JP2014115393A - Optical element having light shielding film and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an optical element having less bright spots seen in white and excellent appearance when an interface between an optical element and a light shielding film is looked into from an optical element side.SOLUTION: The method for manufacturing an optical element having a light shielding film formed on an edge surface of the optical element comprises the steps of: grinding the optical element to form the edge surface; charging cracks of the edge surface with a transparent material having a viscosity of 26 mPa s or less; and applying a light shielding coating to the edge surface charged with the transparent material to form the light shielding film. A refractive index difference between the optical element and the transparent material is 0.19 or less.

Description

  The present invention relates to an optical element having a light-shielding film used in optical equipment such as a camera, binoculars, a microscope, a semiconductor, and a liquid crystal exposure apparatus.

  Conventionally, optical elements used in optical equipment such as cameras, binoculars, microscopes, semiconductor / liquid crystal exposure apparatuses, etc. are provided with a black light-shielding film outside the optically effective part as necessary to reduce stray light. ing. An optical element in which a light shielding film is formed on the edge surface of the optical element will be described with reference to FIG. The stray light that reaches the edge surface 52 of the optical element 51 is sufficiently absorbed by the light shielding film 53, and unnecessary light such as flare and ghost is reduced. This light-shielding film is expected to have an effect of reducing stray light that enters the light-shielding film from the inside of the optical element, and is required to suitably reduce reflected light called internal reflection.

  In order to reduce the internal reflection light, a method is known in which a component having a high refractive index is introduced into the light-shielding film so that the refractive index of the light-shielding film is suitably controlled by bringing it closer to the refractive index of the glass (Patent Document). 1).

  Patent Document 1 discloses a light-shielding film for an optical element that reduces internal reflection light by improving the refractive index using non-black inorganic fine particles and absorbing light with a dye and a pigment.

JP 2011-164494 A

  With recent downsizing and higher performance of optical devices, materials having higher refractive index have been used for optical elements used in optical systems. However, when a light-shielding film is applied to the edge of an optical element using such a material having a high refractive index, incident light is irregularly reflected, white spots appear white, and the appearance is not good. Found.

This problem will be described below. FIG. 6 is a cross-sectional view showing an interface (edge surface) between the optical element 61 and the light shielding film 62. As shown in FIG. 6, many minute cracks 63 exist on the edge surface. Such a crack is generated when the edge surface is processed by grinding, and is often generated in a glass material having a high refractive index. The reason why many cracks occur in glass materials with a high refractive index is that the glass materials with a high refractive index are added with elements such as La other than SiO ₂ to increase the refractive index, so the molecular strength between SiO ₂ and the like decreases. Thus, it is considered that cracks are likely to occur during grinding. The size of the crack is usually 5 μm or less in width and 50 μm or less in length.

  As shown in FIG. 6, when the light shielding film 62 is provided on the edge surface including the minute cracks 63, the light shielding film 62 is not filled in the cracks 63, so that “space (air)” is generated in the cracks 63. Due to the difference in refractive index between the “space (air)” of the crack 63 and the “optical element”, reflected light (scattered light) 65 in which the incident light 64 is irregularly reflected is generated, and the optical element and the light shielding film are separated from the optical element side. When looking into the interface, bright spots that appear white appear and the application is not good.

  The present invention relates to a method of manufacturing an optical element having a light shielding film in which a light shielding film is formed on the edge surface of the optical element, the step of grinding the optical element to create an edge surface, and cracks on the edge surface. A step of filling a transparent material having a viscosity of 26 mPa · s or less, and a step of applying a light-shielding paint to the edge surface filled with the transparent material to form the light-shielding film. The present invention relates to a method for manufacturing an optical element having a light-shielding film, wherein a refractive index difference with a transparent material is 0.19 or less.

  Further, the present invention is an optical element having an optical element and a light shielding film having a light shielding film on the edge surface of the optical element, wherein a transparent material is filled in a crack on the edge surface of the optical element. The present invention relates to an optical element having a light shielding film.

  The optical element of the present invention is filled with a transparent material having a small refractive index difference from the optical element in the crack generated on the edge surface, and can suppress irregular reflection of light entering from the outside. The present invention provides an optical element that has few bright spots that appear white when the interface between the optical element and the light-shielding film is viewed from the optical element side, and has a good appearance.

It is a figure which shows the optical element which has a light shielding film of this invention. It is a figure which shows the edge surface vicinity of the optical element which has a light shielding film of this invention. It is the schematic which shows the grinding method of an evaluation surface. It is the schematic which shows an external appearance evaluation method. It is the schematic of the optical element which has a light shielding film on the edge surface. It is the schematic explaining the cause of the bright spot which looks white which causes the fall of external appearance quality.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings as appropriate.

  The present invention relates to an optical element having a light-shielding film and a method for manufacturing the same, in which cracks generated on the edge surface are filled with a transparent material having a small refractive index difference from the optical element to suppress irregular reflection. As shown in FIG. 1, the optical element having the light shielding film of the present invention is provided with a light shielding film 13 on the edge surface 12 of the optical element 11. Moreover, the transparent material 14 is filled in the crack generated on the edge surface. The transparent material 14 may form a transparent material film. FIG. 2 is an enlarged view of the vicinity of the edge surface of the light shielding film of FIG. The optical element and the light shielding film 21 have a film of a transparent material 22. In the optical element having the light shielding film of the present invention, irregular reflection of incident light is reduced, and appearance defects of bright spots that appear white can be reduced.

  The present invention solves the above problems with the following configuration.

(Method for producing optical element having light shielding film)
The manufacturing method of the optical element which has a light shielding film of this invention has the process of creating an edge surface, the process of filling with a transparent material, and the process of forming a light shielding film.

  The optical element includes all elements that perform the function of condensing, reflecting, refraction, and interfering light, and includes, for example, a mirror and a grating in addition to a lens and a prism. The present invention can be suitably used for glass lenses. Further, the present invention can be suitably used for a high refractive index optical element having a refractive index of 1.7 to 2.2. Examples of the high refractive index optical element include S-LAL18, S-LAH53, S-LAH58, and S-TIH53 manufactured by OHARA.

  In the process of creating the edge surface, the edge surface is created by grinding the optical element. The edge surface is a ground surface of the lens peripheral edge (edge).

  In the step of filling the transparent material, the transparent material is filled into the cracks on the edge surface caused by grinding. The transparent material may be filled by applying a transparent material to form a transparent material film. The viscosity of the transparent material is preferably 26 mPa · s or less, more preferably 10 mPa · s or less and 26 mPa · s or less. When the viscosity of the transparent material paint exceeds 26 Pa · s, it is difficult for the transparent paint to enter the edge surface, and it is difficult to suppress the generation of white bright spots. In the present specification, the transparent material means a material having a thickness of 1 μm and a visible light (400 to 800 nm) transmittance of 90% or more. The transparent material preferably contains at least a thermosetting resin and a curing agent. The transparent material has a refractive index difference of 0.19 or less with respect to the optical element. When the refractive index exceeds 0.19, suppression of irregular reflection of incident light becomes insufficient.

  The thermosetting resin used for the transparent material is preferably an epoxy resin or an acrylic resin. Among these, it is more preferable to use an epoxy resin because it has a high refractive index and good adhesion to glass. These resins may be used alone or in combination of two or more.

  As for the formed transparent material, it is preferable that a main component is an epoxy resin. In the present specification, the main component means that the content is 51% by weight. As the curing agent in the transparent material, a known curing agent or curing accelerator can be used. Preferably polyaddition type or catalyst such as aliphatic polyamine, alicyclic polyamine, aromatic polyamine, acid anhydride, phenol novolac, polymercaptan, aliphatic tertiary amine, aromatic tertiary amine, imidazole compound, Lewis acid complex One type or two or more types of mold curing agents or curing accelerators can be used in combination.

  In the step of forming the light shielding film, the light shielding film is formed by applying a light shielding paint to the edge surface to which the transparent material is applied. It is preferable that the light-shielding paint contains an epoxy resin, an amine curing agent, a dye or pigment, and a solvent.

  In the case where an epoxy resin is used for the light-shielding paint, the dye is preferably a dye having two or more amino groups having reactivity with the epoxy resin. In addition, in order to obtain sufficient blackness for a dye having two or more amino groups, the ratio of the minimum transmittance to the maximum transmittance (minimum transmittance / maximum transmittance) in light with a wavelength of 400 nm to 700 nm of the light shielding film is set to 0. .7 or more is preferable. In order to make the ratio of the minimum absorption rate and the maximum absorption rate in light with a wavelength of 400 nm to 700 nm 0.7 or more, the dye having two or more amino groups may be one kind, black, red, yellow, The absorption wavelength may be adjusted by mixing several kinds of dyes such as blue.

  As the dye having two or more amino groups, azo dyes with a wide variety of colors are preferable, but anthraquino dyes, phthalocyanine dyes, stilbenzene dyes, pyrazolone dyes, thiazole dyes, carbonium dyes, and azine dyes may be used. . In particular, the dye preferably contains an azo group. Moreover, since fastness, such as light resistance, water resistance, and heat resistance, increases, the dye containing metals, such as chromium and copper, is preferable.

  The content of the dye contained in the light-shielding film of the present invention is preferably 10% by mass or less and 50% by mass or less, and more preferably 20% by mass or more and 30% by mass or less. When the content of the dye exceeds 50% by mass, the durability of the light shielding film is lowered, which is not preferable.

  Next, the epoxy resin used for the light-shielding paint is preferably a resin having good adhesion to the optical element and a high refractive index. As the type of epoxy resin, a wide variety of bisphenol A type epoxy resins, bisphenol F type epoxy resins, fluorene type epoxy resins having a high refractive index, and epoxy resins containing sulfur are preferable, but other types of epoxy resins may be used. Absent. Two or more types of epoxy resins may be mixed and used.

  The content of the epoxy resin contained in the light-shielding film of the present invention is 15% by mass or less and 60% by mass or less, and preferably 20% by mass or more and 30% by mass or less in terms of the weight ratio at the time of coating. When the content of the epoxy resin is less than 15% by mass, the durability of the coating film is lowered, which is not preferable.

  As a solvent for the light-shielding coating material, it is sufficient that the pigment and the particles for improving the refractive index are dispersed and the dye can be dissolved. Examples include toluene, hexane, cyclohexane, xylene, 1-butanol, butyl acetate, ethyl acetate, methyl isobutyl ketone (MIBK), propylene glycol monomethyl ether (PGME), and the like, but are not limited thereto.

  Moreover, you may contain additives, such as a hardening | curing agent for hardening resin, a coupling agent, a dispersing agent, antiseptic | preservative, antioxidant, as another component contained in a light shielding film.

  The light-shielding film for optical elements of the present invention is obtained by curing the light-shielding paint for optical elements described above.

(Optical element having a light-shielding film)
The optical element having a light-shielding film of the present invention has a light-shielding film on the edge of the optical element and the optical element, and a transparent material is filled in the cracks on the edge.

  The optical element serving as the light shielding film of the present invention preferably has a transparent material film having a transparent material between the optical element and the light shielding film. The film of the transparent material is preferably 0.1 μm or more and 5 μm or less, and more preferably 0.1 μm or more and 3 μm or less. When the thickness is less than 0.1 μm, it is difficult to form a film, and when it is thicker than 0.5 μm, the transparent material film tends to crack after the durability test. The transparent material preferably contains inorganic fine particles. The transparent material preferably contains an epoxy resin.

  Moreover, what was described in the said manufacturing method can be used for the optical element, light shielding film, transparent material, etc. which are used for the optical element which has the light shielding film of this invention.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. The present invention is not limited to these examples.

  In addition, the evaluation in the Example and comparative example of this invention was performed with the following method.

(Evaluation of appearance of bright spots that appear white)
As shown in FIG. 4, light was applied from the glass side 42 of the flat glass on which the light shielding film 41 was formed, and a bright spot that looked white at the interface between the light shielding film and the glass was photographed by the CCD camera 43. The captured image was subjected to image processing using image analysis software (Image-Pro Plus manufactured by Media Cybernetics), and the number of bright spots that looked white with an area of 150 μm ² or more in 6 mm ² was counted.

  Appearance was evaluated according to the following criteria. An optical element having a light-shielding film having an average of 150 or less bright spots has a good appearance (◯), and when the average number of bright spots exceeds 150, the external application is insufficient (×). As evaluated.

(Measurement of refractive index of film made of transparent material)
The refractive index of a film made of a transparent material is measured by forming a light-shielding film on the mirror surface side of a flat glass (Φ30 mm, thickness 1 mm) of BK7 whose one side is a mirror surface and the other side is a ground surface. It was measured. An ellipsometer (JA WOOLLAM CO., INC. UB-250, HS-190) was used for the measurement.

(Measurement of viscosity of transparent paint)
The viscosity of the transparent material paint was measured with a tuning fork vibration viscometer (SV-1H manufactured by A & D Co., Ltd.) before applying the transparent material paint to the flat glass.

(Example)
The optical elements and transparent materials used in Examples and Comparative Examples are shown in Tables 1 and 2. Further, the light-shielding paint is described in Table 3.

Example 1
Epoxy resin jER828 [product name] (Mitsubishi Chemical Co., Ltd.) 5.00 g, titania dispersion ND291 [product name] (Taika Co., Ltd., titania concentration 25 mass% PGMEA dispersion, primary particle number average particle diameter in a stirring vessel : 15 nm) 10.48 g and PGMEA (manufactured by Kishida Chemical Co., Ltd.) 15.00 g were added and stirred for 5 minutes with a planetary rotary stirrer HM-500 [product name] (manufactured by Keyence Corporation). Add 1.77 g of amine-based curing agent jER113 [product name] (manufactured by Mitsubishi Chemical Corporation) to 30.48 g of the obtained epoxy resin composition, and use a planetary rotary stirrer HM-500 [product name] (manufactured by Keyence Corporation) for 3 minutes. Stir. The viscosity of the obtained transparent material was 19 mPa · s.

  A grindstone while rotating one surface of a flat glass 31 (Φ30 mm, thickness 10 mm) of a high refractive index glass material (S-LAH53 nd: 1.80, S-TIH53 nd: 1.84 manufactured by OHARA) shown in FIG. Grinding was performed at 32, and a grinding surface 33 was formed to face evaluation. As the grindstone 32, a grindstone electrodeposited with diamond abrasive grains having an average particle diameter of about 45 μm was used. The grinding conditions were as follows: the rotation speed of the flat glass 31 was 200 rpm, the rotation speed of the grindstone 32 was 13000 rpm, and the cutting speed of the grindstone 32 was 20 μm / sec. After applying the transparent material obtained on the evaluation surface (grinding surface 33) using a spin coat method so that the film thickness after firing becomes 2 μm, the ground surface is dried at room temperature for 1 hour to form a transparent material film. Formed. Thereafter, the light-shielding paint having the composition shown in Table 3 was stirred on the transparent material film with a roll coater at 66 rpm for 48 hours to obtain a light-shielding paint. The obtained light-shielding paint was applied to the edge surface using a spin coating method so that the film thickness after firing was 3 μm, dried at room temperature for 1 hour, and then fired in a constant temperature oven at 80 ° C. for 2 hours. Table 4 shows the results of the appearance evaluation of the white light spots of the obtained light-shielding film.

(Example 2)
Epoxy resin jER828 [product name] (manufactured by Mitsubishi Chemical) 5.00 g, titania dispersion ND291 [product name] (manufactured by Teica, titania concentration 25 mass% PGMEA dispersion, average primary particle size 15 nm) 4 .40 g and PGMEA (manufactured by Kishida Chemical Co., Ltd.) 7.00 g were added, and the mixture was stirred with a planetary rotary stirrer HM-500 [product name] (manufactured by Keyence Corporation) for 5 minutes. Add 1.77 g of amine-based curing agent jER113 [product name] (manufactured by Mitsubishi Chemical Corporation) to 16.40 g of the obtained epoxy resin composition, and use a planetary rotary stirrer HM-500 [product name] (manufactured by Keyence Corporation) for 3 minutes. Stir. The viscosity of the obtained transparent material was 19 mPa · s.

  A ground surface was formed by grinding in the same manner as in Example 1 except that flat glass (S-LAH53 nd: 1.80 manufactured by OHARA) was used. The obtained transparent liquid was applied to the ground surface in the same manner as in Example 1, and then dried at room temperature for 1 hour to form a transparent material film. Thereafter, the light-shielding paint used in Example 1 was applied onto the transparent material film in the same manner as in Example 1, dried at room temperature for 1 hour, and then baked at 80 ° C. for 2 hours in a thermostatic oven. Table 4 shows the results of the appearance evaluation of the white light spots of the obtained light-shielding film.

(Example 3)
Epoxy resin jER828 [product name] (manufactured by Mitsubishi Chemical) 5.00 g, titania dispersion ND291 [product name] (manufactured by Teika, titania concentration 25 mass% PGMEA dispersion, average primary particle size 15 nm) 2 0.000 g and 7.70 g of PGMEA (manufactured by Kishida Chemical Co., Ltd.) were added and stirred for 5 minutes with a planetary rotary stirrer HM-500 [product name] (manufactured by Keyence Corporation). Add 1.77 g of amine curing agent jER113 [product name] (manufactured by Mitsubishi Chemical Corporation) to 14.70 g of the obtained epoxy resin composition and add 3 minutes with planetary rotary stirrer HM-500 [product name] (manufactured by Keyence Corporation). Stir. The viscosity of the obtained transparent material was 19 mPa · s.

  A ground surface was formed by grinding in the same manner as in Example 1 except that flat glass (S-LAH53 nd: 1.80 manufactured by OHARA) was used. The obtained transparent liquid was applied to the ground surface in the same manner as in Example 1, and then dried at room temperature for 1 hour to form a transparent material film. Thereafter, the light-shielding paint used in Example 1 was applied onto the transparent material film in the same manner as in Example 1, dried at room temperature for 1 hour, and then baked at 80 ° C. for 2 hours in a thermostatic oven. Table 4 shows the results of the appearance evaluation of the white light spots of the obtained light-shielding film.

Example 4
Epoxy resin jER828 [product name] (manufactured by Mitsubishi Chemical Corporation) 5.00 g, titania dispersion ND291 [product name] (manufactured by Teika, titania concentration 25 mass% PGMEA dispersion, average primary particle size 15 nm) 10 .48 g and 10.00 g of PGMEA (manufactured by Kishida Chemical Co., Ltd.) were added and stirred for 5 minutes with a planetary rotary stirrer HM-500 [product name] (manufactured by Keyence Corporation). 1.25 g of amine curing agent jER113 [product name] (manufactured by Mitsubishi Chemical Corporation) is added to 25.48 g of the obtained epoxy resin composition, and the planetary rotary stirrer HM-500 [product name] (manufactured by Keyence Corporation) is used for 3 minutes. Stir. The viscosity of the obtained transparent material was 25 mPa · s.

  A ground surface was formed by grinding in the same manner as in Example 1 except that flat glass (S-LAH53 nd: 1.80 manufactured by OHARA) was used. The obtained transparent liquid was applied to the ground surface in the same manner as in Example 1, and then dried at room temperature for 1 hour to form a transparent material film. Thereafter, the light-shielding paint used in Example 1 was applied onto the transparent material film in the same manner as in Example 1, dried at room temperature for 1 hour, and then baked at 80 ° C. for 2 hours in a thermostatic oven. Table 4 shows the results of the appearance evaluation of the white light spots of the obtained light-shielding film.

(Example 5)
Epoxy resin Ogsol EG-200 [product name] (Osaka Gas Chemical Co., Ltd.) 5.00 g and PGMEA (Kishida Chemical Co., Ltd.) 11.00 g were put into a stirring vessel, and planetary rotary stirrer HM-500 [product name]. (Manufactured by KEYENCE) for 5 minutes. 1.54 g of anhydride curing agent Ricacid MH-700 [product name] (manufactured by Nippon Rika Co., Ltd.) is added to 16.00 g of the obtained epoxy resin composition, and planetary rotary stirrer HM-500 [product name] (manufactured by Keyence Corporation) is added. ) For 3 minutes. The viscosity of the obtained transparent material was 26 mPa · s.

  A ground surface was formed by grinding in the same manner as in Example 1 except that flat glass (S-LAH53 nd: 1.80 manufactured by OHARA) was used. The obtained transparent material was applied to the ground surface in the same manner as in Example 1, and then dried at room temperature for 1 hour to form a transparent material film. Thereafter, the light-shielding paint used in Example 1 was applied onto the transparent material film in the same manner as in Example 1, dried at room temperature for 1 hour, and then baked at 80 ° C. for 2 hours in a thermostatic oven. Table 4 shows the results of the appearance evaluation of the white light spots of the obtained light-shielding film.

(Example 6)
Epoxy resin jER828 [product name] (manufactured by Mitsubishi Chemical) 5.00 g, titania dispersion ND291 [product name] (manufactured by Teika, titania concentration 25 mass% PGMEA dispersion, average primary particle size 15 nm) 2 0.000 g and 7.70 g of PGMEA (manufactured by Kishida Chemical Co., Ltd.) were added and stirred for 5 minutes with a planetary rotary stirrer HM-500 [product name] (manufactured by Keyence Corporation). Add 1.77 g of amine curing agent jER113 [product name] (manufactured by Mitsubishi Chemical Corporation) to 14.70 g of the obtained epoxy resin composition and add 3 minutes with planetary rotary stirrer HM-500 [product name] (manufactured by Keyence Corporation). Stir. The viscosity of the obtained transparent material was 19 mPa · s.

  A ground surface was formed by grinding in the same manner as in Example 1 except that flat glass (S-TIH53 nd: 1.84 manufactured by OHARA) was used. The obtained transparent material was applied to the ground surface in the same manner as in Example 1, and then dried at room temperature for 1 hour to form a transparent material film. Thereafter, the light-shielding paint used in Example 1 was applied onto the transparent material film in the same manner as in Example 1, dried at room temperature for 1 hour, and then baked at 80 ° C. for 2 hours in a thermostatic oven. Table 4 shows the results of the appearance evaluation of the white light spots of the obtained light-shielding film.

(Comparative Example 1)
Epoxy resin jER828 [product name] (Mitsubishi Chemical Co., Ltd.) 5.00 g and PGMEA (Kishida Chemical Co., Ltd.) 8.40 g are charged into the stirring vessel, and planetary rotary stirrer HM-500 [Product Name] (Keyence Co., Ltd.). ) For 5 minutes. 1.77 g of amine curing agent jER113 [product name] (manufactured by Mitsubishi Chemical Corporation) is added to 13.40 g of the obtained epoxy resin composition, and the planetary rotary stirrer HM-500 [product name] (manufactured by Keyence Corporation) is used for 3 minutes. Stir. The viscosity of the obtained transparent liquid was 19 mPa · s.

  A ground surface was formed by grinding in the same manner as in Example 1 except that flat glass (S-LAH53 nd: 1.80 manufactured by OHARA) was used. The obtained transparent material was applied to the ground surface in the same manner as in Example 1, and then dried at room temperature for 1 hour to form a transparent material film. Thereafter, the light-shielding paint used in Example 1 was applied onto the transparent material film in the same manner as in Example 1, dried at room temperature for 1 hour, and then baked at 80 ° C. for 2 hours in a thermostatic oven. Table 4 shows the evaluation results of the appearance defects of the bright spots that appear white in the obtained light-shielding film.

(Comparative Example 2)
Silicone resin KER-6075F [product name] (manufactured by Shin-Etsu Silicon Co., Ltd.) 15.00 g and PGMEA (manufactured by Kishida Chemical Co., Ltd.) 5.00 g are charged into the stirring vessel, and planetary rotary stirrer HM-500 [product name] (Keyence) For 5 minutes. The viscosity of the obtained transparent material was 19 mPa · s.

  A ground surface was formed by grinding in the same manner as in Example 1 except that flat glass (S-LAH53 nd: 1.80 manufactured by OHARA) was used. The obtained transparent liquid was applied to the ground surface in the same manner as in Example 1, then dried at room temperature for 1 hour, and baked in a constant temperature oven at 100 ° C. for 1 hour to form a transparent material film. Thereafter, the light-shielding paint used in Example 1 was applied onto the transparent material film in the same manner as in Example 1, dried at room temperature for 1 hour, and then baked at 80 ° C. for 2 hours in a thermostatic oven. Table 4 shows the results of the appearance evaluation of the white light spots of the obtained light-shielding film.

(Comparative Example 3)
Epoxy resin jER828 [product name] (manufactured by Mitsubishi Chemical Corporation) 5.00 g, titania dispersion ND291 [product name] (manufactured by Teika, titania concentration 25 mass% PGMEA dispersion, average primary particle size 15 nm) 20 .48 g and PGMEA (manufactured by Kishida Chemical Co., Ltd.) 5.00 g were added and stirred for 5 minutes with a planetary rotary stirrer HM-500 [product name] (manufactured by Keyence Corporation). 1.77 g of amine curing agent jER113 [product name] (manufactured by Mitsubishi Chemical Corporation) is added to 17.50 g of the obtained epoxy resin composition, and planetary rotating stirrer HM-500 [product name] (manufactured by Keyence Corporation) is used for 3 minutes. Stir. The viscosity of the obtained transparent material was 30 mPa · s.

  A ground surface was formed by grinding in the same manner as in Example 1 except that flat glass (S-LAH53 nd: 1.80 manufactured by OHARA) was used. The obtained transparent liquid was applied to the ground surface in the same manner as in Example 1, and then dried at room temperature for 1 hour to form a transparent material film. Thereafter, the light-shielding paint used in Example 1 was applied onto the transparent material film in the same manner as in Example 1, dried at room temperature for 1 hour, and then baked at 80 ° C. for 2 hours in a thermostatic oven. Table 4 shows the results of the appearance evaluation of the white light spots of the obtained light-shielding film.

(Comparative Example 4)
Epoxy resin jER828 [product name] (manufactured by Mitsubishi Chemical Corporation) 5.00 g, titania dispersion ND291 [product name] (manufactured by Teika, titania concentration 25 mass% PGMEA dispersion, average primary particle size 15 nm) 20 .48 g was added and stirred for 5 minutes with a planetary rotary stirrer HM-500 [product name] (manufactured by Keyence Corporation). Add 1.77 g of amine curing agent jER113 [product name] (manufactured by Mitsubishi Chemical Corporation) to 15.48 g of the obtained epoxy resin composition, and use a planetary rotary stirrer HM-500 [product name] (manufactured by Keyence Corporation) for 3 minutes. Stir. The viscosity of the obtained transparent material was 40 mPa · s.

  A ground surface was formed by grinding in the same manner as in Example 1 except that flat glass (S-LAH53 nd: 1.80 manufactured by OHARA) was used. The obtained transparent liquid was applied to the ground surface in the same manner as in Example 1, and then dried at room temperature for 1 hour to form a transparent material film. Thereafter, the light-shielding paint used in Example 1 was applied onto the transparent material film in the same manner as in Example 1, dried at room temperature for 1 hour, and then baked at 80 ° C. for 2 hours in a thermostatic oven. Table 4 shows the results of the appearance evaluation of the white light spots of the obtained light-shielding film.

(Example 7)
An optical lens having a ground surface similar to that of Example 1 was prepared except that optical glass (S-LAH53 nd: 1.88 manufactured by OHARA) was used. A transparent material and a light-shielding paint similar to those in Example 1 were prepared, applied to the ground surface using a sponge, and a transparent film and a light-shielding film were formed in the same manner as in Example 1. The obtained optical lens was a good optical lens with few white bright spots.

(Evaluation)
From Examples 1 to 6, the difference in refractive index between the optical element and the film made of a transparent material attached on the edge surface of the optical element and filled in the crack generated on the edge surface is 0.19 or less, and transparent. It was confirmed that the appearance defect was reduced when the viscosity of the material was 26 mPa · s or less.

  From Comparative Examples 1 and 2, the appearance was not good when the refractive index difference between the transparent material film and the optical element exceeded 0.19.

  From Comparative Examples 3 and 4, when the viscosity of the transparent material paint exceeded 26 mPa · s, the appearance was not good.

  From Example 7, it was found that even if the glass material used in Examples 1 to 6 was used for an optical lens, an optical lens with few bright spots that appeared white could be obtained.

DESCRIPTION OF SYMBOLS 11 Optical element 12 Edge 13 Light shielding film 14 Transparent material 21 Light shielding film 22 Transparent material

Claims (10)

A method of manufacturing an optical element having a light shielding film in which a light shielding film is formed on the edge of the optical element,
Grinding the optical element to create a edge surface;
Filling the cracks on the edge surface with a transparent material having a viscosity of 26 mPa · s or less;
Applying a light-shielding paint to the edge surface filled with the transparent material to form the light-shielding film,
A method for producing an optical element having a light-shielding film, wherein a difference in refractive index between the optical element and the transparent material is 0.19 or less.   The method of manufacturing an optical element having a light-shielding film according to claim 1, wherein a refractive index of the optical element is 1.7 to 2.2.   The method for producing an optical element having a light-shielding film according to claim 1, wherein the transparent material contains inorganic fine particles.   The method for manufacturing an optical element having a light-shielding film according to claim 1, wherein the transparent material contains an epoxy resin or an acrylic resin.   The method of manufacturing an optical element having a light-shielding film according to any one of claims 1 to 4, wherein the optical element is a glass lens.   6. The optical according to claim 1, wherein in the step of filling with the transparent material, a film of the transparent material is formed between the edge surface of the optical element and the light shielding film. Device manufacturing method. An optical element having an optical element and a light shielding film having a light shielding film on the edge surface of the optical element,
The crack on the edge surface of the optical element is filled with a transparent material,
An optical element having a light-shielding film, wherein a refractive index difference between the optical element and the transparent material is 0.19 or less.   The optical element having a light shielding film according to claim 7, further comprising a transparent material film having the transparent material between the optical element and the light shielding film.   The optical element having a light-shielding film according to claim 7 or 8, wherein the transparent material contains inorganic fine particles.   The optical element having a light shielding film according to claim 7, wherein the transparent material contains an epoxy resin.

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