 according to the second embodiment. Using a TAFD45 (manufactured by HOYA) substrate, the first layer, the second layer, and the twelfth layer are formed by a vacuum film formation method from the substrate side to form the first layer, the third layer, the fifth layer, and the seventh layer. The ninth and eleventh layers are low refractive index layers made of silicon oxide, and the second, fourth, sixth, eighth, tenth and twelfth layers are high refractive index layers made of niobium oxide. It has a structure of. The thirteenth layer, which is the uppermost layer, is an ultra-low refractive index layer having a refractive index of 1.25 and made of porous silica formed by a wet film forming method.

  FIG. 15 shows the spectral reflectance data of the antireflection film according to Example 14 at incident angles of 0 °, 30 °, and 60 ° at wavelengths of 400 nm to 700 nm. As shown in FIG. 15 and Table 24, the highest reflectance is 0.20% and the average reflectance is 0.10% or less in the incident angle range of 0 to 30 degrees, and the maximum of the incidence angle of 60 degrees. The reflectance was 2.32%, and the average reflectance was 2.10%, indicating that a film having a low reflectance was obtained regardless of the incident angle. Further, also in the coat reflection color, it was possible to prevent a rapid hue change due to the incident angle, and the appearance was good.

  Example 15 is an antireflection film having a film structure of 13 layers shown in Table 15 according to the second embodiment. Using a TAFD65 (manufactured by HOYA) substrate, a first layer, a second layer, and a twelfth layer are formed by a vacuum film forming method from the substrate side to form a first layer, a third layer, a fifth layer, and a seventh layer. The ninth and eleventh layers are low refractive index layers made of silicon oxide, and the second, fourth, sixth, eighth, tenth and twelfth layers are high refractive index layers made of niobium oxide. It has a structure of. The thirteenth layer, which is the uppermost layer, is an ultra-low refractive index layer having a refractive index of 1.25 and made of porous silica formed by a wet film forming method.

  FIG. 16 shows the spectral reflectance data of the antireflection film according to Example 15 at incident angles of 0 °, 30 °, and 60 ° at wavelengths of 400 nm to 700 nm. As shown in FIG. 16 and Table 24, the highest reflectance is 0.21% and the average reflectance is 0.11% or less in the range of the incident angle of 0 to 30 degrees, and the maximum of the incident angle of 60 degrees. The reflectance was 2.31% and the average reflectance was 2.06%, indicating that a film having a low reflectance was obtained regardless of the incident angle. Further, also in the coat reflection color, it was possible to prevent a rapid hue change due to the incident angle, and the appearance was good.

  Example 16 is an antireflection film having a film configuration of 14 layers shown in Table 16 according to the third embodiment. Using an FCD100 (manufactured by HOYA) substrate, the first layer, the second layer, and the thirteenth layer are sequentially formed from the substrate side by a vacuum deposition method to form the first layer, the third layer, the fifth layer, and the seventh layer. , The ninth layer, the eleventh layer, and the thirteenth layer are high-refractive-index layers made of niobium oxide, the second layer, the fourth layer, the sixth layer, the eighth layer, the tenth layer, and the twelfth layer are made of silicon oxide. It has a structure of a low refractive index layer. The fourteenth layer, which is the uppermost layer, is an ultra-low refractive index layer having a refractive index of 1.25 and made of porous silica formed by a wet film forming method.

  FIG. 17 shows the spectral reflectance data of the antireflection film according to Example 16 at incident angles of 0 °, 30 °, and 60 ° at wavelengths of 400 nm to 700 nm. As shown in FIG. 17 and Table 24, the highest reflectance is 0.15% and the average reflectance is 0.09% or less in the range of the incident angle of 0 to 30 degrees, and the maximum of the incident angle of 60 degrees. The reflectance was 2.28% and the average reflectance was 2.10%, indicating that a film having a low reflectance was obtained regardless of the incident angle. Further, also in the coat reflection color, it was possible to prevent a rapid hue change due to the incident angle, and the appearance was good.

  Example 17 is an antireflection film having a film configuration of 14 layers shown in Table 17 according to the third embodiment. Using FCD705 (manufactured by HOYA) substrate, the first layer, the second layer, and the thirteenth layer from the substrate side are formed by a vacuum film forming method to form the first layer, the third layer, the fifth layer, and the seventh layer. , The ninth layer, the eleventh layer, and the thirteenth layer are high-refractive-index layers made of niobium oxide, the second layer, the fourth layer, the sixth layer, the eighth layer, the tenth layer, and the twelfth layer are made of silicon oxide. It has a structure of a low refractive index layer. The fourteenth layer, which is the uppermost layer, is an ultra-low refractive index layer having a refractive index of 1.25 and made of porous silica formed by a wet film forming method.

  FIG. 18 shows the spectral reflectance data of the antireflection film according to Example 17 at incident angles of 0 °, 30 °, and 60 ° at wavelengths of 400 nm to 700 nm. As shown in FIG. 18 and Table 24, the highest reflectance is 0.20%, the average reflectance is 0.09% or less in the incident angle range of 0 to 30 degrees, and the maximum of the incidence angle of 60 degrees. The reflectance was 2.21%, and the average reflectance was 2.06%, indicating that a film having a low reflectance was obtained regardless of the incident angle. Further, also in the coat reflection color, it was possible to prevent a rapid hue change due to the incident angle, and the appearance was good.

  Example 18 is an antireflection film having a film configuration of 14 layers shown in Table 18 according to the third embodiment. Using an E-FD2 (manufactured by HOYA) substrate, the first layer, the second layer, and the thirteenth layer from the substrate side are formed by a vacuum film forming method to form the first layer, the third layer, the fifth layer, and the third layer. 7th layer, 9th layer, 11th layer and 13th layer are high refractive index layers made of niobium oxide, 2nd layer, 4th layer, 6th layer, 8th layer, 10th layer and 12th layer are silicon oxide The low refractive index layer is composed of The fourteenth layer, which is the uppermost layer, is an ultra-low refractive index layer having a refractive index of 1.25 and made of porous silica formed by a wet film forming method.

  FIG. 19 shows the spectral reflectance data of the antireflection film according to Example 18 at incident angles of 0 °, 30 °, and 60 ° at wavelengths of 400 nm to 700 nm. As shown in FIG. 19 and Table 24, the highest reflectance is 0.20% and the average reflectance is 0.11% or less in the range of the incident angle of 0 to 30 degrees, and the maximum of the incident angle of 60 degrees. The reflectance was 2.22%, and the average reflectance was 2.06%, indicating that a film having a low reflectance was obtained regardless of the incident angle. Further, also in the coat reflection color, it was possible to prevent a rapid hue change due to the incident angle, and the appearance was good.

  Example 19 is an antireflection film having a film configuration of 14 layers shown in Table 19 according to the third embodiment. Using a LAC14 (manufactured by HOYA) substrate, the first layer, the second layer, and the thirteenth layer from the substrate side are vacuum-deposited to form the first layer, the third layer, the fifth layer, and the seventh layer. , The ninth layer, the eleventh layer, and the thirteenth layer are high-refractive-index layers made of niobium oxide, the second layer, the fourth layer, the sixth layer, the eighth layer, the tenth layer, and the twelfth layer are made of silicon oxide. It has a structure of a low refractive index layer. The fourteenth layer, which is the uppermost layer, is an ultra-low refractive index layer having a refractive index of 1.25 and made of porous silica formed by a wet film forming method.

  FIG. 20 shows the spectral reflectance data of the antireflection film according to Example 19 at incident angles of 0 °, 30 °, and 60 ° at wavelengths of 400 nm to 700 nm. As shown in FIG. 20 and Table 24, the highest reflectance is 0.12% and the average reflectance is 0.07% or less in the range of the incident angle of 0 to 30 degrees, and the maximum of the incident angle of 60 degrees. The reflectance was 2.26% and the average reflectance was 2.15%, indicating that a film having a low reflectance was obtained regardless of the incident angle. Further, also in the coat reflection color, it was possible to prevent a rapid hue change due to the incident angle, and the appearance was good.

  Example 20 is an antireflection film having a film configuration of 14 layers shown in Table 20 according to the third embodiment. Using a TAF3D (manufactured by HOYA) substrate, the first layer, the second layer, and the thirteenth layer are sequentially formed from the substrate side by a vacuum film forming method to form the first layer, the third layer, the fifth layer, and the seventh layer. , The ninth layer, the eleventh layer, and the thirteenth layer are high-refractive-index layers made of niobium oxide, the second layer, the fourth layer, the sixth layer, the eighth layer, the tenth layer, and the twelfth layer are made of silicon oxide. It has a structure of a low refractive index layer. The fourteenth layer, which is the uppermost layer, is an ultra-low refractive index layer having a refractive index of 1.25 and made of porous silica formed by a wet film forming method.

  FIG. 21 shows spectral reflectance data of the antireflection film according to Example 20 at incident angles of 0 °, 30 °, and 60 ° at wavelengths of 400 nm to 700 nm. As shown in FIG. 21 and Table 24, the highest reflectance is 0.23% and the average reflectance is 0.08% or less in the range of the incident angle of 0 to 30 degrees, and the maximum of the incident angle of 60 degrees. The reflectance was 2.21%, and the average reflectance was 2.11%, indicating that a film having a low reflectance was obtained regardless of the incident angle. Further, also in the coat reflection color, it was possible to prevent a rapid hue change due to the incident angle, and the appearance was good.

  Example 21 is an antireflection film having a film structure of 14 layers shown in Table 21 according to the third embodiment. Using a TAFD45 (manufactured by HOYA) substrate, a first layer, a second layer and a thirteenth layer are sequentially formed from the substrate side by a vacuum film forming method to form a first layer, a third layer, a fifth layer and a seventh layer. , The ninth layer, the eleventh layer, and the thirteenth layer are high-refractive-index layers made of niobium oxide, the second layer, the fourth layer, the sixth layer, the eighth layer, the tenth layer, and the twelfth layer are made of silicon oxide. It has a structure of a low refractive index layer. The fourteenth layer, which is the uppermost layer, is an ultra-low refractive index layer having a refractive index of 1.25 and made of porous silica formed by a wet film forming method.

  FIG. 22 shows the spectral reflectance data of the antireflection film according to Example 21 at incident angles of 0 °, 30 °, and 60 ° at wavelengths of 400 nm to 700 nm. As shown in FIG. 22 and Table 24, the highest reflectance is 0.20%, the average reflectance is 0.10% or less in the incident angle range of 0 to 30 degrees, and the maximum of the incidence angle of 60 degrees. The reflectance was 2.20% and the average reflectance was 2.05%, indicating that a film having a low reflectance was obtained regardless of the incident angle. Further, also in the coat reflection color, it was possible to prevent a rapid hue change due to the incident angle, and the appearance was good.

  Example 22 is an antireflection film having a film structure of 14 layers shown in Table 22 according to the third embodiment. Using a TAFD65 (manufactured by HOYA) substrate, the first layer, the second layer, and the thirteenth layer from the substrate side are vacuum-deposited to form the first layer, the third layer, the fifth layer, and the seventh layer. , The ninth layer, the eleventh layer, and the thirteenth layer are high-refractive-index layers made of niobium oxide, the second layer, the fourth layer, the sixth layer, the eighth layer, the tenth layer, and the twelfth layer are made of silicon oxide. It has a structure of a low refractive index layer. The fourteenth layer, which is the uppermost layer, is an ultra-low refractive index layer having a refractive index of 1.25 and made of porous silica formed by a wet film forming method.

  FIG. 23 shows the spectral reflectance data of the antireflection film according to Example 22 at incident angles of 0 °, 30 °, and 60 ° at wavelengths of 400 nm to 700 nm. As shown in FIG. 23 and Table 24, the highest reflectance is 0.16% and the average reflectance is 0.08% or less in the range of the incident angle of 0 to 30 degrees, and the maximum of the incident angle of 60 degrees. The reflectance was 2.28% and the average reflectance was 2.14%, indicating that a film having a low reflectance was obtained regardless of the incident angle. Further, also in the coat reflection color, it was possible to prevent a rapid hue change due to the incident angle, and the appearance was good.

Comparative example

  Table 23 shows an antireflection film consisting of 6 layers disclosed in Example 10 of JP-A-2018-101132 as a comparative example. Using a substrate having a refractive index of 1.6, the first layer, the second layer, and the fifth layer are sequentially formed from the substrate side by a vacuum deposition method, and the first layer, the third layer, and the fifth layer have refractive indices. The high refractive index layer of 2.08, the second layer, and the fourth layer are low refractive index layers of 1.38. The sixth uppermost layer is an ultralow refractive index layer having a refractive index of 1.25 and made of porous silica formed by a wet film forming method.

  As shown in FIG. 24 and Table 24, the reflectance at wavelengths 400 nm to 700 nm has a maximum reflectance of 0.07% and an average reflectance of 0.03% at an incident angle of 0 degree, and the ghost light rays have a maximum reflectance of 0.03%. When the angle of incidence on the surface is small, a very good low reflection characteristic is shown, but as the angle of incidence increases, the reflectance rapidly increases, and the maximum reflectance at an angle of incidence of 60 degrees is 4.78. %, The average reflectance also deteriorates to 2.69%. Further, as is clear from FIG. 24, the spectral reflectance at an incident angle of 60 degrees increases more greatly on the long wavelength side than that of 600 nm. When the film is formed, the spectral reflectance characteristics of the central part and the peripheral part of the film change, and the appearance is not good. From the above, it can be seen that in Examples 1 to 22, low reflection characteristics were obtained regardless of the incident angle and the hue change was suppressed as compared with the comparative example.

  As described above, according to the antireflection film of the present invention, the appearance is good for substrates having various refractive indices, low reflection in a wide wavelength range of visible light, and high reflection for a wide incident ray. It is possible to provide an antireflection film having an anti-reflection effect and capable of reducing the occurrence of ghost and flare, and an optical component having the antireflection film.

1 1st layer 2 2nd layer 3 3rd layer 4 X-1 layer 5 X layer 6 Substrate

Claims (7)

On the substrate, from the substrate side, the first layer, the second layer, the third layer, the fourth layer, the fifth layer, the sixth layer, the seventh layer, the eighth layer, the ninth layer, the tenth layer, and the eleventh layer. An antireflection film having a layer and a twelfth layer laminated in this order,
The refractive index of the substrate is 1.40 to 2.10 at a reference wavelength λ = 520 nm,
The 1st, 3rd, 5th, 7th, 9th, and 11th layers are high refractive index materials having a refractive index of 1.9 or more and 2.5 or less,
The second, fourth, sixth, eighth, and tenth layers are low refractive index materials having a refractive index of 1.35 or more and 1.55 or less,
The twelfth layer is an ultra-low refractive index material having a refractive index of 1.15 or more and 1.3 or less,
The antireflection film, wherein the optical thicknesses of the 1st to 12th layers are in the following ranges.
First layer: 0.022λ or more and 0.074λ or less Second layer: 0.065λ or more, 0.237λ or less Third layer: 0.043λ or more, 0.136λ or less Fourth layer: 0.134λ or more, 0. 295λ or less Fifth layer: 0.022λ or more, 0.165λ or less Sixth layer: 0.097λ or more, 0.379λ or less Seventh layer: 0.057λ or more, 0.228λ or less Eightth layer: 0.063 or more, 0.184λ or less 9th layer: 0.111λ or more, 0.253λ or less 10th layer: 0.111λ or more, 0.188λ or less 11th layer: 0.064λ or more, 0.094 or less 12th layer: 0.288λ Above, 0.359λ or less On the substrate, from the substrate side, the first layer, the second layer, the third layer, the fourth layer, the fifth layer, the sixth layer, the seventh layer, the eighth layer, the ninth layer, the tenth layer, and the eleventh layer. A layer, a twelfth layer, and a thirteenth layer, which are laminated in this order,
The refractive index of the substrate is 1.40 to 2.10 at a reference wavelength λ = 520 nm,
The 1st, 3rd, 5th, 7th, 9th, and 11th layers are low refractive index materials having a refractive index of 1.35 or more and 1.55 or less,
The second, fourth, sixth, eighth, tenth and twelfth layers are high refractive index materials having a refractive index of 1.9 or more and 2.5 or less,
The thirteenth layer is an ultra low refractive index material having a refractive index of 1.15 or more and 1.3 or less,
The antireflection film, wherein the optical thicknesses of the 1st to 13th layers are in the following ranges.
First layer: 0.024λ or more and 0.705λ or less Second layer: 0.03λ or more, 0.108λ or less Third layer: 0.072λ or more, 0.756λ or less Fourth layer: 0.022λ or more, 0. 106λ or less Fifth layer: 0.056λ or more, 0.58λ or less Sixth layer: 0.021λ or more, 0.072λ or less Seventh layer: 0.029λ or more, 0.654λ or less Eightth layer: 0.019λ or more, 0.134λ or less 9th layer: 0.087λ or more, 0.205λ or less 10th layer: 0.024λ or more, 0.175λ or less 11th layer: 0.066λ or more, 0.215λ or less 12th layer: 0.05λ Above, 0.087λ or less 13th layer: 0.281λ or more, 0.357λ or less On the substrate, from the substrate side, the first layer, the second layer, the third layer, the fourth layer, the fifth layer, the sixth layer, the seventh layer, the eighth layer, the ninth layer, the tenth layer, and the eleventh layer. An antireflection film comprising a layer, a twelfth layer, a thirteenth layer, and a fourteenth layer laminated in this order,
The refractive index of the substrate is 1.40 to 2.10 at a reference wavelength λ = 520 nm,
The 1st, 3rd, 5th, 7th, 9th, 9th, 11th, and 13th layers are high refractive index materials having a refractive index of 1.9 or more and 2.5 or less,
The second, fourth, sixth, eighth, tenth and twelfth layers are low refractive index materials having a refractive index of 1.35 or more and 1.55 or less,
The fourteenth layer is an ultra-low refractive index material having a refractive index of 1.15 or more and 1.3 or less,
An antireflection film, wherein the optical thicknesses of the 1st to 14th layers are in the following ranges.
First layer: 0.018λ or more and 0.115λ or less Second layer: 0.03λ or more, 0.233λ or less Third layer: 0.08λ or more, 0.3λ or less Fourth layer: 0.037λ or more, 0. 173λ or less Fifth layer: 0.097λ or more, 0.676λ or less Sixth layer: 0.101λ or more, 0.22λ or less Seventh layer: 0.046λ or more, 0.085λ or less Eightth layer: 0.274λ or more, 0.631λ or less 9th layer: 0.027λ or more, 0.076λ or less 10th layer: 0.124λ or more, 0.226λ or less 11th layer: 0.08λ or more, 0.16λ or less 12th layer: 0.14λ Above, 0.208λ or less 13th layer: 0.054λ or more, 0.088λ or less 14th layer: 0.281λ or more, 0.357λ or less The high refractive index material is cerium oxide, hafnium oxide, indium oxide, niobium oxide, tin oxide, tantalum oxide, titanium oxide, yttrium oxide, zirconium oxide, any one of zinc oxide, or a mixture of the oxides,
The low refractive index material is made of aluminum oxide, magnesium fluoride, silicon oxide, or a mixture thereof,
The antireflection film according to any one of claims 1 to 3, wherein the ultra-low refractive index material is a porous material made of any one of magnesium fluoride, silicon oxide, and aluminum oxide, or a mixture thereof. .   The outermost layer from the substrate side is formed by a wet film forming method, and the other layers are formed by any one of a vacuum evaporation method, a sputtering method, a CVD method, and an ALD method. The antireflection film according to claim 4. The average reflectance at a wavelength of 400 nm to 700 nm at an incident angle of 0 to 30 degrees is 0.2% or less,
The antireflection film according to any one of claims 1 to 5, which has an average reflectance of 2.4% or less at a wavelength of 400 nm to 700 nm with an incident angle of 60 degrees.   An optical component comprising the antireflection film according to any one of claims 1 to 6.

Images