JP2018180237A - Optical instrument, film on surface of optical instrument, and coating used in optical instrument - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating film for an optical instrument, a coating for an optical instrument, and an optical instrument which are improved in weather resistance and scratch resistance, and have a high solar reflectance.SOLUTION: In an optical instrument, a film is formed at least on a lens barrel surface. The film includes at least resin, inorganic particles, pigment, and polyrotaxane having the molecular mass of 180,000 or more and 700,000 or less. The content of the inorganic particles is 23 vol% or more and 34 vol% or less. The content of the polyrotaxane is 0.24 mass% or more and 4.9 mass% or less.SELECTED DRAWING: None

Description

  The present invention is provided on the surface of a lens barrel of an optical device such as a camera, a video, or a broadcast device, or other camera body that may be used outdoors, a video body, a surveillance camera, or an optical device such as a weather camera. It relates to films, paints, and optical devices.

When an optical instrument is used outdoors and sunlight is directly irradiated to the optical instrument, a change in physical properties of the optical material or deterioration may occur due to a rapid rise in temperature.
The film provided on the surface of the optical device is a film having a function of suppressing the temperature rise of the member due to sunlight when used outdoors. Heretofore, as a method of suppressing the temperature rise of the member due to sunlight, a method of reflecting the incident light 1 by the sun as the reflected light 2 by the infrared reflection film 4 on the substrate 5 as shown in FIG. 1 is known By increasing the ratio of the reflected light 2 to the incident light 1, heat generation by the transmitted light 3 can be suppressed. As a material for increasing the reflectance, titanium oxide having a high reflectance in the visible to infrared region is often used. Further, the sunlight energy distribution is 47% in the visible light region and 50% in the infrared region, and it is required that the reflectance in a wide range from visible light to the infrared region is high.
In addition to such heat shielding performance, environmental resistance that reduces the occurrence of defects such as cracking and peeling under severe high temperature and high humidity conditions such as midsummer or just under the equator from the viewpoint of continuous heat shielding performance and appearance And scratch resistance is required to reduce the occurrence of scratches during use.
In addition, the surface of the optical device generally has a complicated shape, and a paint is applied to form a coating film. For this reason, it is important that the paint does not deteriorate its heat shielding property and environmental resistance over time.
In Patent Document 1, in order to improve the environmental performance of the film, a film using a paint containing fine particles and polyrotaxane is formed, and the drug intrusion path around the polyrotaxane is blocked to suppress swelling of the film by the drug. ing. In general, it is known that the inclusion of polyrotaxane in a resin imparts flaw repairability, flexibility and impact resistance.
Further, in Patent Document 2, in order to improve the water resistance and weather resistance of the heat shielding film, the weather resistance is improved by forming an optically transparent organic film and an inorganic film on the surface of the heat shielding pigment. There is.

WO 2010092948 A1 Unexamined-Japanese-Patent No. 1-121371

However, in Patent Document 1, the content of titanium oxide having a high reflectance is small, and sufficient heat shielding can not be obtained. In addition, when used on the surface of an optical device, for example, when used on the surface of a lens barrel etc., it is necessary to apply a film thickness of about several tens of μm in order to improve the accuracy of the movable part to have a zoom function. . When using it as a general heat shielding film like patent document 2, the film thickness of a coating film will be about several hundred micrometers, and can not be used for an optical instrument surface.
The present invention has been made in view of such background art, and provides a film having high heat shielding performance and environmental resistance even on a film thickness of 100 μm or less on a surface for optical devices, for optical devices Provide paints and optical devices.

The present invention is an optical apparatus in which a film is formed on at least a lens and a surface of a lens barrel,
The film contains at least a resin, inorganic particles, a pigment, and a polyrotaxane having a molecular weight of 180,000 to 700,000,
The present invention relates to an optical device characterized in that the content of the inorganic particles is 23 vol% or more and 34 vol% or less, and the content of the polyrotaxane is 0.24 mass% or more and 4.9 mass% or less.

Further, the present invention includes at least a resin, an inorganic particle, a pigment, and a polyrotaxane having a molecular weight of 180,000 to 700,000,
The present invention relates to an optical coating film characterized in that the content of the inorganic particles is 23 vol% or more and 34 vol% or less, and the content of the polyrotaxane is 0.24 mass% or more and 4.9 mass% or less.

  Furthermore, the present invention contains at least a resin, an inorganic particle, a pigment, and a polyrotaxane having a molecular weight of 180,000 to 700,000, and the content of the inorganic particle is 35% by mass to 55% by mass. It relates to paint.

  According to the present invention, there is provided an optical coating film provided on a surface for an optical device having a high heat shielding performance and having weatherability sufficient to withstand actual use, an optical coating material used on a surface for an optical device, and an optical device. I can do it.

It is a cross-sectional schematic diagram which shows the state of reflection and absorption of sunlight at the time of forming the film provided in the surface for optical instruments on the upper surface of a substrate. It is an external view which shows an example of the interchangeable lens for cameras which has a lens-barrel which is one aspect | mode of the optical instrument of this invention. It is a cross-sectional schematic diagram which shows the state which irradiated the sunlight to the film | membrane which the inorganic particle which has a thermal insulation performance disperse | distributed in resin. It is a cross-sectional schematic diagram which shows the state which irradiated the sunlight to the film which the inorganic particle which has a thermal insulation performance aggregated in resin. It is a schematic diagram which shows the measurement form of the reflectance by a spectrophotometer.

  Hereinafter, preferred embodiments of the present invention will be described.

  The optical device of the present invention has a film formed on at least the surface of the lens and the lens barrel, and FIG. 2 shows the appearance of an interchangeable lens for a camera having a lens barrel, which is one aspect of the optical device of the present invention. ing. The interchangeable lens has a lens barrel 20 and a tripod seat 23. The lens barrel 20 is constituted by a lens, a fixed barrel 21, an annular member 22 and the like. Among them, the feature of the optical device of the present invention lies in the film formed on the surface of the fixed barrel 21 of the lens barrel 20, the annular member 22 and the like.

  Therefore, the coating formed on the upper surface of the optical device having high thermal insulation and weather resistance and the configuration of the film formed on the upper surface of the optical device will be mainly described.

[About coating film with high thermal insulation and weather resistance]
Generally, in order to increase the heat shielding property, the component density for reflecting sunlight is increased by increasing the amount of inorganic particles having the heat shielding performance with respect to the amount of resin. Alternatively, it can be realized by eliminating the reflection leak of sunlight due to the uneven distribution of the inorganic particles having the heat shielding performance by enhancing the dispersibility of the inorganic particles having the heat shielding performance (FIG. 3). However, when the number of the inorganic particles having the heat shielding performance is increased, the amount of resin relatively decreases, so that problems such as cracking due to deterioration of the film due to sunlight or increased stress due to increase in hardness occur. In addition, when the distance between the inorganic particles having the heat shielding performance in the coating decreases, aggregation of the inorganic particles having the heat shielding performance occurs. For this reason, the uneven distribution of the inorganic particle which has the thermal insulation performance after coating-film formation generate | occur | produces, and the reflectance by reflection leak reduces (FIG. 4). For this reason, generally, the dispersibility can be improved by using a large amount of the dispersing agent in order to improve the aggregation. However, the heat shielding performance is deteriorated due to the decrease of the amount of inorganic particles having the heat shielding performance relatively, and the weatherability is deteriorated due to the decrease of the resin amount. Thus, it was difficult to improve the weather resistance without deteriorating the heat shielding properties.

  However, when the molecular weight of the polyrotaxane is 180,000 to 700,000 and the addition amount as the coating film is 0.24 mass% to 4.9 mass%, the heat resistance is maintained while maintaining the heat shielding property. It was possible to obtain a high film.

  As described above, it was found that by using the polyrotaxane, the inorganic particles having the heat shielding performance in the film relatively decrease, but the heat shielding property is improved. This is a steric hindrance between the inorganic particles having the heat shielding performance, because the polymer polyrotaxane, which is a polymer, is adsorbed to the inorganic particles having the heat shielding performance in the paint. For this reason, it acts as a dispersant that suppresses the aggregation of inorganic particles having heat shielding performance or the aggregation of particles such as pigments. Furthermore, since the polyrotaxane is bonded to the resin, a coating film in which inorganic particles having the heat shielding performance are effectively dispersed is formed. For this reason, it is estimated that the weather resistance is also improved. Moreover, since it was possible to add flexibility as an effect as a polyrotaxane, it turned out that thermal insulation, weather resistance, and scratch resistance can be compatible.

[Paint for forming on top of optical equipment]
Hereinafter, the material configuration of the coating material for the optical device of the present invention and the method for producing the coating material for the optical device of the present invention will be described.

«Material composition»
(Polyrotaxane)
The polyrotaxane contained in the optical paint of the present invention will be described.

  Rotaxanes are molecules in which rod-like molecules penetrate through cyclic molecules, and by forming bulky parts at both ends of rod-like molecules, the cyclic molecules can not escape from the rod-like molecules by steric hindrance. A rotaxane consisting of one rod-like molecule and a large number of cyclic molecules is called a polyrotaxane.

  The polyrotaxane of the present invention is selected from polyethylene glycol, alkyl chain, amide, ammonium and the like as a rod-like molecule. As a weight average molecular weight of rod-like molecules, 10,000 or more and 40,000 or less can be used. If the weight average molecular weight is less than 10,000, the adsorption to the particles is weak and the particles can not be dispersed well. In addition, when the weight average molecular weight is larger than 40,000, rotaxane itself is steric hindrance and particles and rod-like molecules can not be adsorbed well. The measurement method of the weight average molecular weight at this time was measured using the method as in WO2012124218A1.

  The cyclic molecule is selected from cyclodextrin, cyclophane, cyclic amide, pillar arene, crown ether, calixarene curbituryl and the like.

  As molecular weight of polyrotaxane, 180,000 or more and 700,000 or less can be used. If the molecular weight is less than 180,000, the heat shielding properties are degraded. It is presumed that this is because the molecular weight is small, and therefore, when adsorbed with the inorganic particles having the heat shielding performance, it does not sufficiently act as a steric hindrance to prevent aggregation with other inorganic particles having the heat shielding performance. Ru. Further, if the molecular weight is more than 700,000, the viscosity as a paint becomes too high, and the coatability deteriorates, and a desired film thickness can not be obtained. The addition amount may be adjusted so that the addition amount as a coating film is 0.24% by mass or more and 4.9% by mass or less. As a kind, it selects suitably from the thing of thermosetting and UV curing.

(Inorganic particles)
The inorganic particles having a heat shielding performance contained in the paint of the present invention will be described.

  Rutile type titanium oxide, anatase type titanium oxide, zirconia, zinc oxide or the like can be used as the inorganic particles having the heat shielding performance of the present invention. In addition, in order to suppress the reaction between the inorganic particles having heat shielding performance and the resin when the sunlight is irradiated, the surface of the inorganic particles having the heat shielding performance may be subjected to inactivation treatment. For example, titanium oxide may be coated with one or more layers of silica, zirconium oxide, aluminum oxide, organic substances, and the like.

  The content of the inorganic particles having the heat shielding performance in the paint is 35% by mass or more and 55% by mass or less. When the content of the inorganic particles having the heat shielding performance is less than 35% by mass, the amount thereof is small when it is formed into a coating, and there is a possibility that the sunlight is transmitted to deteriorate the reflectance. In addition, when the content of the inorganic particles having the heat shielding performance exceeds 55% by mass, when the coating is formed, the amount is large and the brittleness of the film may be deteriorated.

  As for the particle diameter of the inorganic particle which has a thermal insulation performance, it is preferable that an average particle diameter is 0.2 micrometer or more and 5.0 micrometers or less. If the average particle size is less than 0.2 μm, it is difficult to efficiently reflect sunlight. Further, when the average particle diameter exceeds 5.0 μm, the unevenness of the coating film becomes large and the film thickness accuracy is deteriorated, so that the accuracy such as focusing may be deteriorated.

(resin)
Next, the resin contained in the paint of the present invention will be described.

  As the resin of the present invention, any material may be used as long as adhesion to the substrate can be secured. Examples of the resin include epoxy resin, urethane resin, acrylic resin, urethane acrylic resin, fluorine resin, silicone resin, phenol resin, alkyd resin and the like. These resins may use one kind or plural kinds.

  Further, the content of the resin of the present invention is preferably 10% by mass to 80% by mass, and more preferably 20% by mass to 50% by mass. When the content of the resin of the present invention is less than 10% by mass, the adhesion to the substrate may be deteriorated. Moreover, when content of resin of this invention exceeds 80 mass%, the solar radiation reflectance of sunlight deteriorates.

(Pigment)
Next, the pigment contained in the paint of the present invention will be described.

  It is preferable that the pigment of the present invention can be adjusted so that the coating film has a lightness of 50 or more, and a more preferable range is 55 to 85. When the pigment of the present invention has a lightness of less than 50, the solar reflectance decreases and the temperature reduction effect deteriorates. When the lightness of the film of the present invention is greater than 85, the reflected light from the surface of the coating becomes strong, and the reflected light that enters the eye at the time of use becomes strong, which has an adverse effect on handling. The pigment of the present invention preferably reflects or transmits infrared light.

  The pigment of the present invention refers to a colorant, which may be an organic pigment, an inorganic pigment or a combination thereof.

  Examples of the organic pigment include azomethine black, perylene pigment and the like. Examples of the inorganic pigment include Co-Zn-Si, Co-Al, Co-Al-Cr, Co-Al-Cr-Zn, Co-Al-Zn-Ti, and Co-Ni-Zn-. Ti system, Ti-Cr-Sb system, Ti-Fe-Zn system, Fe-Zn system, Fe-Cr system, Mn-Bi system, Co-Cr-Zn-Sb system, Cu-Cr system, Cu-Cr- Mn, Cu-Fe-Mn, Mn-Y, Mn-Sr, Co-Cr-Zn-Al-Ti, Co-Cr-Zn-Ti, Ti-Cr-Sb, P-Ba -Sr system etc. are mentioned.

  As the pigment of the present invention, pigments of any color can be used. Examples include black, brown, yellow, red, blue, purple, pink, green and orange. These pigments may be used alone or in combination of two or more.

  The average particle diameter of the pigment of the present invention is preferably 10 nm to 5000 nm, and more preferably 100 nm to 3000 nm. When the average particle diameter of the pigment of the present invention is less than 10 nm, the light resistance is deteriorated. In addition, when the average particle diameter of the pigment of the present invention exceeds 5000 nm, the unevenness of the coating film becomes large, and the film thickness accuracy that can be used for the exterior of the optical device can not be cleared. When assembling the optical devices, there is a possibility that the accuracy of integration, such as deterioration of the assembling accuracy and the deviation of the optical axis, may deteriorate.

  The content of the pigment of the present invention is preferably 1% by mass or less. When the content of the pigment of the present invention exceeds 1% by mass, the color tone of the coating film becomes deep, and the lightness decreases sharply. Although the lower limit is not particularly limited, it can be appropriately selected so as to be an arbitrary color that facilitates handling as an optical member.

(solvent)
Next, the solvent contained in the paint will be described.

  Any material may be used as the solvent. Examples of the solvent include water, thinner, ethanol, isopropyl alcohol, n-butyl alcohol, ethyl acetate, propyl acetate, isobutyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl ether, toluene, xylene, acetone, cellosolve And glycol ethers and ethers. These solvents may be used alone or in combination of two or more.

  The preferable viscosity of the paint of the present invention is 10 mPa · s or more and 10000 mPa · s or less, more preferably 50 mPa · s or more and 500 mPa · s or less. When the viscosity of the paint is less than 10 mPa · s, there may be a place where the film thickness of the heat-shielding film after coating becomes thin. On the other hand, if it exceeds 10000 mPa · s, the coating properties of the paint may be reduced. The solvent can be optionally diluted and adjusted so that the paint has a desired concentration.

(Additive)
The thermal barrier coating of the present invention may contain other optional additives as part of the resin, as long as the thermal barrier properties, weather resistance and scratch resistance are not deteriorated. Examples thereof include dispersants, curing agents, curing catalysts, plasticizers, thixotropic agents, leveling agents, matting agents, preservatives, UV absorbers, antioxidants, coupling agents, inorganic fine particles and organic fine particles, etc. Can be mentioned.

«Method of manufacturing paint for forming on top of optical device»
Below, the manufacturing method of the coating material for optics of this invention is demonstrated.

  As a method of producing a paint for forming on the upper surface of the optical device of the present invention, any method can be used as long as the inorganic particles, the pigment, the polyrotaxane and other components having the heat shielding performance of the present invention can be dispersed in the paint. . Examples include bead mills, ball mills, jet mills, triple rollers, planetary rotators, mixers, ultrasonic dispersers, homogenizers, and the like.

[Film formed on top of optical instrument]
Hereinafter, the material configuration of the film formed on the upper surface of the optical device of the present invention will be described. The film formed on the upper surface of the optical device of the present invention contains at least a resin, inorganic particles having a heat shielding performance, a pigment and a polyrotaxane.

«Material composition»
(Polyrotaxane)
The content of the polyrotaxane of the present invention is 0.24 mass% or more and 4.9 mass% or less, preferably 2.4 mass% or more and 3.7 mass% or less with respect to the film. When the content of the polyrotaxane of the present invention is less than 0.24% by mass, sufficient polyrotaxane is not adsorbed to the inorganic particles having the heat shielding performance, and the dispersibility is deteriorated. In addition, when the content of the polyrotaxane exceeds 4.9% by mass, the polyrotaxane becomes excessive with respect to the inorganic particles having the heat shielding performance, so that the weather resistance is deteriorated.

(Inorganic particles)
The content of the inorganic particles having the heat shielding performance in the film is 23 vol% or more and 34 vol% or less, and preferably 25 vol% or more and 30 vol% or less. When the content of the inorganic particles having the heat shielding performance is less than 23 vol%, sunlight is transmitted through the coating film, so that the reflectance may be deteriorated. In addition, when the content of the inorganic particles having the heat shielding performance exceeds 34 vol%, the brittleness of the film may be deteriorated.

(resin)
The content of the resin of the present invention is preferably 39 vol% or more and 60 vol% or less, more preferably 45 vol% or more and 55 vol% or less. If the content of the resin of the present invention is less than 39 vol%, the adhesion to the substrate may be deteriorated. Moreover, when content of resin of this invention exceeds 60 vol%, the solar radiation reflectance of sunlight deteriorates.

(Pigment)
The content of the pigment of the present invention is preferably 10% by mass or less, more preferably 5% by mass or less. When the content of the pigment of the present invention exceeds 10% by mass, the color tone of the coating film may become dark and the lightness may be lowered.

(Additive)
The heat shielding film of the present invention may contain other optional additives as part of the resin, as long as the heat shielding property, the weather resistance and the scratch resistance are not deteriorated. Examples thereof include dispersants, curing agents, curing catalysts, plasticizers, thixotropic agents, leveling agents, matting agents, preservatives, UV absorbers, antioxidants, coupling agents, inorganic fine particles and organic fine particles, etc. Can be mentioned.

«Film composition»
The film formed on the upper surface of the optical device of the present invention is formed at least outside the substrate. As the form, it may be in close contact with the substrate, or a primer layer may be provided between the substrate and the film formed on the upper surface of the optical device to improve adhesion.

(Base material)
Although any material can be used as a base material, metal and plastic are preferable. Examples of the metal material include alloys containing aluminum, titanium, stainless steel, and magnesium. Examples of the plastic include polycarbonate resin, acrylic resin, ABS resin, fluorine resin and the like.

  Moreover, although it can have arbitrary thickness as a film thickness of a base material, 0.5 mm or more and 5 mm or less are preferable, More preferably, they are 0.5 mm or more and 2 mm or less. If the film thickness is less than 0.5 mm, it is difficult to maintain the shape of the lens barrel. In addition, when the film thickness exceeds 5 mm, the weight of the member increases, making it difficult to handle.

(Primer)
The primer may be used for the purpose of improving the adhesion between the substrate and the membrane. Although any material can be used as a primer, an epoxy resin, a urethane resin, an acrylic resin, a silicone resin, a fluorine resin etc. are mentioned as an example. In the primer, particles of the present invention and particles other than the present invention, colorants, dispersants, curing agents, curing catalysts, plasticizers, thixo transfer agents, leveling agents, organic colorants, inorganic colorants, preservatives, ultraviolet rays Absorbents, antioxidants, coupling agents, solvent residues may be included.

  Moreover, as a film thickness of a primer, 2 micrometers or more and 30 micrometers or less are preferable, and 5 micrometers or more and 20 micrometers or less are more preferable. If the film thickness is less than 2 μm, the adhesion of the film may be lowered, and if it exceeds 30 μm, the accuracy of the optical instrument may be adversely affected.

(The film thickness of the film of the present invention)
The optical coating film of the present invention preferably has a thickness of 10 μm to 70 μm. If the film thickness is less than 10 μm, sufficient solar radiation reflectance can not be reached as a heat shielding film for optical devices. If the film thickness is greater than 70 μm, the positional accuracy of the optical instrument may be adversely affected.

<< Method for forming a film of the present invention >>
The coating film for optics of the present invention can use any coating method and curing method as long as the thermal barrier coating of the present invention can be uniformly coated at 10 μm to 70 μm.

  Brush coating, spray coating, dip coating, transfer etc. are mentioned as an example of the coating method of the heat insulation film | membrane for optical devices of this invention. Further, the heat shielding film may be coated in one layer or in multiple layers, and may be embossed to obtain design.

  Moreover, as a hardening method of the heat shielding film for optical devices of this invention, you may leave it at room temperature, or you may accelerate | stimulate hardening with arbitrary heat and may give an ultraviolet-ray. As a method of giving and hardening heat, a heating furnace, a heater, infrared rays heating etc. are mentioned. The curing temperature is preferably from room temperature to 400 ° C., and more preferably from room temperature to 200 ° C.

<< The characteristics of the film of the present invention >>
(Solar reflectance)
The film formed on the upper surface of the optical device of the present invention has a solar reflectance of 70% to 98%. When the solar reflectance is less than 70%, the temperature reduction effect is reduced. In addition, in order for the solar reflectance to exceed 98%, it is necessary to contain a large amount of titanium oxide, and the brittleness of the film is deteriorated.

  Hereinafter, preferred embodiments of the present invention will be described.

  Preparation of paint in Examples 1 to 11, preparation of film, appearance evaluation before and after weathering test, solar reflectance evaluation, and hardness measurement were performed by the following methods.

<Fabrication of membrane>
As a sample for evaluation, the film of the present invention was formed on a metal plate of 30 mm square and 1 mm in thickness. A magnesium alloy was used for the metal plate. In addition, the film of the present invention was applied to a metal plate by a spin coater so as to obtain a desired film thickness, and the film was fired.

Weatherability test
The film of the present invention was introduced for 1000 hours in a thermostatic bath set to high temperature and high humidity (temperature: 60 ° C., humidity: 90%), and the weather resistance was examined.

<Evaluation of weatherability>
The evaluation of the weather resistance was performed according to JIS K 5600-5-4 (scratch hardness (pencil method)) by comparison before and after the weather resistance test. Before and after the weather resistance test, 3H or more was evaluated as ○, less than 3H as x.

<Sunlight reflectance evaluation>
The solar radiation reflectance was converted to a solar radiation reflectance after measuring the reflectance using a spectrophotometer (U-4000, Hitachi High-Tech), as shown in FIG.

  First, the reflectance measurement method will be described. As shown in FIG. 5, incident light 1 having a wavelength of 300 nm to a wavelength of 2500 nm was made incident on the integrating sphere 8. First, a blank of an alumina sintered body in which 100% reflection occurs in a test piece inclined at 5 ° with respect to the incident light 1 was set at the mounting portion 9 and baseline measurement was performed. Subsequently, a test piece on which the film of the present invention was formed was placed on the test piece attachment portion 9 instead of the blank, light having a wavelength of 300 nm to a wavelength of 2500 nm was incident, and detection was performed by the detector 10 to measure the reflectance. Next, based on JIS-K 560 (how to determine the solar radiation reflectance of the coating film), the measured reflectance was multiplied by the weighting value (weight coefficient) and integrated, and the solar radiation reflectance was calculated from the integral value .

  As a sample for measurement, the film of the present invention was formed on a metal plate of 30 mm square and 1 mm in thickness. A magnesium alloy was used for the metal plate. In addition, the film of the present invention was applied to a metal plate by a spin coater so as to obtain a desired film thickness, and the film was fired.

Example 1
<Preparation of Polyrotaxane>
The polyrotaxane used was produced using the preparation method as described in patent 3475252, and selected polyethylene glycol as a rod-like molecule and cyclodextrin as a cyclic molecule.

<Preparation of membrane>
In Example 1, a membrane was produced by the following method. 0.66 g of polyrotaxane having a molecular weight of 180,000, 15 g of titanium oxide as inorganic particles having heat shielding performance, 13 g of resin (40% by mass as solvent), 0.75 g of silica as thixotropic agent, 0.2 g of pigment, curing agent 3 The paint of Example 1 was obtained by weighing 9 g of a thinner and 3 g of a thinner and stirring for 10 minutes with a planetary rotation device (AR-100, manufactured by Shinky Co., Ltd.). As titanium oxide, D-970 (manufactured by Sakai Chemical Co., Ltd .; average particle diameter 0.26 μm) was used. As a resin, WFU-580 (manufactured by DIC Corporation), which is an acrylic polyol resin, was used. Aerosil R-972 (manufactured by Nippon Aerosil Co., Ltd.) was used as the silica. Chromo fine black A1103 (manufactured by Dainichi Seika Kogyo Co., Ltd.) was used as the pigment. DN-981 (manufactured by DIC Corporation) was used as the curing agent.

<Fabrication of membrane>
In Example 1, a membrane was produced by the following method. Apply the above paint on the test pieces for appearance evaluation, the hardness test pieces before and after the weathering test in a high temperature and high humidity atmosphere, and the solar reflectance evaluation test pieces so that the film thickness is 50 μm and dry at room temperature for 6 hours or more Thereafter, the film was baked at 130 ° C. for 30 minutes to obtain the film of Example 1.

[Examples 2 to 11]
In Examples 2 to 11, paints and films were produced in the same manner as in Example 1 except that the materials and conditions in Table 1 were used.

  The following materials were used for titanium oxide. For titanium oxide having an average particle diameter of 0.26 μm, FTR-700 (manufactured by Sakai Chemical Co., Ltd., silica surface coating) was used, and for titanium oxide having an average particle diameter of 2 μm, ET0210 (manufactured by Toho Titanium Co., Ltd.) was used.

(Evaluation results)
Table 2 shows the appearance of the films of Examples 1 to 11, the hardness before and after the weathering test in a high temperature and high humidity atmosphere, and the solar reflectance by the above-mentioned method.

  As a measurement result, it is preferable that the appearance is free from cracking and peeling. Further, in the tint sample in the present examination, the solar radiation reflectance is preferably 69% or more, and more preferably 74% or more. Moreover, as for pencil hardness evaluation before and behind a weathering test, 3 H or more and 5 H or less are desirable.

  As shown in Table 2, the appearance of Example 1 was good without cracking and peeling. The solar reflectance was 76.1% and was good. The pencil hardness was good at 3 H before and after the weathering test.

  Example 2 in Table 2 shows the evaluation results when the amount of polyrotaxane was reduced relative to Example 1. The appearance of Example 2 was good without cracking and peeling. The solar reflectance was 76.0%, which was good. The pencil hardness was good at 3 H before and after the weathering test.

  Example 3 in Table 2 shows the evaluation results when the amount of polyrotaxane was increased relative to Example 1. The appearance of Example 3 was good without cracking and peeling. The solar reflectance was 76.2% and was good. The pencil hardness was good at 3 H before and after the weathering test.

  Example 4 in Table 2 shows the evaluation results when the amount of titanium oxide is increased relative to Example 1. The appearance of Example 4 was good without cracking and peeling. The solar reflectance was 77.0%, which was good. The pencil hardness was 5H and was very good before and after the weathering test.

  Example 5 in Table 2 shows the evaluation results when the amount of titanium oxide is reduced relative to Example 1. The appearance of Example 5 was good without cracking and peeling. The solar reflectance was 70.0% and was good. The pencil hardness was good at 3 H before and after the weathering test.

  Example 6 in Table 2 shows the evaluation results when the molecular weight of polyrotaxane added to Example 1 is 400,000. The appearance of Example 6 was good without cracking and peeling. The solar reflectance was 76.2% and was good. The pencil hardness was good at 3 H before and after the weathering test.

  In Example 7 of Table 2, the evaluation result which made the polyrotaxane molecular weight added with respect to Example 1 700,000 is shown. The appearance of Example 7 was good without cracking and peeling. The solar reflectance was 76.4 and was good. The pencil hardness was good at 3 H before and after the weathering test.

  Example 8 in Table 2 shows the evaluation results in which the average particle size of titania added to Example 1 is 2 μm. The appearance of Example 8 was good without cracking and peeling. The solar reflectance was 77.2% and was good. The pencil hardness was good at 3 H before and after the weathering test.

  Example 9 in Table 2 shows the evaluation results in which the average particle size of titania added to Example 1 is 0.26 μm. The appearance of Example 9 was good without cracking and peeling. The solar reflectance was 75.3% and was good. The pencil hardness was good at 3 H before and after the weathering test.

  In Example 10 of Table 2, the evaluation result which made film thickness 30 micrometers with respect to Example 1 is shown. The appearance of Example 10 was good without cracking and peeling. The solar reflectance was 74.0% and was good. The pencil hardness was good at 3 H before and after the weathering test.

  Example 11 in Table 2 shows the evaluation results when the film thickness is 70 μm for Example 1. The appearance of Example 11 was good without cracking and peeling. The solar reflectance was 79.2% and was good. The pencil hardness was good at 3 H before and after the weathering test.

Comparative Examples 1 to 5
For comparison, preparation of thermal barrier coating, preparation of thermal barrier film, appearance before and after weathering test, hardness before and after weathering test under high temperature and high humidity atmosphere, and solar reflectance were performed in the same manner as in Examples 1 to 11. . The differences from Examples 1 to 11 will be described below.

  Table 3 shows materials and addition amounts that constitute the heat shielding film of Comparative Examples 1 to 5. The result of having evaluated the heat insulation film of Comparative Examples 1-5 in Table 4 is shown.

  Table 4 shows the evaluation results of Comparative Example 1 when no polyrotaxane is added to Example 1. The hardness after the weathering test was lowered to 2H and was bad.

  Table 4 shows the evaluation results of Comparative Example 2 when a small amount of polyrotaxane was added to Example 1. The solar reflectance was worse than when no polyrotaxane was added. The hardness after the weathering test was lowered to 2H and was bad.

  Table 4 shows the evaluation results of Comparative Example 3 when a large amount of polyrotaxane was added to Example 1. The hardness after the weathering test was lowered to 1 H and was bad.

  Table 4 shows the evaluation results of Comparative Example 4 when a large amount of titanium oxide was added to Example 1. The appearance after the weathering test was cracked and was bad.

  Table 4 shows the evaluation results of Comparative Example 5 when a small amount of titanium oxide is added to Example 1. The solar reflectance was as bad as 65%. The hardness before and after the weathering test was also bad at 2H.

  The film formed on the upper surface of the optical device according to the present invention may be a lens barrel of an optical device such as a camera, a video, or a broadcasting device, or a camera body, video body, surveillance camera, weather which may be used outdoors. It can be used for cameras etc.

  1. Incident light, 2. Reflected light, 3. Transmitted light, 4. Infrared reflective film, 5. Base material, 6; Inorganic particles having dispersed heat shielding performance, 7. Inorganic particles having aggregated heat shielding performance, 8. Integrating sphere, 9. Test piece attachment portion 10. Detector, 20. Lens barrel, 21. Fixed cylinder, 22. An annular member, 23. Tripod seat

Claims (11)

An optical apparatus in which a film is formed on at least a lens and a surface of a lens barrel,
The film contains at least a resin, inorganic particles, a pigment, and a polyrotaxane having a molecular weight of 180,000 to 700,000,
An optical device characterized in that the content of the inorganic particles is 23 vol% or more and 34 vol% or less, and the content of the polyrotaxane is 0.24 mass% or more and 4.9 mass% or less.   The optical apparatus according to claim 1, wherein the film has a hardness of 3H or more and 5H or less.   The optical apparatus according to claim 1 or 2, wherein the film thickness of the film is 10 μm or more and 70 μm or less.   The optical apparatus according to any one of claims 1 to 3, wherein the inorganic particles contain any one of rutile type titanium oxide, anatase type titanium oxide, zirconia and zinc oxide.   The resin according to any one of claims 1 to 4, wherein the resin comprises any one of an epoxy resin, a urethane resin, an acrylic resin, a urethane acrylic resin, a fluorine resin, a silicone resin, a phenol resin, and an alkyd resin. Optical equipment. At least resin, inorganic particles, pigment, and polyrotaxane having a molecular weight of 180,000 to 700,000,
The coating film for optics characterized in that the content of the inorganic particles is 23 vol% or more and 34 vol% or less, and the content of the polyrotaxane is 0.24 mass% or more and 4.9 mass% or less.   The coating film for optics according to claim 6, wherein hardness of said film is 3H or more and 5H or less.   The coating film for optics according to claim 6 or 7 whose film thickness of said film is 10 micrometers or more and 70 micrometers or less.   The coating film for optics according to any one of claims 6 to 8, wherein the inorganic particles have any one of rutile type titanium oxide, anatase type titanium oxide, zirconia and zinc oxide.   10. The resin according to any one of claims 6 to 9, wherein the resin comprises any one of an epoxy resin, a urethane resin, an acrylic resin, a urethane acrylic resin, a fluorine resin, a silicone resin, a phenol resin, and an alkyd resin. Coating for optics.   A paint for optics, comprising at least a resin, an inorganic particle, a pigment, and a polyrotaxane having a molecular weight of 180,000 to 700,000, and a content of the inorganic particle of 35 to 55% by mass.

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