JPWO2014017332A1 - Optical components - Google Patents

Abstract

In the optical component formed by vapor-depositing the optical multilayer film 13 on the surface of the substrate 11, the material of the high refractive index layer of the optical multilayer film 13 is formed of niobium-containing titanium suboxide, whereby the niobium-containing titanium suboxide is obtained. The thin film formed by vapor deposition can be improved in conductivity while being in an amorphous state, and without reheating treatment for improving crystallinity for the purpose of increasing conductivity, and three kinds Therefore, it is possible to obtain high antistatic properties without modifying the vapor deposition apparatus in order to handle these materials.

Description

  The present invention relates to an optical component, and more particularly to an optical component using a vapor deposition material containing titanium oxide as a component as a part of an optical multilayer film.

  In general, plastic optical parts such as lenses, prisms, mirrors, and filters tend to generate static electricity, and dirt such as dust and dust tends to adhere to the optical parts. If the optical component is wiped off with the dirt attached, the surface of the component is scratched due to the dirt. Further, the performance and performance of the optical component is adversely affected, for example, the permeability and reflectivity deteriorate due to the adhesion of dirt.

  Therefore, conventionally, in order to prevent dirt from adhering to the optical component, a conductive thin film is inserted into the optical multilayer film that is thinly coated on the surface of the optical component in order to suppress the generation of static electricity (suppress charging). Has been done. Depending on the application, it is also necessary to ensure high translucency. In that case, as a material used for forming a thin film for imparting antistatic properties to the optical component, it is necessary to use a material that can achieve both high conductivity and high light transmission. For this reason, ITO (indium tin oxide), SnO (tin oxide), ZnO (zinc oxide), and the like have been used as the material for the conductive thin film.

  Examples of the method for forming such an optical thin film include a vacuum deposition method, a sputtering method, an ion plating method, a CVD method, a sol-gel method, and a PLD method. In particular, the vacuum deposition method can easily handle changes in the film material and the base material to which the film is attached, using the same equipment, and the film formation speed is fast, so the processing time is short and the cost is lower than other methods. Since it has the advantage of being easily realized, it is used in many industrial fields including optical components.

Titanium oxide is a representative material of a transparent thin film material having a high refractive index, and is generally used in a vapor deposition method as a lens coating material. In addition, it is known that when anatase-type titanium oxide (TiO ₂ ) is doped with niobium (Nb) in a small amount (0.1 mol% to 20 mol%), the conductivity is improved as compared with 100% titanium oxide (for example, , See Patent Document 1). In this patent document 1, a sintered body of niobium-containing titanium oxide (Nb: TiO ₂ ) having an anatase type crystal structure is used as a material for forming a thin film, and this is deposited on a substrate such as a display panel by a PLD method. Thus, it is described that it is used as a transparent conductive film.

WO2006 / 016608

When a niobium-containing titanium oxide (Nb: TiO ₂ ) film having an anatase type crystal structure is used, it is necessary to increase the crystallinity of the coated thin film in order to improve conductivity. Therefore, the crystallinity is improved by performing reheating (annealing) after film formation. However, in the case of an optical component made of plastic, there is a problem that a technique for improving crystallinity by reheating cannot be applied because the plastic melts when reheating is performed after film formation.

On the other hand, as described above, there is a method of inserting a conductive thin film (film made of ITO, SnO, ZnO, etc.) into an optical multilayer film coated on the surface of an optical component. There was a problem that remodeling was necessary. That is, the optical multilayer film is formed by alternately laminating a low refractive index layer and a high refractive index layer, and is usually made of two kinds of materials (for example, SiO ₂ and TiO ₂ having a higher refractive index than this). It has a binary film structure. If an ITO film or the like is further inserted into this, a ternary film structure is formed, and the vapor deposition apparatus must be modified to handle the ternary system.

  The present invention has been made to solve such a problem, and does not apply a technique for enhancing crystallinity such as reheating after film formation, and is vapor-deposited to handle three kinds of materials. It is an object of the present invention to obtain an optical component having a high antistatic effect without modifying the apparatus.

  In order to solve the above problems, in the present invention, in an optical component formed by vapor-depositing an optical multilayer film on the surface of a substrate, the material of the high refractive index layer of the optical multilayer film is composed of titanium and niobium as components. It is formed of a metal oxide melt containing oxygen vacancies (referred to as niobium-containing titanium suboxide). That is, in the present invention, an optical component is configured by forming a film on the surface of a substrate by a vapor deposition method using a material made of niobium-containing titanium suboxide.

  According to the present invention configured as described above, a metal oxide in which niobium is doped in a small amount with respect to titanium is used for the high refractive index layer in the optical multilayer film. As compared with the case of using other high refractive index substances, the conductivity is improved and high antistatic properties can be obtained. In addition, when a material composed of niobium-containing titanium suboxide having such properties is deposited by vapor deposition, the thin film becomes amorphous without crystallinity. Therefore, in order to improve crystallinity, reheating treatment is performed after deposition. There is no need to do it. Furthermore, since it is not necessary to insert a conductive thin film such as ITO, the optical multilayer film has a binary film structure in which low refractive index layers and high refractive index layers are alternately laminated. As a result, it is possible to obtain an optical component having a high antistatic effect without performing reheating after film formation on the surface of the substrate and without modifying the vapor deposition apparatus to handle three types of materials. it can.

It is a figure which shows the structural example of the optical component by this embodiment. It is a figure which shows the experimental result which performed the X-ray diffraction analysis with respect to the niobium containing titanium suboxide of this embodiment. It is a figure which shows the film | membrane structure of the optical multilayer film which concerns on Example 1 regarding the spectacles lens, and Comparative Examples 1-1 and 1-2. It is a figure which shows the experimental result regarding the antistatic property of the optical multilayer film concerning Example 1 and Comparative Examples 1-1 and 1-2 regarding the lens for spectacles. It is a figure which shows the simulation result regarding the reflectance characteristic of the optical multilayer film which concerns on Example 1 and Comparative Examples 1-1 and 1-2 regarding the lens for spectacles. It is a figure which shows the film | membrane structure of the optical multilayer film which concerns on Example 2 and Comparative Examples 2-1 and 2-2 regarding the lens for spectacles. It is a figure which shows the experimental result regarding the antistatic property of the optical multilayer film which concerns on Example 2 and Comparative Examples 2-1 and 2-2 regarding the lens for spectacles. It is a figure which shows the simulation result regarding the reflectance characteristic of the optical multilayer film which concerns on Example 2 and Comparative Examples 2-1 and 2-2 regarding the lens for spectacles. It is a figure which shows the film | membrane structure of the optical multilayer film concerning Example 3 regarding a band pass filter. It is a figure which shows the film | membrane structure of the optical multilayer film which concerns on the comparative example 3 regarding a band pass filter. It is a figure which shows the experimental result regarding the antistatic property of the optical multilayer film which concerns on Example 3 and the comparative example 3 regarding a band pass filter. It is a figure which shows the simulation result regarding the reflectance characteristic of the optical multilayer film which concerns on Example 3 and Comparative Example 3 regarding a band pass filter. It is a figure which shows the film | membrane structure of the optical multilayer film which concerns on Example 4 and the comparative example 4 regarding a half mirror. It is a figure which shows the experimental result regarding the antistatic property of the optical multilayer film which concerns on Example 4 and the comparative example 4 regarding a half mirror. It is a figure which shows the simulation result regarding the reflectance characteristic of the optical multilayer film which concerns on Example 4 and the comparative example 4 regarding a half mirror.

  Hereinafter, an embodiment of the present invention will be described with reference to the drawings. FIG. 1 is a diagram illustrating a configuration example of the optical component according to the present embodiment. As shown in FIG. 1, in the optical component of this embodiment, a hard coat film 12, an optical multilayer film 13, and an antifouling film 14 are formed in this order from the base 11 on the surface of the base 11. FIG. 1 schematically shows a configuration example of an optical component, and does not represent the actual thickness of the substrate 11 and the actual thickness of each of the films 12 to 14 in an accurate ratio.

  A primer layer is formed between the surface of the substrate 11 and the hard coat film 12, or between the surface of the substrate 11 and the hard coat film 12, between the hard coat film 12 and the optical multilayer film 13, or optical multilayer. For example, an intermediate layer may be formed between the film 13 and the antifouling film 14 or the like. Further, the hard coat film 12 or the optical multilayer film 13 may be formed on the back surface or both the front and back surfaces of the substrate 11.

  Examples of the material (base material) of the substrate 11 include polyurethane resin, episulfide resin, polycarbonate resin, polyester resin, acrylic resin, polyether sulfone resin, poly-4-methylpentene-1 resin, diethyl glycol bisallyl carbonate resin, and the like. Is mentioned. Moreover, as a suitable thing with a high refractive index, the polyurethane resin obtained by addition-polymerizing a polyisocyanate compound, a polythiol, and / or a sulfur-containing polyol can be mentioned, for example. Furthermore, as a suitable thing with a high refractive index, the episulfide resin obtained by addition-polymerizing an episulfide group and a polythiol and / or sulfur-containing polyol can be mentioned.

  The hard coat film 12 is formed by uniformly applying a hard coat liquid to the substrate 11 by a known method such as a dipping method, a spin coat method, or a spray method. As a material of the hard coat film 12, for example, an organosiloxane resin containing inorganic oxide fine particles is used. The hard coat liquid in this case is produced by dispersing (mixing) an organosiloxane resin and an inorganic oxide fine particle sol in water or an alcohol solvent.

  Here, the organosiloxane resin is preferably obtained by hydrolyzing and condensing alkoxysilane. Specific examples of the alkoxysilane include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, methyltrimethoxysilane, and ethyl silicate. These alkoxysilane hydrolysis condensates are produced by hydrolyzing the alkoxysilane compound or a combination thereof with an acidic aqueous solution such as hydrochloric acid.

  Specific examples of the inorganic oxide fine particles include zinc oxide, silicon dioxide, aluminum oxide, titanium oxide, zirconium oxide, tin oxide, beryllium oxide, antimony oxide, tungsten oxide, and cerium oxide sol alone or in two types. What mixed the above can be mentioned. From the viewpoint of ensuring the transparency of the hard coat film 12, the size of the inorganic oxide fine particles is preferably 1 to 100 nanometers (nm), and more preferably 1 to 50 nm. Moreover, it is preferable that the compounding quantity of inorganic oxide microparticles occupies 40-60 wt% in a hard-coat component from a viewpoint of ensuring the hardness in the hard-coat film | membrane 12 and the appropriate degree of toughness.

  In addition, an acetylacetone metal salt, ethylenediaminetetraacetic acid metal salt, etc. can be added to a hard-coat liquid as a curing catalyst. Further, a surfactant, a colorant, a solvent and the like can be added for adjustment as necessary.

  The thickness of the hard coat film 12 is preferably 0.5 to 4.0 micrometers (μm), and more preferably 1.0 to 3.0 μm. The lower limit of the film thickness is determined from a limit value that a sufficient hardness cannot be obtained if the thickness is smaller than this. On the other hand, the upper limit is determined from a limit value that, if thicker than this, the possibility of occurrence of problems related to physical properties such as occurrence of cracks and brittleness is dramatically increased.

The optical multilayer film 13 is formed by alternately laminating low refractive index layers and high refractive index layers by vacuum deposition. Examples of the material of the thin film forming the low refractive index layer include SiO ₂ (silicon dioxide) and MgF ₂ (magnesium fluoride).

  On the other hand, a metal oxide (niobium-containing titanium suboxide) melt having oxygen vacancies containing titanium and niobium as components is used as the material for the thin film forming the high refractive index layer. The melt is formed by melting titanium and niobium in a state having oxygen vacancies, cooling it, pulverizing to a desired grain size (for example, 3 mm or less) and sieving.

The ratio of the metal element (Ti _1-x Nb _x ) and the oxygen element (O) in the niobium-containing titanium suboxide is, for example, 3: 5. Hereinafter, this is expressed as (Ti _1-x Nb _x ) ₃ O ₅ . The doping amount of niobium in the niobium-containing titanium suboxide is preferably 2 mol% or more and 16 mol% or less with respect to titanium.

  The antifouling film 14 is formed in order to improve the water and oil repellency of the lens surface and prevent water scuffing, and is made of a fluorine compound. The antifouling film 14 can be formed by a known method such as a dipping method, a spin method, a spray method, or a vapor deposition method.

Hereinafter, the nature of the niobium-containing titanium suboxide _{(Ti 1-x Nb x)} 3 O 5 used in the optical multilayer film 13 will be described with reference to the drawings. FIG. 2 is a diagram showing experimental results obtained by performing X-ray diffraction analysis (XRD: X-Ray Diffraction analysis) on niobium-containing titanium suboxide. In the experiment shown in FIG. 2, a plurality of types of melts were formed with different amounts of niobium in the niobium-containing titanium suboxide, and XRD analysis was performed on the melts. The doping amount of niobium is changed in increments of 2 mol% from 2 mol% to 16 mol%.

  The XRD analysis measures the intensity of a reflected wave from a material while changing the incident angle of X-rays to the material. By this measurement, as shown in FIG. 2, a graph is obtained with the horizontal axis representing the incident angle and the vertical axis representing the intensity. In FIG. 2, the reference value (intensity zero) on the vertical axis is shifted in the vertical direction so that the measurement results obtained by changing the doping amount of niobium are not overlapped and difficult to see.

  As can be seen from the experimental results in FIG. 2, no intensity peak appears at any incident angle. This indicates that the thin film formed by vapor deposition of niobium-containing titanium suboxide is in an amorphous state.

  Next, specific examples of optical components using niobium-containing titanium suboxide for the high refractive index layer of the optical multilayer film 13 will be described. Here, examples of spectacle lenses, bandpass filters, and half mirrors will be described as examples of optical components. Examples 1 and 2 are spectacle lenses, Example 3 is a band-pass filter, and Example 4 is a half mirror.

<Example 1>
FIG. 3 is a diagram illustrating a film configuration of the optical multilayer film 13 constituting the eyeglass lens according to Example 1, and a film configuration of the optical multilayer film according to Comparative Examples 1-1 and 1-2. 3A shows Example 1, FIG. 3B shows Comparative Example 1-1, and FIG. 3C shows Comparative Example 1-2. In FIG. 3, (Ti _1-x Nb _x ) ₃ O ₅ is abbreviated as TNO.

As shown in FIG. 3A, in Example 1, the layers of the optical multilayer film 13 are L1 to L7 layers in order from the side closer to the substrate 11. In Example 1, the odd-numbered layer is formed of silicon dioxide (SiO ₂ ) as a low-refractive index material, and the even-numbered layer is niobium-containing titanium suboxide ((Ti _1-x Nb _x ) ₃ O ₅ ) as a high-refractive index material. Formed with. That is, the optical multilayer film 13 of Example 1 has a binary film configuration. The refractive index, physical film thickness, and optical film thickness in each of the layers L1 to L7 are as shown in FIG.

Further, as shown in FIG. 3B, in Comparative Example 1-1, an optical multilayer film is formed of seven layers L1 to L7 as in Example 1, and an odd layer is formed of silicon dioxide (low refractive index material). SiO ₂ ), and even layers were made of zirconium dioxide (ZrO ₂ ) as a high refractive index material. The optical multilayer film of Comparative Example 1-1 also has a binary film configuration. The refractive index, physical film thickness, and optical film thickness in each of the layers L1 to L7 are as shown in FIG.

Further, as shown in FIG. 3C, in Comparative Example 1-2, an optical multilayer film was formed of eight layers L1 to L8 by further inserting an ITO film as a conductive thin film. Specifically, each layer of L1, L3, L5, and L8 is formed of silicon dioxide (SiO ₂ ) as a low refractive index material, and each layer of L2, L4, and L6 is formed of zirconium dioxide (ZrO ₂ ) as a high refractive index material. And one layer of L7 was formed of indium tin oxide (ITO). The optical multilayer film of Comparative Example 1-2 has a ternary film configuration. The refractive index, physical film thickness, and optical film thickness in each of the layers L1 to L8 are as shown in FIG.

  With respect to Example 1 and Comparative Examples 1-1 and 1-2 in which an optical multilayer film was formed as shown in FIG. 3, an experiment regarding the presence or absence of antistatic properties was performed as follows. In other words, using a non-woven fabric (“Pure Leaf” manufactured by Ozu Sangyo Co., Ltd.), the charged potential (kilovolt: kV) immediately after rubbing the lens convex surface for 20 seconds with a 1 kilogram load for 20 seconds was measured, and the lens convex surface of the steel wool piece. The presence or absence of adhesion to was observed. The charged potential was measured with a static electricity meter (“FMX-003” manufactured by Simco Japan Co., Ltd.).

FIG. 4 is a diagram showing experimental results regarding this antistatic property. In FIG. 4, as shown in Comparative Example 1-1, in the _binary film structure composed of SiO ₂ and ZrO ₂ , the absolute value of the charging potential is 3 minutes after the non-woven fabric is rubbed. The steel wool piece remained attached to the convex surface of the lens without approaching zero. This indicates that there is no antistatic property.

On the other hand, in the case of Comparative Example 1-2, the absolute value of the charging potential was zero immediately after rubbing the nonwoven fabric, and the steel wool piece did not adhere to the convex surface of the lens at all. This indicates that there is antistatic properties. However, since Comparative Example 1-2 has a ternary film structure composed of SiO ₂ , ZrO _2, and ITO, there is a problem that the vapor deposition apparatus needs to be modified.

On the other hand, in the case of Example 1, since it is a _binary film structure composed of SiO ₂ and (Ti _1-x Nb _x ) ₃ O _5, it is not necessary to modify the vapor deposition apparatus. Moreover, the absolute value of the charging potential is fairly small and almost zero immediately after the rubbing of the nonwoven fabric, and the charging potential is zero when 1 minute has passed. Therefore, the steel wool piece did not adhere to the lens convex surface.

  Thus, it was found that by using niobium-containing titanium suboxide as the thin film material of the optical multilayer film 13, the deposited thin film is amorphous, but the conductivity is improved and high antistatic properties can be obtained. Further, since the deposited thin film is in an amorphous state having no crystallinity, it is not necessary to perform a reheating (annealing) treatment after the film formation in order to improve crystallinity.

Moreover, the simulation regarding a reflectance characteristic was performed about Example 1 and Comparative Examples 1-1 and 1-2 which formed the optical multilayer film like FIG. FIG. 5 is a diagram showing a simulation result regarding the reflectance characteristic. As shown in FIG. 5, in both Example 1 and Comparative Examples 1-1 and 1-2, the reflectance is low in the visible wavelength range. Thus, even with the _{(Ti 1-x Nb x)} 3 O 5 to the high refractive index layer as in Example 1, the visibility of the ophthalmic lens is found not to decrease.

<Example 2>
FIG. 6 is a diagram illustrating a film configuration of the optical multilayer film 13 constituting the eyeglass lens according to Example 2, and a film configuration of the optical multilayer film according to Comparative Examples 2-1 and 2-2. 6A shows Example 2, FIG. 6B shows Comparative Example 2-1, and FIG. 6C shows Comparative Example 2-2. In FIG. 6 as well, (Ti _1-x Nb _x ) ₃ O ₅ is abbreviated as TNO.

As shown in FIG. 6A, in Example 2, the layers of the optical multilayer film 13 are L1 to L5 layers in order from the side closer to the substrate 11. In Example 2, the odd-numbered layer is formed of silicon dioxide (SiO ₂ ) as a low refractive index material, and the even-numbered layer is a niobium-containing titanium suboxide ((Ti _1-x Nb _x ) ₃ O ₅ ) as a high refractive index material. Formed with. That is, the optical multilayer film 13 of Example 2 also has a binary film configuration. The refractive index, physical film thickness, and optical film thickness in each of the layers L1 to L5 are as shown in FIG.

Further, as shown in FIG. 6B, in Comparative Example 2-1, an optical multilayer film is formed of five layers L1 to L5 as in Example 2, and an odd layer is formed of silicon dioxide (low refractive index material). SiO ₂ ), and even layers were made of titanium dioxide (TiO ₂ ) as a high refractive index material. The optical multilayer film of Comparative Example 2 also has a binary film configuration. The refractive index, physical film thickness, and optical film thickness in each of the layers L1 to L5 are as shown in FIG.

Further, as shown in FIG. 6C, in Comparative Example 2-2, the optical multilayer film is formed of five layers L1 to L5 as in Example 2, and the odd-numbered layer is formed of silicon dioxide (low refractive index material). SiO ₂ ), and even layers were made of zirconium dioxide (ZrO ₂ ) as a high refractive index material. The optical multilayer film of Comparative Example 2-2 also has a binary film configuration. The refractive index, physical film thickness, and optical film thickness in each of the layers L1 to L5 are as shown in FIG.

With respect to Example 2 and Comparative Examples 2-1 and 2-2 in which an optical multilayer film was formed as shown in FIG. 6, an experiment on the presence or absence of antistatic properties was performed by the same method as in Example 1. FIG. 7 is a diagram showing experimental results regarding the antistatic property. In FIG. 7, as shown in Comparative Examples 2-1 and 2-2, in the _binary film configuration composed of SiO ₂ and TiO ₂ , or SiO ₂ and ZrO ₂ , 3 minutes after the non-woven fabric is rubbed. The absolute value of the charging potential did not approach zero even after the lapse of time, and the steel wool piece remained attached to the convex surface of the lens. This indicates that there is no antistatic property.

  On the other hand, in the case of Example 2, the absolute value of the charging potential is quite small and almost zero immediately after the rubbing of the nonwoven fabric, and approaches zero as time passes. Therefore, the steel wool piece did not adhere to the lens convex surface. Thus, it was found that Example 2 also exhibited antistatic properties.

Further, a simulation regarding reflectance characteristics was performed for Example 2 and Comparative Examples 2-1 and 2-2 in which an optical multilayer film was formed as shown in FIG. FIG. 8 is a diagram showing a simulation result relating to the reflectance characteristic. As shown in FIG. 8, in any of Example 2 and Comparative Examples 2-1 and 2-2, the reflectance is low in the visible wavelength range. Thus, even with the _{(Ti 1-x Nb x)} 3 O 5 to the high refractive index layer as in Example 2, the visibility of the ophthalmic lens is found not to decrease.

<Example 3>
FIG. 9 is a diagram illustrating a film configuration of the optical multilayer film 13 constituting the bandpass filter according to the third embodiment. FIG. 10 is a diagram showing a film configuration of an optical multilayer film according to Comparative Example 3. 9 and 10, (Ti _1-x Nb _x ) ₃ O ₅ is abbreviated as TNO.

As shown in FIG. 9, in Example 3, the layers of the optical multilayer film 13 are L1 to L36 layers in order from the side closer to the substrate 11. In Example 3, the odd layers of high refractive index material niobium-containing titanium suboxides with when formed of _{((Ti 1-x Nb x} ) 3 O 5), silicon dioxide even layer low refractive index material _(SiO 2) Formed with. That is, the optical multilayer film 13 of Example 3 has a binary film configuration. The refractive index, physical film thickness, optical film thickness, and center wavelength in each of the layers L1 to L36 are as shown in FIG.

As shown in FIG. 10, in Comparative Example 3, the optical multilayer film is formed of 36 layers L1 to L36 as in Example 3, and the odd layer is made of titanium dioxide (TiO ₂ ) as a high refractive index material, The even layer was made of silicon dioxide (SiO ₂ ) as a low refractive index material. The optical multilayer film of Comparative Example 3 also has a binary film configuration. The refractive index, physical film thickness, optical film thickness, and center wavelength in each of the layers L1 to L36 are as shown in FIG.

  With respect to Example 3 and Comparative Example 3 in which an optical multilayer film was formed as shown in FIGS. 9 and 10, an experiment regarding the presence or absence of antistatic properties was performed as follows. That is, the surface of a component was rubbed 20 reciprocations for 10 seconds at a load of 1 kilogram using a nonwoven fabric (“Pure Leaf” manufactured by Ozu Sangyo Co., Ltd.), and the presence or absence of adhesion of a steel wool piece to the component surface was observed. In addition, the surface resistance of the parts was measured with a high resistivity meter (“Hiresta-UP” manufactured by Mitsubishi Chemical). The surface resistance value was measured with an applied voltage of 500 [V] and a measurement holding time of 30 seconds, and this was repeated three times to calculate an average value.

FIG. 11 is a diagram showing experimental results regarding this antistatic property. In FIG. 11, as shown in Example 3, the average value of the surface resistance is 1.74 × 10 ¹⁰ [Ω / □], and the steel wool piece does not adhere to the surface of the component immediately after the non-woven fabric is rubbed. It was. In general, it is known that the smaller the resistance value of the film, the higher the conductivity and the antistatic property, and the antistatic property can be obtained almost certainly if the resistance value is 10 ¹¹ [Ω / □] or less. Yes. Therefore, the above experimental results show that Example 3 exhibits antistatic properties.

On the other hand, as shown in Comparative Example 3, in the _binary film configuration composed of TiO ₂ and SiO ₂ , the steel wool piece remained attached to the part surface. The average value of the surface resistance was 4.84 × 10 ¹² [Ω / □]. This indicates that Comparative Example 3 has no antistatic property.

  Moreover, about Example 3 and the comparative example 3, the simulation regarding a reflectance characteristic was performed. FIG. 12 is a diagram illustrating a simulation result regarding the reflectance characteristic. As shown in FIG. 12, in both Example 3 and Comparative Example 3, the reflectance is low in the desired wavelength range. As a result, it was found that the desired bandpass filter characteristics were obtained in both cases of Example 3 and Comparative Example 3.

<Example 4>
FIG. 13 is a diagram illustrating a film configuration of the optical multilayer film 13 constituting the half mirror according to Example 4 and a film configuration of the optical multilayer film according to Comparative Example 4. FIG. 13A shows Example 4 and FIG. 13B shows Comparative Example 4. In FIG. 13 as well, (Ti _1-x Nb _x ) ₃ O ₅ is abbreviated as TNO.

As shown in FIG. 13A, in Example 4, the layers of the optical multilayer film 13 are L1 to L12 layers in order from the side closer to the substrate 11. In Example 4, the odd layers of high refractive index material niobium-containing titanium suboxides with when formed of _{((Ti 1-x Nb x} ) 3 O 5), silicon dioxide even layer low refractive index material _(SiO 2) Formed with. That is, the optical multilayer film 13 of Example 4 has a binary film configuration. The refractive index, physical film thickness, optical film thickness, and center wavelength in each of the layers L1 to L12 are as shown in FIG.

Further, as shown in FIG. 13B, in Comparative Example 4, the optical multilayer film is formed of 12 layers L1 to L12 as in Example 4, and the odd-numbered layer is made of titanium dioxide (TiO 2) of a high refractive index material. ₂ ) The even layer was made of silicon dioxide (SiO ₂ ) as a low refractive index material. The optical multilayer film of Comparative Example 4 also has a binary film configuration. The refractive index, physical film thickness, optical film thickness, and center wavelength in each of the layers L1 to L12 are as shown in FIG.

For Example 4 and Comparative Example 4 in which an optical multilayer film was formed as shown in FIG. 13, an experiment was conducted regarding the presence or absence of antistatic properties by the same method as in Example 3. FIG. 14 is a diagram showing experimental results regarding this antistatic property. In FIG. 14, as shown in Comparative Example 4, in the _binary film configuration composed of TiO ₂ and SiO ₂ , the steel wool piece remained attached to the part surface. Further, the surface resistance value was too large to be measured. This indicates that Comparative Example 4 has no antistatic property.

On the other hand, in the case of Example 4, the average value of the surface resistance was 3.18 × 10 ¹² [Ω / □], and the steel wool piece did not adhere to the surface of the component immediately after rubbing the nonwoven fabric. . Although the surface resistance value is 10 ¹¹ [Ω / □] or more, since the steel wool piece did not adhere to the surface of the part, Example 4 shows that it has antistatic properties.

  Moreover, about Example 4 and the comparative example 4, the simulation regarding a reflectance characteristic was performed. FIG. 15 is a diagram showing a simulation result related to the reflectance characteristic. As shown in FIG. 15, in both Example 4 and Comparative Example 4, the reflectance is high in most wavelength ranges. Thus, it was found that the characteristics of the half mirror can be obtained in both cases of Example 4 and Comparative Example 4.

  As described above in detail, in this embodiment, in the optical component formed by vapor-depositing the optical multilayer film 13 on the surface of the substrate 11, the thin film material of the high refractive index layer in the optical multilayer film 13 is converted to niobium-containing suboxide. Made of titanium. Thereby, although the thin film formed by vapor-depositing niobium containing titanium suboxide will be in an amorphous state, it has high electroconductivity and can obtain high antistatic property. Further, since it is amorphous, it is not necessary to perform reheating (annealing) after film formation in order to improve crystallinity. Furthermore, since it is not necessary to insert a conductive thin film such as ITO, the optical multilayer film 13 has a binary film configuration in which low refractive index layers and high refractive index layers are alternately laminated. Accordingly, an optical component having a high antistatic effect can be obtained without performing reheating after film formation on the surface of the substrate 11 that is vulnerable to high heat, and without modifying the vapor deposition apparatus to handle three types of materials. Can be obtained.

  In the above embodiment, three examples of spectacle lenses, a band-pass filter, and a half mirror have been described as examples of optical components, but the present invention is not limited to this. For example, it can be applied to other optical components such as lenses other than glasses, filters other than bandpass filters, mirrors other than half mirrors, beam splitters, prisms, polarizing elements, wave plates, light shielding plates, and ground glass. .

  Moreover, although the said embodiment demonstrated the example provided with the base | substrate 11, the hard-coat film | membrane 12, the optical multilayer film 13, and the antifouling film | membrane 14 as a structure of an optical component as shown in FIG. 1, this invention is limited to this. Not. In other words, the base 11 and the optical multilayer film 13 are essential components, and the hard coat film 12 and the antifouling film 14 may be used in accordance with the applications of the various optical parts as described above.

  In addition, the said embodiment is only what showed the example in implementation in implementing this invention, and, as a result, the technical scope of this invention should not be interpreted limitedly. That is, the present invention can be implemented in various forms without departing from the gist or the main features thereof.

11 Substrate 12 Hard coat film 13 Optical multilayer film 14 Antifouling film

[0003]
[0010]
In order to solve the above problems, in the present invention, in an optical component formed by vapor-depositing an optical multilayer film on the surface of a substrate, the material of the high refractive index layer of the optical multilayer film is composed of titanium and niobium as components. It is formed of a metal oxide melt containing oxygen vacancies (referred to as niobium-containing titanium suboxide). That is, in the present invention, an optical component is configured by forming a film on the surface of a substrate by a vapor deposition method using a material made of niobium-containing titanium suboxide.
[0011]
According to the present invention configured as described above, a metal oxide in which niobium is doped in a small amount with respect to titanium is used for the high refractive index layer in the optical multilayer film. As compared with the case of using other high refractive index substances, the conductivity is improved and high antistatic properties can be obtained. In addition, when a material composed of niobium-containing titanium suboxide having such properties is deposited by a vapor deposition method, the thin film is in an amorphous state without crystallinity but has conductivity, so that the crystallinity is improved. In addition, it is not necessary to perform reheating after film formation. Furthermore, since it is not necessary to insert a conductive thin film such as ITO, the optical multilayer film has a binary film structure in which low refractive index layers and high refractive index layers are alternately laminated. As a result, it is possible to obtain an optical component having a high antistatic effect without performing reheating after film formation on the surface of the substrate and without modifying the vapor deposition apparatus to handle three types of materials. it can.
BRIEF DESCRIPTION OF THE DRAWINGS [0012]
FIG. 1 is a diagram showing a configuration example of an optical component according to the present embodiment.
FIG. 2 is a diagram showing experimental results obtained by performing X-ray diffraction analysis on the niobium-containing titanium suboxide of the present embodiment.
FIG. 3 is a diagram showing a film configuration of an optical multilayer film according to Example 1 and Comparative Examples 1-1 and 1-2 for a spectacle lens.
FIG. 4 is a diagram showing experimental results on antistatic properties of the optical multilayer films according to Example 1 and Comparative Examples 1-1 and 1-2 for eyeglass lenses.
FIG. 5 is a diagram showing simulation results regarding the reflectance characteristics of the optical multilayer film according to Example 1 and Comparative Examples 1-1 and 1-2 regarding a spectacle lens.
[FIG. 6] Optics according to Example 2 and Comparative Examples 2-1 and 2-2 regarding spectacle lenses.

[0009]
The charging potential (kilovolt: kV) immediately after rubbing for 20 seconds with a ram load for 20 seconds was measured, and the presence or absence of adhesion of the steel wool piece to the lens convex surface was observed. The charged potential was measured with a static electricity meter ("FMX-003" manufactured by Simco Japan Co., Ltd.).
[0034]
FIG. 4 is a diagram showing experimental results regarding this antistatic property. In FIG. 4, as shown in Comparative Example 1-1, in the _binary film structure composed of SiO ₂ and ZrO ₂ , the absolute value of the charging potential is 3 minutes after the non-woven fabric is rubbed. The steel wool piece remained attached to the convex surface of the lens without approaching zero. This indicates that there is no antistatic property.
[0035]
On the other hand, in the case of Comparative Example 1-2, the absolute value of the charging potential was zero immediately after rubbing the nonwoven fabric, and the steel wool piece did not adhere to the convex surface of the lens at all. This indicates that there is antistatic properties. However, since Comparative Example 1-2 has a ternary film structure composed of SiO ₂ , ZrO _2, and ITO, there is a problem that the vapor deposition apparatus needs to be modified.
[0036]
On the other hand, in the case of Example 1, since it is a _binary film structure composed of SiO ₂ and (Ti _1-x Nb _x ) ₃ O _5, it is not necessary to modify the vapor deposition apparatus. Moreover, the absolute value of the charging potential is fairly small and almost zero immediately after the rubbing of the nonwoven fabric, and the charging potential is zero when 1 minute has passed. Therefore, the steel wool piece did not adhere to the lens convex surface.
[0037]
Thus, it was found that by using niobium-containing titanium suboxide as the thin film material of the optical multilayer film 13, the deposited thin film is amorphous, but the conductivity is improved and high antistatic properties can be obtained. In addition, the deposited thin film is in an amorphous state with no crystallinity but has conductivity, so that it is not necessary to perform a reheating (annealing) treatment after the film formation in order to improve crystallinity.
[0038]
Moreover, the simulation regarding a reflectance characteristic was performed about Example 1 and Comparative Examples 1-1 and 1-2 which formed the optical multilayer film like FIG. FIG. 5 is a diagram showing a simulation result regarding the reflectance characteristic. As shown in FIG. 5, in any of Example 1 and Comparative Examples 1-1 and 1-2, the visible region and

  The present invention relates to an optical component, and more particularly to an optical component using a vapor deposition material containing titanium oxide as a component as a part of an optical multilayer film.

  In general, plastic optical parts such as lenses, prisms, mirrors, and filters tend to generate static electricity, and dirt such as dust and dust tends to adhere to the optical parts. If the optical component is wiped off with the dirt attached, the surface of the component is scratched due to the dirt. Further, the performance and performance of the optical component is adversely affected, for example, the permeability and reflectivity deteriorate due to the adhesion of dirt.

  Therefore, conventionally, in order to prevent dirt from adhering to the optical component, a conductive thin film is inserted into the optical multilayer film that is thinly coated on the surface of the optical component in order to suppress the generation of static electricity (suppress charging). Has been done. Depending on the application, it is also necessary to ensure high translucency. In that case, as a material used for forming a thin film for imparting antistatic properties to the optical component, it is necessary to use a material that can achieve both high conductivity and high light transmission. For this reason, ITO (indium tin oxide), SnO (tin oxide), ZnO (zinc oxide), and the like have been used as the material for the conductive thin film.

  Examples of the method for forming such an optical thin film include a vacuum deposition method, a sputtering method, an ion plating method, a CVD method, a sol-gel method, and a PLD method. In particular, the vacuum deposition method can easily handle changes in the film material and the base material to which the film is attached, using the same equipment, and the film formation speed is fast, so the processing time is short and the cost is lower than other methods. Since it has the advantage of being easily realized, it is used in many industrial fields including optical components.

Titanium oxide is a representative material of a transparent thin film material having a high refractive index, and is generally used in a vapor deposition method as a lens coating material. In addition, it is known that when anatase-type titanium oxide (TiO ₂ ) is doped with niobium (Nb) in a small amount (0.1 mol% to 20 mol%), the conductivity is improved as compared with 100% titanium oxide (for example, , See Patent Document 1). In this patent document 1, a sintered body of niobium-containing titanium oxide (Nb: TiO ₂ ) having an anatase type crystal structure is used as a material for forming a thin film, and this is deposited on a substrate such as a display panel by a PLD method. Thus, it is described that it is used as a transparent conductive film.

WO2006 / 016608

When a niobium-containing titanium oxide (Nb: TiO ₂ ) film having an anatase type crystal structure is used, it is necessary to increase the crystallinity of the coated thin film in order to improve conductivity. Therefore, the crystallinity is improved by performing reheating (annealing) after film formation. However, in the case of an optical component made of plastic, there is a problem that a technique for improving crystallinity by reheating cannot be applied because the plastic melts when reheating is performed after film formation.

On the other hand, as described above, there is a method of inserting a conductive thin film (film made of ITO, SnO, ZnO, etc.) into an optical multilayer film coated on the surface of an optical component. There was a problem that remodeling was necessary. That is, the optical multilayer film is formed by alternately laminating a low refractive index layer and a high refractive index layer, and is usually made of two kinds of materials (for example, SiO ₂ and TiO ₂ having a higher refractive index than this). It has a binary film structure. If an ITO film or the like is further inserted into this, a ternary film structure is formed, and the vapor deposition apparatus must be modified to handle the ternary system.

  The present invention has been made to solve such a problem, and does not apply a technique for enhancing crystallinity such as reheating after film formation, and is vapor-deposited to handle three kinds of materials. It is an object of the present invention to obtain an optical component having a high antistatic effect without modifying the apparatus.

In order to solve the above problems, in the present invention, in an optical component formed by vapor-depositing an optical multilayer film on the surface of a substrate, the material of the high refractive index layer of the optical multilayer film is composed of titanium and niobium as components. A thin film formed from a metal oxide melt (referred to as niobium-containing titanium suboxide) containing oxygen vacancies and deposited with the material, has no crystallinity and has a reflected wave regardless of the X-ray incident angle. In the amorphous state, no intensity peak appears . That is, in the present invention, an optical component is configured by forming a film on the surface of a substrate by a vapor deposition method using a material made of niobium-containing titanium suboxide.

  According to the present invention configured as described above, a metal oxide in which niobium is doped in a small amount with respect to titanium is used for the high refractive index layer in the optical multilayer film. As compared with the case of using other high refractive index substances, the conductivity is improved and high antistatic properties can be obtained. In addition, when a material composed of niobium-containing titanium suboxide having such properties is deposited by a vapor deposition method, the thin film is in an amorphous state without crystallinity but has conductivity, so that the crystallinity is improved. In addition, it is not necessary to perform reheating after film formation. Furthermore, since it is not necessary to insert a conductive thin film such as ITO, the optical multilayer film has a binary film structure in which low refractive index layers and high refractive index layers are alternately laminated. As a result, it is possible to obtain an optical component having a high antistatic effect without performing reheating after film formation on the surface of the substrate and without modifying the vapor deposition apparatus to handle three types of materials. it can.

It is a figure which shows the structural example of the optical component by this embodiment. It is a figure which shows the experimental result which performed the X-ray diffraction analysis with respect to the niobium containing titanium suboxide of this embodiment. It is a figure which shows the film | membrane structure of the optical multilayer film which concerns on Example 1 regarding the spectacles lens, and Comparative Examples 1-1 and 1-2. It is a figure which shows the experimental result regarding the antistatic property of the optical multilayer film concerning Example 1 and Comparative Examples 1-1 and 1-2 regarding the lens for spectacles. It is a figure which shows the simulation result regarding the reflectance characteristic of the optical multilayer film which concerns on Example 1 and Comparative Examples 1-1 and 1-2 regarding the lens for spectacles. It is a figure which shows the film | membrane structure of the optical multilayer film which concerns on Example 2 and Comparative Examples 2-1 and 2-2 regarding the lens for spectacles. It is a figure which shows the experimental result regarding the antistatic property of the optical multilayer film which concerns on Example 2 and Comparative Examples 2-1 and 2-2 regarding the lens for spectacles. It is a figure which shows the simulation result regarding the reflectance characteristic of the optical multilayer film which concerns on Example 2 and Comparative Examples 2-1 and 2-2 regarding the lens for spectacles. It is a figure which shows the film | membrane structure of the optical multilayer film concerning Example 3 regarding a band pass filter. It is a figure which shows the film | membrane structure of the optical multilayer film which concerns on the comparative example 3 regarding a band pass filter. It is a figure which shows the experimental result regarding the antistatic property of the optical multilayer film which concerns on Example 3 and the comparative example 3 regarding a band pass filter. It is a figure which shows the simulation result regarding the reflectance characteristic of the optical multilayer film which concerns on Example 3 and Comparative Example 3 regarding a band pass filter. It is a figure which shows the film | membrane structure of the optical multilayer film which concerns on Example 4 and the comparative example 4 regarding a half mirror. It is a figure which shows the experimental result regarding the antistatic property of the optical multilayer film which concerns on Example 4 and the comparative example 4 regarding a half mirror. It is a figure which shows the simulation result regarding the reflectance characteristic of the optical multilayer film which concerns on Example 4 and the comparative example 4 regarding a half mirror.

  Hereinafter, an embodiment of the present invention will be described with reference to the drawings. FIG. 1 is a diagram illustrating a configuration example of the optical component according to the present embodiment. As shown in FIG. 1, in the optical component of this embodiment, a hard coat film 12, an optical multilayer film 13, and an antifouling film 14 are formed in this order from the base 11 on the surface of the base 11. FIG. 1 schematically shows a configuration example of an optical component, and does not represent the actual thickness of the substrate 11 and the actual thickness of each of the films 12 to 14 in an accurate ratio.

  A primer layer is formed between the surface of the substrate 11 and the hard coat film 12, or between the surface of the substrate 11 and the hard coat film 12, between the hard coat film 12 and the optical multilayer film 13, or optical multilayer. For example, an intermediate layer may be formed between the film 13 and the antifouling film 14 or the like. Further, the hard coat film 12 or the optical multilayer film 13 may be formed on the back surface or both the front and back surfaces of the substrate 11.

  Examples of the material (base material) of the substrate 11 include polyurethane resin, episulfide resin, polycarbonate resin, polyester resin, acrylic resin, polyether sulfone resin, poly-4-methylpentene-1 resin, diethyl glycol bisallyl carbonate resin, and the like. Is mentioned. Moreover, as a suitable thing with a high refractive index, the polyurethane resin obtained by addition-polymerizing a polyisocyanate compound, a polythiol, and / or a sulfur-containing polyol can be mentioned, for example. Furthermore, as a suitable thing with a high refractive index, the episulfide resin obtained by addition-polymerizing an episulfide group and a polythiol and / or sulfur-containing polyol can be mentioned.

  The hard coat film 12 is formed by uniformly applying a hard coat liquid to the substrate 11 by a known method such as a dipping method, a spin coat method, or a spray method. As a material of the hard coat film 12, for example, an organosiloxane resin containing inorganic oxide fine particles is used. The hard coat liquid in this case is produced by dispersing (mixing) an organosiloxane resin and an inorganic oxide fine particle sol in water or an alcohol solvent.

  Here, the organosiloxane resin is preferably obtained by hydrolyzing and condensing alkoxysilane. Specific examples of the alkoxysilane include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, methyltrimethoxysilane, and ethyl silicate. These alkoxysilane hydrolysis condensates are produced by hydrolyzing the alkoxysilane compound or a combination thereof with an acidic aqueous solution such as hydrochloric acid.

  Specific examples of the inorganic oxide fine particles include zinc oxide, silicon dioxide, aluminum oxide, titanium oxide, zirconium oxide, tin oxide, beryllium oxide, antimony oxide, tungsten oxide, and cerium oxide sol alone or in two types. What mixed the above can be mentioned. From the viewpoint of ensuring the transparency of the hard coat film 12, the size of the inorganic oxide fine particles is preferably 1 to 100 nanometers (nm), and more preferably 1 to 50 nm. Moreover, it is preferable that the compounding quantity of inorganic oxide microparticles occupies 40-60 wt% in a hard-coat component from a viewpoint of ensuring the hardness in the hard-coat film | membrane 12 and the appropriate degree of toughness.

  In addition, an acetylacetone metal salt, ethylenediaminetetraacetic acid metal salt, etc. can be added to a hard-coat liquid as a curing catalyst. Further, a surfactant, a colorant, a solvent and the like can be added for adjustment as necessary.

  The thickness of the hard coat film 12 is preferably 0.5 to 4.0 micrometers (μm), and more preferably 1.0 to 3.0 μm. The lower limit of the film thickness is determined from a limit value that a sufficient hardness cannot be obtained if the thickness is smaller than this. On the other hand, the upper limit is determined from a limit value that, if thicker than this, the possibility of occurrence of problems related to physical properties such as occurrence of cracks and brittleness is dramatically increased.

The optical multilayer film 13 is formed by alternately laminating low refractive index layers and high refractive index layers by vacuum deposition. Examples of the material of the thin film forming the low refractive index layer include SiO ₂ (silicon dioxide) and MgF ₂ (magnesium fluoride).

  On the other hand, a metal oxide (niobium-containing titanium suboxide) melt having oxygen vacancies containing titanium and niobium as components is used as the material for the thin film forming the high refractive index layer. The melt is formed by melting titanium and niobium in a state having oxygen vacancies, cooling it, pulverizing to a desired grain size (for example, 3 mm or less) and sieving.

The ratio of metal elements of niobium-containing titanium suboxide _{(Ti 1-x} Nb x) and oxygen element (O), for example 3: 5. Hereinafter, this is expressed as (Ti _1-x Nb _x ) ₃ O ₅ . The doping amount of niobium in the niobium-containing titanium suboxide is preferably 2 mol% or more and 16 mol% or less with respect to titanium.

  The antifouling film 14 is formed in order to improve the water and oil repellency of the lens surface and prevent water scuffing, and is made of a fluorine compound. The antifouling film 14 can be formed by a known method such as a dipping method, a spin method, a spray method, or a vapor deposition method.

Hereinafter, the nature of the niobium-containing titanium suboxide _{(Ti 1-x Nb x)} 3 O 5 used in the optical multilayer film 13 will be described with reference to the drawings. FIG. 2 is a diagram showing experimental results obtained by performing X-ray diffraction analysis (XRD: X-Ray Diffraction analysis) on niobium-containing titanium suboxide. In the experiment shown in FIG. 2, a plurality of types of melts were formed with different amounts of niobium in the niobium-containing titanium suboxide, and XRD analysis was performed on the melts. The doping amount of niobium is changed in increments of 2 mol% from 2 mol% to 16 mol%.

  The XRD analysis measures the intensity of a reflected wave from a material while changing the incident angle of X-rays to the material. By this measurement, as shown in FIG. 2, a graph is obtained with the horizontal axis representing the incident angle and the vertical axis representing the intensity. In FIG. 2, the reference value (intensity zero) on the vertical axis is shifted in the vertical direction so that the measurement results obtained by changing the doping amount of niobium are not overlapped and difficult to see.

  As can be seen from the experimental results in FIG. 2, no intensity peak appears at any incident angle. This indicates that the thin film formed by vapor deposition of niobium-containing titanium suboxide is in an amorphous state.

  Next, specific examples of optical components using niobium-containing titanium suboxide for the high refractive index layer of the optical multilayer film 13 will be described. Here, examples of spectacle lenses, bandpass filters, and half mirrors will be described as examples of optical components. Examples 1 and 2 are spectacle lenses, Example 3 is a band-pass filter, and Example 4 is a half mirror.

<Example 1>
FIG. 3 is a diagram illustrating a film configuration of the optical multilayer film 13 constituting the eyeglass lens according to Example 1, and a film configuration of the optical multilayer film according to Comparative Examples 1-1 and 1-2. 3A shows Example 1, FIG. 3B shows Comparative Example 1-1, and FIG. 3C shows Comparative Example 1-2. In FIG. 3, (Ti _1-x Nb _x ) ₃ O ₅ is abbreviated as TNO.

As shown in FIG. 3A, in Example 1, the layers of the optical multilayer film 13 are L1 to L7 layers in order from the side closer to the substrate 11. In Example 1, the odd-numbered layer is formed of silicon dioxide (SiO ₂ ) as a low-refractive index material, and the even-numbered layer is niobium-containing titanium suboxide ((Ti _1-x Nb _x ) ₃ O ₅ ) as a high-refractive index material. Formed with. That is, the optical multilayer film 13 of Example 1 has a binary film configuration. The refractive index, physical film thickness, and optical film thickness in each of the layers L1 to L7 are as shown in FIG.

Further, as shown in FIG. 3B, in Comparative Example 1-1, an optical multilayer film is formed of seven layers L1 to L7 as in Example 1, and an odd layer is formed of silicon dioxide (low refractive index material). SiO ₂ ), and even layers were made of zirconium dioxide (ZrO ₂ ) as a high refractive index material. The optical multilayer film of Comparative Example 1-1 also has a binary film configuration. The refractive index, physical film thickness, and optical film thickness in each of the layers L1 to L7 are as shown in FIG.

Further, as shown in FIG. 3C, in Comparative Example 1-2, an optical multilayer film was formed of eight layers L1 to L8 by further inserting an ITO film as a conductive thin film. Specifically, each layer of L1, L3, L5, and L8 is formed of silicon dioxide (SiO ₂ ) as a low refractive index material, and each layer of L2, L4, and L6 is formed of zirconium dioxide (ZrO ₂ ) as a high refractive index material. And one layer of L7 was formed of indium tin oxide (ITO). The optical multilayer film of Comparative Example 1-2 has a ternary film configuration. The refractive index, physical film thickness, and optical film thickness in each of the layers L1 to L8 are as shown in FIG.

  With respect to Example 1 and Comparative Examples 1-1 and 1-2 in which an optical multilayer film was formed as shown in FIG. 3, an experiment regarding the presence or absence of antistatic properties was performed as follows. In other words, using a non-woven fabric (“Pure Leaf” manufactured by Ozu Sangyo Co., Ltd.), the charged potential (kilovolt: kV) immediately after rubbing the lens convex surface for 20 seconds with a 1 kilogram load for 20 seconds was measured, and the lens convex surface of the steel wool piece. The presence or absence of adhesion to was observed. The charged potential was measured with a static electricity meter (“FMX-003” manufactured by Simco Japan Co., Ltd.).

FIG. 4 is a diagram showing experimental results regarding this antistatic property. In FIG. 4, as shown in Comparative Example 1-1, in the _binary film structure composed of SiO ₂ and ZrO ₂ , the absolute value of the charging potential is 3 minutes after the non-woven fabric is rubbed. The steel wool piece remained attached to the convex surface of the lens without approaching zero. This indicates that there is no antistatic property.

On the other hand, in the case of Comparative Example 1-2, the absolute value of the charging potential was zero immediately after rubbing the nonwoven fabric, and the steel wool piece did not adhere to the convex surface of the lens at all. This indicates that there is antistatic properties. However, since Comparative Example 1-2 has a ternary film structure composed of SiO ₂ , ZrO _2, and ITO, there is a problem that the vapor deposition apparatus needs to be modified.

On the other hand, in the case of Example 1, since it is a _binary film structure composed of SiO ₂ and (Ti _1-x Nb _x ) ₃ O _5, it is not necessary to modify the vapor deposition apparatus. Moreover, the absolute value of the charging potential is fairly small and almost zero immediately after the rubbing of the nonwoven fabric, and the charging potential is zero when 1 minute has passed. Therefore, the steel wool piece did not adhere to the lens convex surface.

  Thus, it was found that by using niobium-containing titanium suboxide as the thin film material of the optical multilayer film 13, the deposited thin film is amorphous, but the conductivity is improved and high antistatic properties can be obtained. In addition, the deposited thin film is in an amorphous state with no crystallinity but has conductivity, so that it is not necessary to perform a reheating (annealing) treatment after the film formation in order to improve crystallinity.

Moreover, the simulation regarding a reflectance characteristic was performed about Example 1 and Comparative Examples 1-1 and 1-2 which formed the optical multilayer film like FIG. FIG. 5 is a diagram showing a simulation result regarding the reflectance characteristic. As shown in FIG. 5, in both Example 1 and Comparative Examples 1-1 and 1-2, the reflectance is low in the visible wavelength range. Thus, even with the _{(Ti 1-x Nb x)} 3 O 5 to the high refractive index layer as in Example 1, the visibility of the ophthalmic lens is found not to decrease.

<Example 2>
FIG. 6 is a diagram illustrating a film configuration of the optical multilayer film 13 constituting the eyeglass lens according to Example 2, and a film configuration of the optical multilayer film according to Comparative Examples 2-1 and 2-2. 6A shows Example 2, FIG. 6B shows Comparative Example 2-1, and FIG. 6C shows Comparative Example 2-2. In FIG. 6 as well, (Ti _1-x Nb _x ) ₃ O ₅ is abbreviated as TNO.

As shown in FIG. 6A, in Example 2, the layers of the optical multilayer film 13 are L1 to L5 layers in order from the side closer to the substrate 11. In Example 2, the odd-numbered layer is formed of silicon dioxide (SiO ₂ ) as a low refractive index material, and the even-numbered layer is a niobium-containing titanium suboxide ((Ti _1-x Nb _x ) ₃ O ₅ ) as a high refractive index material. Formed with. That is, the optical multilayer film 13 of Example 2 also has a binary film configuration. The refractive index, physical film thickness, and optical film thickness in each of the layers L1 to L5 are as shown in FIG.

Further, as shown in FIG. 6B, in Comparative Example 2-1, an optical multilayer film is formed of five layers L1 to L5 as in Example 2, and an odd layer is formed of silicon dioxide (low refractive index material). SiO ₂ ), and even layers were made of titanium dioxide (TiO ₂ ) as a high refractive index material. The optical multilayer film of Comparative Example 2 also has a binary film configuration. The refractive index, physical film thickness, and optical film thickness in each of the layers L1 to L5 are as shown in FIG.

Further, as shown in FIG. 6C, in Comparative Example 2-2, the optical multilayer film is formed of five layers L1 to L5 as in Example 2, and the odd-numbered layer is formed of silicon dioxide (low refractive index material). SiO ₂ ), and even layers were made of zirconium dioxide (ZrO ₂ ) as a high refractive index material. The optical multilayer film of Comparative Example 2-2 also has a binary film configuration. The refractive index, physical film thickness, and optical film thickness in each of the layers L1 to L5 are as shown in FIG.

With respect to Example 2 and Comparative Examples 2-1 and 2-2 in which an optical multilayer film was formed as shown in FIG. 6, an experiment on the presence or absence of antistatic properties was performed by the same method as in Example 1. FIG. 7 is a diagram showing experimental results regarding the antistatic property. In FIG. 7, as shown in Comparative Examples 2-1 and 2-2, in the _binary film configuration composed of SiO ₂ and TiO ₂ , or SiO ₂ and ZrO ₂ , 3 minutes after the non-woven fabric is rubbed. The absolute value of the charging potential did not approach zero even after the lapse of time, and the steel wool piece remained attached to the convex surface of the lens. This indicates that there is no antistatic property.

  On the other hand, in the case of Example 2, the absolute value of the charging potential is quite small and almost zero immediately after the rubbing of the nonwoven fabric, and approaches zero as time passes. Therefore, the steel wool piece did not adhere to the lens convex surface. Thus, it was found that Example 2 also exhibited antistatic properties.

Further, a simulation regarding reflectance characteristics was performed for Example 2 and Comparative Examples 2-1 and 2-2 in which an optical multilayer film was formed as shown in FIG. FIG. 8 is a diagram showing a simulation result relating to the reflectance characteristic. As shown in FIG. 8, in any of Example 2 and Comparative Examples 2-1 and 2-2, the reflectance is low in the visible wavelength range. Thus, even with the _{(Ti 1-x Nb x)} 3 O 5 to the high refractive index layer as in Example 2, the visibility of the ophthalmic lens is found not to decrease.

<Example 3>
FIG. 9 is a diagram illustrating a film configuration of the optical multilayer film 13 constituting the bandpass filter according to the third embodiment. FIG. 10 is a diagram showing a film configuration of an optical multilayer film according to Comparative Example 3. 9 and 10, (Ti _1-x Nb _x ) ₃ O ₅ is abbreviated as TNO.

As shown in FIG. 9, in Example 3, the layers of the optical multilayer film 13 are L1 to L36 layers in order from the side closer to the substrate 11. In Example 3, the odd layers of high refractive index material niobium-containing titanium suboxides with when formed of _{((Ti 1-x Nb x} ) 3 O 5), silicon dioxide even layer low refractive index material _(SiO 2) Formed with. That is, the optical multilayer film 13 of Example 3 has a binary film configuration. The refractive index, physical film thickness, optical film thickness, and center wavelength in each of the layers L1 to L36 are as shown in FIG.

As shown in FIG. 10, in Comparative Example 3, the optical multilayer film is formed of 36 layers L1 to L36 as in Example 3, and the odd layer is made of titanium dioxide (TiO ₂ ) as a high refractive index material, The even layer was made of silicon dioxide (SiO ₂ ) as a low refractive index material. The optical multilayer film of Comparative Example 3 also has a binary film configuration. The refractive index, physical film thickness, optical film thickness, and center wavelength in each of the layers L1 to L36 are as shown in FIG.

  With respect to Example 3 and Comparative Example 3 in which an optical multilayer film was formed as shown in FIGS. 9 and 10, an experiment regarding the presence or absence of antistatic properties was performed as follows. That is, the surface of a component was rubbed 20 reciprocations for 10 seconds at a load of 1 kilogram using a nonwoven fabric (“Pure Leaf” manufactured by Ozu Sangyo Co., Ltd.), and the presence or absence of adhesion of a steel wool piece to the component surface was observed. In addition, the surface resistance of the parts was measured with a high resistivity meter (“Hiresta-UP” manufactured by Mitsubishi Chemical). The surface resistance value was measured with an applied voltage of 500 [V] and a measurement holding time of 30 seconds, and this was repeated three times to calculate an average value.

FIG. 11 is a diagram showing experimental results regarding this antistatic property. In FIG. 11, as shown in Example 3, the average value of the surface resistance is 1.74 × 10 ¹⁰ [Ω / □], and the steel wool piece does not adhere to the surface of the component immediately after the non-woven fabric is rubbed. It was. In general, it is known that the smaller the resistance value of the film, the higher the conductivity and the antistatic property, and the antistatic property can be obtained almost certainly if the resistance value is 10 ¹¹ [Ω / □] or less. Yes. Therefore, the above experimental results show that Example 3 exhibits antistatic properties.

On the other hand, as shown in Comparative Example 3, in the _binary film configuration composed of TiO ₂ and SiO ₂ , the steel wool piece remained attached to the part surface. The average value of the surface resistance was 4.84 × 10 ¹² [Ω / □]. This indicates that Comparative Example 3 has no antistatic property.

  Moreover, about Example 3 and the comparative example 3, the simulation regarding a reflectance characteristic was performed. FIG. 12 is a diagram illustrating a simulation result regarding the reflectance characteristic. As shown in FIG. 12, in both Example 3 and Comparative Example 3, the reflectance is low in the desired wavelength range. As a result, it was found that the desired bandpass filter characteristics were obtained in both cases of Example 3 and Comparative Example 3.

<Example 4>
FIG. 13 is a diagram illustrating a film configuration of the optical multilayer film 13 constituting the half mirror according to Example 4 and a film configuration of the optical multilayer film according to Comparative Example 4. FIG. 13A shows Example 4 and FIG. 13B shows Comparative Example 4. In FIG. 13 as well, (Ti _1-x Nb _x ) ₃ O ₅ is abbreviated as TNO.

As shown in FIG. 13A, in Example 4, the layers of the optical multilayer film 13 are L1 to L12 layers in order from the side closer to the substrate 11. In Example 4, the odd layers of high refractive index material niobium-containing titanium suboxides with when formed of _{((Ti 1-x Nb x} ) 3 O 5), silicon dioxide even layer low refractive index material _(SiO 2) Formed with. That is, the optical multilayer film 13 of Example 4 has a binary film configuration. The refractive index, physical film thickness, optical film thickness, and center wavelength in each of the layers L1 to L12 are as shown in FIG.

Further, as shown in FIG. 13B, in Comparative Example 4, the optical multilayer film is formed of 12 layers L1 to L12 as in Example 4, and the odd-numbered layer is made of titanium dioxide (TiO 2) of a high refractive index material. ₂ ) The even layer was made of silicon dioxide (SiO ₂ ) as a low refractive index material. The optical multilayer film of Comparative Example 4 also has a binary film configuration. The refractive index, physical film thickness, optical film thickness, and center wavelength in each of the layers L1 to L12 are as shown in FIG.

For Example 4 and Comparative Example 4 in which an optical multilayer film was formed as shown in FIG. 13, an experiment was conducted regarding the presence or absence of antistatic properties by the same method as in Example 3. FIG. 14 is a diagram showing experimental results regarding this antistatic property. In FIG. 14, as shown in Comparative Example 4, in the _binary film configuration composed of TiO ₂ and SiO ₂ , the steel wool piece remained attached to the part surface. Further, the surface resistance value was too large to be measured. This indicates that Comparative Example 4 has no antistatic property.

On the other hand, in the case of Example 4, the average value of the surface resistance was 3.18 × 10 ¹² [Ω / □], and the steel wool piece did not adhere to the surface of the component immediately after rubbing the nonwoven fabric. . Although the surface resistance value is 10 ¹¹ [Ω / □] or more, since the steel wool piece did not adhere to the surface of the part, Example 4 shows that it has antistatic properties.

  Moreover, about Example 4 and the comparative example 4, the simulation regarding a reflectance characteristic was performed. FIG. 15 is a diagram showing a simulation result related to the reflectance characteristic. As shown in FIG. 15, in both Example 4 and Comparative Example 4, the reflectance is high in most wavelength ranges. Thus, it was found that the characteristics of the half mirror can be obtained in both cases of Example 4 and Comparative Example 4.

  As described above in detail, in this embodiment, in the optical component formed by vapor-depositing the optical multilayer film 13 on the surface of the substrate 11, the thin film material of the high refractive index layer in the optical multilayer film 13 is converted to niobium-containing suboxide. Made of titanium. Thereby, although the thin film formed by vapor-depositing niobium containing titanium suboxide will be in an amorphous state, it has high electroconductivity and can obtain high antistatic property. Further, since it is amorphous, it is not necessary to perform reheating (annealing) after film formation in order to improve crystallinity. Furthermore, since it is not necessary to insert a conductive thin film such as ITO, the optical multilayer film 13 has a binary film configuration in which low refractive index layers and high refractive index layers are alternately laminated. Accordingly, an optical component having a high antistatic effect can be obtained without performing reheating after film formation on the surface of the substrate 11 that is vulnerable to high heat, and without modifying the vapor deposition apparatus to handle three types of materials. Can be obtained.

  In the above embodiment, three examples of spectacle lenses, a band-pass filter, and a half mirror have been described as examples of optical components, but the present invention is not limited to this. For example, it can be applied to other optical components such as lenses other than glasses, filters other than bandpass filters, mirrors other than half mirrors, beam splitters, prisms, polarizing elements, wave plates, light shielding plates, and ground glass. .

  Moreover, although the said embodiment demonstrated the example provided with the base | substrate 11, the hard-coat film | membrane 12, the optical multilayer film 13, and the antifouling film | membrane 14 as a structure of an optical component as shown in FIG. 1, this invention is limited to this. Not. In other words, the base 11 and the optical multilayer film 13 are essential components, and the hard coat film 12 and the antifouling film 14 may be used in accordance with the applications of the various optical parts as described above.

  In addition, the said embodiment is only what showed the example in implementation in implementing this invention, and, as a result, the technical scope of this invention should not be interpreted limitedly. That is, the present invention can be implemented in various forms without departing from the gist or the main features thereof.

11 Substrate 12 Hard coat film 13 Optical multilayer film 14 Antifouling film

In order to solve the above problems, in the present invention, in an optical component formed by vapor-depositing an optical multilayer film on the surface of a substrate, the material of the high refractive index layer of the optical multilayer film is composed of titanium and niobium as components. A metal oxide melt containing oxygen vacancies (referred to as niobium-containing titanium suboxide) , wherein the ratio of the number of metal elements to the number of oxygen elements in the niobium-containing titanium suboxide is 3: 5, and the doping amount of niobium is titanium. In contrast, a thin film formed by vapor deposition of the material formed from a melt of 2 mol% or more and 16 mol% or less has no crystallinity, and an intensity peak does not appear in the reflected wave regardless of the incident angle of X-rays. It is in an amorphous state. That is, in the present invention, an optical component is configured by forming a film on the surface of a substrate by a vapor deposition method using a material made of niobium-containing titanium suboxide.

Claims (4)

An optical component formed by vapor-depositing an optical multilayer film on the surface of a substrate,
An optical component characterized in that the material of the high refractive index layer in the optical multilayer film comprises a melt of niobium-containing titanium suboxide which is a metal oxide having oxygen deficiency containing titanium and niobium as components. 2. The optical component according to claim 1, wherein in the niobium-containing titanium suboxide, the ratio of the number of metal elements to the number of oxygen elements is 3: 5. The optical multilayer film is composed of an odd number of layers, the odd layer counted from the substrate is composed of a low refractive index material, the even layer is composed of a high refractive index material, and the niobium-containing titanium suboxide is used in the even layer. The optical component according to claim 1, wherein the optical component is characterized by the following. The optical multilayer film is composed of an even number of layers, the odd layer counted from the substrate is composed of a high refractive index material, the even layer is composed of a low refractive index material, and the niobium-containing titanium suboxide is used in the odd layer. The optical component according to claim 1, wherein the optical component is characterized by the following.

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