CN112513682A - Coating method, optical element and lens assembly - Google Patents
Coating method, optical element and lens assembly Download PDFInfo
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- CN112513682A CN112513682A CN201980050301.6A CN201980050301A CN112513682A CN 112513682 A CN112513682 A CN 112513682A CN 201980050301 A CN201980050301 A CN 201980050301A CN 112513682 A CN112513682 A CN 112513682A
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- light
- test
- optical element
- waterproof film
- weather resistance
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- 230000003287 optical effect Effects 0.000 title claims abstract description 79
- 238000000576 coating method Methods 0.000 title claims abstract description 45
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 29
- 239000011737 fluorine Substances 0.000 claims abstract description 29
- 239000005871 repellent Substances 0.000 claims abstract description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000003961 organosilicon compounds Chemical class 0.000 claims abstract description 12
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 5
- 238000012360 testing method Methods 0.000 claims description 95
- 239000011248 coating agent Substances 0.000 claims description 28
- 238000011282 treatment Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000009832 plasma treatment Methods 0.000 claims description 9
- 238000010894 electron beam technology Methods 0.000 claims description 5
- 238000003851 corona treatment Methods 0.000 claims description 4
- 238000002203 pretreatment Methods 0.000 abstract 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 32
- 230000000052 comparative effect Effects 0.000 description 18
- 238000005259 measurement Methods 0.000 description 15
- 239000000126 substance Substances 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 10
- 150000001367 organochlorosilanes Chemical class 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 7
- 125000003368 amide group Chemical group 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- -1 organosilane compound Chemical class 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 206010059866 Drug resistance Diseases 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000005304 optical glass Substances 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical group II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/023—Optical properties
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Surface Treatment Of Optical Elements (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
Abstract
Provided is a coating method capable of improving the weather resistance of an optical element. The coating method comprises the following steps: a step of pretreating the surface of a light-transmitting member (10) including a lens (11); and a step of forming a water-repellent film (20) on the surface (10a) of the light-transmitting member (10) after the pretreatment. The outermost layer of the light-transmitting member (10) contains silicon oxide. Through the pre-treatment process,the number of hydroxyl groups bonded to the surface (10a) of the light-transmitting member (10) increases. The water-repellent film (20) contains a fluorine-containing organosilicon compound. The polar component of the surface energy of the light-transmitting member (10) after the pretreatment is 35mJ/mm2Above 55mJ/mm2The following.
Description
Technical Field
The invention relates to a coating method, an optical element and a lens assembly.
Background
A camera used outdoors is known as a camera mounted on a vehicle. Such a camera is in an environment where liquid droplets are easily attached to the lens. Therefore, a waterproof coating is sometimes applied to the surface of the lens (for example, patent document 1).
Documents of the prior art
Patent document
Patent document 1: japanese laid-open gazette: japanese laid-open patent publication No. 2008-148276
Disclosure of Invention
Technical problem to be solved by the invention
A lens of a camera used outdoors is required to have not only water resistance but also weather resistance. However, when the lens is merely water-repellent coated, the weather resistance cannot be improved.
The inventors of the present application completed the present invention after repeated careful studies on weather resistance of an optical element including a lens. That is, an object of the present invention is to provide a coating method capable of improving weather resistance of an optical element. Further, an object of the present invention is to provide an optical element having improved weather resistance. Further, it is an object of the present invention to provide a lens assembly with improved weatherability.
Technical scheme for solving technical problem
An exemplary coating method of the present invention includes: a step of performing pretreatment on the surface of a light-transmitting member including a lens; and forming a water-repellent film on the surface of the light-transmitting member after the pretreatment. The outermost layer of the light-transmitting member contains silicon oxide. By the pretreatment, the number of hydroxyl groups bonded to the surface of the light-transmissive member increases. The waterproof film contains a fluorine-containing organosilicon compound. The pretreated light-transmitting member has a polar component of surface energy of 35mJ/mm2Above 55mJ/mm2The following.
An exemplary optical element of the present invention includes a light-transmitting member and a water-repellent film. The light-transmissive member includes a lens. The waterproof film is formed on the surface of the light-transmitting member. The outermost layer of the light-transmitting member contains silicon oxide. The waterproof film contains a fluorine-containing organosilicon compound. The contact angle of the waterproof film after the specific weather resistance test is performed for 1000 hours is 100 ° or more. The specific weather resistance test is a test in which a first test and a second test are alternately performed. The first test is a test in which the optical element is irradiated with ultraviolet light. The unit test time for the first test was 102 minutes. The second test is a test in which the optical element is irradiated with ultraviolet rays while being sprayed with water. The unit test time for the second test was 18 minutes.
The lens assembly exemplified by the present invention includes the above optical element and the holding member. The holding member holds the optical element. The waterproof film of the optical element is exposed to the outside from the holding member.
Effects of the invention
According to the exemplary invention, the weather resistance of the optical element can be improved.
Drawings
Fig. 1 (a) to 1 (c) show a coating method according to an embodiment of the present invention.
FIG. 2 is a cross-sectional view showing a lens assembly according to an embodiment of the present invention.
Fig. 3 is an enlarged cross-sectional view showing a part of a lens assembly according to an embodiment of the present invention.
Fig. 4 is a graph showing the measurement results of example 1 and comparative example 1.
Fig. 5 is a graph showing the measurement results of example 1 and comparative example 1.
Fig. 6 is a graph showing the measurement results of example 2.
Detailed Description
Hereinafter, embodiments of the present invention will be described with reference to the drawings. However, the present invention is not limited to the following embodiments. Note that, for parts overlapping the description, the description may be omitted appropriately. In the drawings, the same or corresponding portions are denoted by the same reference numerals, and description thereof will not be repeated.
First, a coating method according to the present embodiment will be described with reference to fig. 1 (a) to 1 (c). Fig. 1 (a) to 1 (c) are diagrams illustrating a coating method according to the present embodiment. The coating method of the present embodiment includes the steps shown in fig. 1 (a) to 1 (c). Fig. 1 (a) shows a step of preparing the light-transmissive member 10. Fig. 1 (b) shows a pretreatment step. Fig. 1 (c) shows a step of forming the waterproof film 20.
First, as shown in fig. 1 (a), the light-transmissive member 10 is prepared. The light-transmitting member 10 has light-transmitting properties. The light-transmissive member 10 transmits light. The translucent member 10 may be transparent or translucent. The light-transmissive member 10 is used for an outdoor camera such as an in-vehicle camera, for example. The light-transmissive member 10 of the present embodiment includes a lens 11 and a functional coating 12.
The lens 11 may be a glass lens or a plastic lens. The glass lens is made of quartz glass, for example. The material of the plastic lens is, for example, cycloolefin polymer, polymethyl methacrylate, or polycarbonate.
The functional coating 12 is formed on the lens 11. More specifically, the functional coating 12 is formed on an incident surface 11a on which light enters, of the surface of the lens 11. The radius of curvature of the incident surface 11a of the lens 11 is 10mm to 15 mm.
The functional film 12 is not particularly limited as long as the outermost layer contains silicon oxide. The functional coating 12 has a film thickness of 0.001 to 5 μm. The outermost layer of the functional coating 12 constitutes the outermost layer of the light-transmissive member 10. Therefore, the outermost layer of the light-transmissive member 10 contains silicon oxide. Further, by making the outermost layer of the light-transmissive member 10 contain silicon oxide, the hardness of the light-transmissive member 10 increases. Therefore, impact resistance and scratch resistance are imparted to the light-transmissive member 10.
The functional coating 12 imparts impact resistance or antireflection property to the light-transmissive member 10, for example. Alternatively, the functional coating 12 may be a filter that transmits light of a specific wavelength or a filter that reflects light of a specific wavelength. The functional coating 12 can impart a desired function to the light-transmissive member 10.
The functional coating 12 of the present embodiment is an antireflection film. By providing the light-transmissive member 10 with the antireflection film, the light-transmissive property of the light-transmissive member 10 is improved. The antireflection film has a structure in which, for example, a high refractive index layer made of silicon nitride and a low refractive index layer made of silicon oxide are alternately stacked, and the outermost layer is made of the low refractive index layer.
Next, the step of the pretreatment will be described with reference to fig. 1 (b). After the light-transmissive member 10 is prepared, as shown in fig. 1 (b), the front surface 10a of the light-transmissive member 10 is pretreated. In the present embodiment, the surface 10a of the light-transmissive member 10 is the surface 12a of the functional coating 12. The surface 12a of the functional coating 12 faces the incident surface 11a of the lens 11. Therefore, the surface 10a of the light-transmissive member 10 is an incident surface on which light is incident. By pretreating the surface 10a of the light-transmissive member 10, the polar component of the surface energy of the light-transmissive member 10 became 35mJ/mm2Above 55mJ/mm2The following.
The pretreatment is not particularly limited as long as it is a treatment for increasing the number of hydroxyl groups bonded to the surface 10a of the light-transmissive member 10. For example, the pretreatment may be at least one of a high-frequency discharge plasma treatment, an electron beam treatment, a corona treatment, an atmospheric pressure glow discharge plasma treatment, and a flame treatment.
The pretreatment is carried out under conditions such that the polar component of the surface energy of the light-transmitting member 10 after the pretreatment is 35mJ/mm2Above 55mJ/mm2The following conditions are not particularly limited. The polar component of the surface energy can be controlled by adjusting the treatment time of the pretreatment, for example.
In addition, when the pretreatment is a high-frequency discharge plasma treatment, the polarity component of the surface energy can be controlled by selecting the gas type, for example, in addition to the adjustment of the treatment time. The corona treatment and the atmospheric glow discharge plasma treatment can also control the polar component of the surface energy by selecting the gas species. When the pretreatment is an electron beam treatment, the polar component of the surface energy can be controlled by adjusting the irradiation amount of the electron beam, for example. In addition, in the case where the pretreatment is a flame treatment, for example, one of the temperature of the fire (flame), the gas pressure, the distance between the surface 10a of the light-transmissive member 10 and the burner, and the treatment time can be adjusted to control the polar component.
As the pretreatment, by using at least one of the high-frequency discharge plasma treatment, the electron beam treatment, the corona treatment, the atmospheric pressure glow discharge plasma treatment, and the flame treatment, it is possible to easily control the polar component of the surface energy of the light-transmissive member 10 after the pretreatment. As the pretreatment, one of the above-described treatments may be performed, or two or more of the above-described treatments may be combined.
Next, a step of forming the waterproof film 20 will be described with reference to fig. 1 (c). After the pretreatment, as shown in fig. 1 (c), a waterproof film 20 is formed on the surface 10a of the light-transmissive member 10 (the surface 12a of the functional coating 12). As a result, the optical element 1 is completed. The film thickness of the waterproof film 20 is 0.3um or less. The surface 20a of the water-repellent film 20 constitutes an incident surface of the optical element 1.
The material of the waterproof film 20 is not particularly limited as long as it contains a fluorine-containing organosilicon compound. More specifically, the material of the water-repellent film 20 contains a fluorine-containing organosilane compound.
The waterproof film 20 can be formed by, for example, a vacuum evaporation method. Specifically, the fluorine-containing organosilicon compound is evaporated in the vacuum chamber and adheres to the surface 10a of the light-transmissive member 10 (the surface 12a of the functional coating 12). Alternatively, the fluorine-containing organosilicon compound may be dissolved in an organic solvent and applied to the surface 10a of the light-transmissive member 10 (the surface 12a of the functional coating 12) to be adjusted to a predetermined concentration.
Further, it is preferable to use a fluorine-containing organosilicon compound such as a fluorine-containing alkoxysilane as the material of the water-repellent film 20. As a result, hydrolysis and dehydration condensation occur between the hydroxyl groups on the surface 10a of the light-transmissive member 10 (the surface 12a of the functional coating 12) and the fluorinated alkoxysilane, and the water-repellent film 20 is chemically bonded to the surface 10a of the light-transmissive member 10 (the surface 12a of the functional coating 12).
Examples of the fluorine-containing alkoxysilane include CF3(CF2)2C2H4Si(OCH3)3、CF3(CF2)4C2H4Si(OCH3)3、CF3(CF2)6C2H4Si(OCH3)3、CF3(CF2)8C2H4Si(OCH3)3、CF3(CF2)10C2H4Si(OCH3)3、CF3(CF2)12C2H4Si(OCH3)3、CF3(CF2)14C2H4Si(OCH3)3、CF3(CF2)16C2H4Si(OCH3)3、CF3(CF2)18C2H4Si(OCH3)3、CF3(CF2)6C2H4Si(OC2H5)3、CF3(CF2)8C2H4Si(OC2H5)3、CF3(CF2)6C3H6Si(OCH3)3、CF3(CF2)8C3H6Si(OCH3)3、CF3(CF2)6C3H6Si(OC2H5)3、CF3(CF2)8C3H6Si(OC2H5)3、CF3(CF2)6C4H8Si(OCH3)3、CF3(CF2)8C4H8Si(OCH3)3、CF3(CF2)6C4H8Si(OC2H5)3、CF3(CF2)8C4H8Si(OC2H5)3、CF3(CF2)6C2H4Si(CH3)(OCH3)2、CF3(CF2)8C2H4Si(CH3)(OCH3)2、CF3(CF2)6C2H4Si(C2H5)(OC2H5)2And CF3(CF2)8C2H4Si(C2H5)(OC2H5)2. In addition, these fluorine-containing alkoxysilanes do not have an amide group.
As the fluorine-containing alkoxysilane, a fluorine-containing alkoxysilane having an amide group is also suitable. Examples of the fluorine-containing alkoxysilane having an amide group include C9F19CONH(CH2)3Si(OC2H5)3、C9F19CONH(CH2)NH(CH2)Si(OC2H5)3、C9F19CONH(CH2)5CONH(CH2)Si(OC2H5)3、C8F17SO2NH(CH2)5CONH(CH2)Si(OC2H5)3、C3F7O(CF(CF3)CF2O)2-CF(CF3)-CONH(CH2)Si(OC2H5)3And C3F7O(CF(CF3)CF2O)m’-CF(CF3)-CONH(CH2)Si(OCH3)3(here, "m'" is an integer of 1 or more).
As the fluorine-containing alkoxysilane, an alkoxysilane having an Rf' group is also suitable. Examples of the alkoxysilane having an Rf 'group include Rf' (CH)2)2Si(OCH3)3、Rf’CONH(CH2)3Si(OC2H5)3、Rf’CONH(CH2)2NH(CH2)3Si(OC2H5)3、Rf’SO2N(CH3)(CH2)2CONH(CH2)3Si(OC2H5)3、Rf’(CH2)2OCO(CH2)2S(CH2)3Si(OCH3)3、Rf’(CH2)2OCONH(CH2)2Si(OC2H5)3、Rf’COO-Cy(OH)-(CH2)2Si(OCH3)3、Rf’(CH2)2NH(CH2)2Si(OCH3)3And Rf' (CH)2)2NH(CH2)2NH(CH2)2Si(OCH2CH2OCH3)3. In each of the above formulae, Cy is a cyclohexane residue, and Rf' is a polyfluoroalkyl group having 4 to 16 carbon atoms.
Preferably, the material of the water-repellent film 20 is a fluorine-containing organosilicon compound such as a fluorine-containing organochlorosilane. As a result, hydrolysis and dehydration condensation occur between the hydroxyl groups on the surface 10a of the light-transmissive member 10 (the surface 12a of the functional coating 12) and the fluorine-containing organochlorosilane, and the water-repellent film 20 is chemically bonded to the surface 10a of the light-transmissive member 10 (the surface 12a of the functional coating 12).
Examples of the fluorine-containing organochlorosilane include CF3(CF2)6C2H4SiCl3、CF3(CF2)8C2H4SiCl3、CF3(CF2)6C3H6SiCl3、CF3(CF2)8C3H6SiCl3、CF3(CF2)6C2H4Si(CH3)Cl2And CF3(CF2)8C2H4Si(CH3)Cl2. In addition, these fluorine-containing organochlorosilanes do not have amide groups.
As the fluorine-containing organochlorosilane, a fluorine-containing organochlorosilane having an amide group is also suitable. Examples of the fluorine-containing organochlorosilane having an amide group include C9F19CONH(CH2)3SiCl3And C9F19CONH(CH2)3Si(CH3)Cl2。
As the fluorine-containing organochlorosilane, organochlorosilane having an Rf' group is also suitable. Examples of the organochlorosilane having an Rf 'group include Rf' (CH)2)2SiCl3、Rf'(CH2)2Si(CH3)Cl2And (Rf' CH)2CH2)2SiCl2. In the above formulae, Rf' is a polyfluoroalkyl group having 4 to 16 carbon atoms.
Further, as a material of the waterproof film 20, a fluorine-containing organosilicon compound represented by the following chemical formula (1) can be used.
[ chemical formula 1]
In the formula (1), Rf 1Represents a perfluoroalkyl group. X represents bromine, iodine, hydrogen or methoxy. Y represents hydrogen or lower alkyl, and Z represents fluorine or trifluoromethyl. R1Represents a group capable of being hydrolyzed, R2Represents hydrogen or a monovalent hydrocarbon group. R2The monovalent hydrocarbon group shown is, for example, a group that is not hydrolyzed by water. a. b, c, d, e are each independently an integer of 0 or 1 or more and a + b + c + d + e is 1 or more, and the arrangement order of the repeating units enclosed by a, b, c, d, e is not limited in the chemical formula. f is 0, 1 or 2. g is 1, 2 or 3. h is an integer of 1 or more.
As a material of the waterproof film 20, a silane compound containing a perfluoro (poly) ethyl ether group represented by the following chemical formula (2) can be used.
Rf-PFPE-X-SiRa kRb lRc m…(2)
In formula (2), PFPE, independently at each occurrence, is represented by formula (la): - (OC)6F12)a-(OC5F10)b-(OC4F8)c-(OC3F6)d-(OC2F4)e-(OCF2)f-a radical of formula (I). Here, a, b, c, d, e, and f are each independently an integer of 0 to 200 inclusive, and a + b + c + d + e + f is 1 or more. The order of arrangement of the repeating units enclosed by a, b, c, d, e, and f is not limited in the chemical formula.
In the chemical formula (2), Rf is independent at each occurrence and represents an alkyl group having 1 to 16 carbon atoms which can be substituted with one or more fluorine atoms.
In the chemical formula (2), X is independent at each occurrence and represents a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms.
In the chemical formula (2), RaIndependently at each occurrence, represents-Z-SiRl pR2 qR3 r. Here, Z represents an oxygen atom or a divalent organic group independently at each occurrence. RlAt each occurrenceAre independently of each other and represent Ra’。Ra' and RaSynonymously. At RaWherein at most 5 Si are bonded in a straight chain via a Z group. In addition, in RaIn, R2Each occurrence independently represents a hydroxyl group or a hydrolyzable group. R3Each occurrence independently represents a hydrogen atom or a lower alkyl group. In addition, in RaWherein p is independently at each occurrence an integer of 0, 1, 2 or 3. q is independently at each occurrence an integer of 0, 1, 2 or 3. r is independently at each occurrence an integer of 0, 1, 2 or 3. However, at each-Z-SiRl pR2 qR3 rWherein p + q + R is 3, two or more groups having at least one R are present2Of (a) is (b).
In the chemical formula (2), RbEach occurrence independently represents a hydroxyl group or a hydrolyzable group. RcEach occurrence independently represents a hydrogen atom or a lower alkyl group.
In equation (2), k is independently at each occurrence an integer of 1, 2 or 3. l is independently at each occurrence an integer of 0, 1 or 2. m is independently at each occurrence an integer of 0, 1 or 2. However, at each-SiRa kRb lRc mIn the formula, k + l + m is 3.
The hydrolyzable group is-OR, -OCOR, -O-N ═ C (R)2、-N(R)2-NHR or a halogen atom. Wherein R represents an alkyl group having 1 to 4 carbon atoms, which may be substituted or unsubstituted. Further, the lower alkyl group is an alkyl group having 1 to 4 carbon atoms.
The coating method of the present embodiment is explained above. According to the present embodiment, the number of hydroxyl groups in the surface 10a of the light-transmissive member 10 is increased by the pretreatment described with reference to fig. 1 (b), and the chemical bonding strength between the surface 10a of the light-transmissive member 10 and the waterproof film 20 is increased. As a result, the adhesiveness (adhesiveness) between the surface 10a of the light-transmitting member 10 and the waterproof film 20 is improved, and the weather resistance of the optical element 1 is improved. In particular, according to this embodiment, light is transmitted by pretreatmentThe polar component of the surface energy of the structural member 10 was set to 35mJ/mm2Above 55mJ/mm2The following. Therefore, the number of hydroxyl groups can be increased to such an extent that the weather resistance of the optical element 1 is improved.
The translucent member 10 of the present embodiment is used for an in-vehicle camera. Therefore, the weather resistance of the light-transmitting member used for the in-vehicle camera is improved.
In the present embodiment, the radius of curvature of the incident surface 11a of the lens 11 is 10mm to 15 mm. In other words, the curvature radius of the surface of the light-transmitting member 10 on which the waterproof film 20 is formed (the incident surface of the light-transmitting member 10) is 10mm to 15 mm. Therefore, the optical characteristics required for the light-transmitting member used in the in-vehicle camera can be satisfied.
Further, the larger the curvature radius of the surface to be pretreated is, the more uniform the pretreatment can be performed on the entire surface of the pretreatment object, and the smaller the curvature radius of the surface to be pretreated is, the more difficult it is to uniformly perform the pretreatment on the entire surface of the pretreatment object. In the present embodiment, since the radius of curvature of the incident surface of the light-transmissive member 10 is 10mm or more and 15mm or less, the pretreatment can be performed more uniformly over the entire surface 10a of the light-transmissive member 10. As a result, the adhesion between the surface 10a of the light-transmissive member 10 and the waterproof film 20 is improved over the entire surface 10a of the light-transmissive member 10, and the weather resistance is further improved.
Next, the optical element 1 will be described with reference to fig. 1 (c). As shown in fig. 1 (c), the optical element 1 includes a light-transmissive member 10 and a waterproof film 20. The waterproof film 20 is formed on the surface 10a of the translucent member 10. In the present embodiment, the light-transmissive member 10 includes a lens 11 and a functional coating 12 formed on the lens 11. The outermost layer of the light-transmitting member 10 contains silicon oxide, and the water-repellent film 20 contains a fluorine-containing organosilicon compound. The surface 12a of the functional coating 12 (the surface 10a of the light-transmissive member 10) is pretreated. The optical element 1 is used for an outdoor camera such as a vehicle-mounted camera.
In the optical element 1, the contact angle of the water-repellent film 20 after the specific weather resistance test for 1000 hours wasAbove 100 deg. Therefore, the optical element 1 has weather resistance. The reason why the contact angle of the waterproof film 20 after the specific weather resistance test for 1000 hours is 100 ° or more is that: by the pretreatment, the polar component of the surface energy of the light-transmissive member 10 was changed to 35mJ/mm2Above 55mJ/mm2Hereinafter, the chemical bonding strength between the surface 10a of the light-transmissive member 10 and the waterproof film 20 is increased. Further, it is preferable that the difference between the contact angle before the specific weather resistance test and the contact angle after the specific weather resistance test is less than 10 °.
The specific weather resistance test is a test in which the first test and the second test are alternately performed. The first test is a test in which the optical element 1 is irradiated with ultraviolet light, and the unit test time of the first test is 102 minutes. The second test is a test in which the optical element 2 is sprayed with water while being irradiated with ultraviolet rays, and the unit test time of the second test is 18 minutes.
In detail, the weather resistance test is a test based on "Japanese Industrial Standard (JIS) K5600-7-7" or "ISO 16474-2". In the first test and the second test, the optical element 1 was irradiated with ultraviolet rays using a 7.5kW xenon lamp. More specifically, the water-repellent film 20 of the optical element 1 is irradiated with ultraviolet rays. The test surface radiation illuminance is 60W/m2Above and 180W/m2The following. In a second test a water spray was used. More specifically, water mist is sprayed from the water sprayer to the water-repellent film 20 of the optical element 1. The spray volume was 720 ml/min. The temperature of the test chamber is 50 ℃ to 95 ℃. The humidity of the test chamber is 50% RH or more and 60% RH or less. In addition, the humidity of the second test was dependent on the conditions of use of the water sprayer.
The optical element 1 of the present embodiment is explained above. According to the present embodiment, the weather resistance of the optical element 1 is improved. Further, a desired function can be imparted to the optical element 1 by the functional coating 12.
The optical element 1 of the present embodiment is used for an in-vehicle camera. Therefore, the weather resistance of the optical element used for the in-vehicle camera can be improved.
In the present embodiment, the radius of curvature of the surface 10a of the light-transmissive member 10 is 10mm or more and 15mm or less. Therefore, optical characteristics required for an optical element used in the in-vehicle camera can be satisfied. In addition, the adhesion between the surface 10a of the light-transmissive member 10 and the waterproof film 20 is improved over the entire surface 10a of the light-transmissive member 10, and the weather resistance is further improved.
Next, the lens unit 100 according to the present embodiment will be described with reference to fig. 2 and 3. Fig. 2 is a sectional view showing the lens assembly 100 of the present embodiment. The lens assembly 100 of the present embodiment is used for an in-vehicle camera.
As shown in fig. 2, the lens assembly 100 includes first to fifth optical elements 1 to 5 and a holding member 6. The holding member 6 holds the first to fifth optical elements 1 to 5. More specifically, the holding member 6 has a cylindrical shape and houses the first to fifth optical elements 1 to 5.
The first optical element 1 is the optical element 1 described with reference to fig. 1 (a) to 1 (c), and includes a water-repellent film 20. The second to fifth optical elements 2 to 5 are glass lenses or plastic lenses. The first to fifth optical elements 1 to 5 are arranged along the optical axis OA, and the water-repellent film 20 of the first optical member 1 is exposed to the outside from the holding member 6. Therefore, according to the present embodiment, the weather resistance of the optical element exposed to the outside from the holding member 6 is improved. As a result, the lens assembly 100 has improved weather resistance.
Next, the lens assembly 100 according to the present embodiment will be further described with reference to fig. 3. Fig. 3 is an enlarged cross-sectional view showing a part of the lens assembly 100 according to the present embodiment. In detail, fig. 3 shows a portion a shown in fig. 2 in an enlarged manner.
As shown in fig. 3, the holding member 6 covers an edge portion (end portion) of the waterproof film 20. More specifically, the holding member 6 has a projection 61. The protruding part 61 is riveted during the manufacturing process of the lens assembly 100. Specifically, after the first to fifth optical elements 1 to 5 are housed in the holding member 6, the protruding portion 61 is bent inward. As a result, the protrusion 61 protrudes toward the optical axis OA (see fig. 2), and the first to fifth optical elements 1 to 5 are held in the holding member 6. The edge of the incident surface of the optical element 1 is covered by caulking the protrusion 61. In other words, the protrusion 61 covers the edge of the waterproof film 20. As a result, the edge portion of the waterproof film 20 is not exposed to the outside, and peeling of the waterproof film 20 from the edge portion can be suppressed.
Hereinafter, embodiments of the present invention will be described with reference to the drawings. However, the present invention is not limited to the above embodiment, and can be implemented in various forms without departing from the spirit thereof. Further, a plurality of constituent elements disclosed in the above embodiments can be changed as appropriate.
In addition, in order to facilitate understanding of the present invention, the main body of each component is schematically illustrated in the drawings, and for convenience of drawing, the thickness, length, number, interval, and the like of each component illustrated in the drawings may be different from the actual ones. It is needless to say that the configuration of each component shown in the above embodiments is an example, and is not particularly limited, and various changes can be made without substantially departing from the effect of the present invention.
For example, the functional coating 12 may be formed on at least the incident surface 11a of the lens 11, or may be further formed on a surface other than the incident surface 11a of the lens 11. Similarly, the waterproof film 20 may be formed at least on the incident surface (the surface 10a) of the light-transmissive member 10, or may be further formed on a surface other than the incident surface of the light-transmissive member 10.
In addition, the functional coating 12 may be omitted. In the above case, the waterproof film 20 is formed at least on the incident surface 11a of the lens 11. In the case where the functional coating 12 is omitted, a material containing silicon oxide such as quartz glass is used as the material of the lens 11.
The radius of curvature of the incident surface 11a of the lens 11 is not limited to 10mm to 15 mm. The radius of curvature of the incident surface 11a of the lens 11 may be any value according to the specification of the device in which the optical element 1 (translucent member 10) is incorporated.
Further, the light-transmissive member 10, the optical element 1, and the lens assembly 100 may also be used in a camera for indoor use.
Examples
The present invention will be described more specifically below with reference to examples. The present invention is not limited to the examples.
[ example 1]An antireflection film (composition: SiO) was coated2、Ta2O5、TiO2) The optical glass lens of (1). The antireflection film was subjected to atmospheric glow discharge plasma treatment (pretreatment) using an atmospheric pressure plasma apparatus. The gas species is air.
After the pretreatment, a water-repellent film was formed on the antireflection film by a vacuum evaporation method to produce an optical element.
Comparative example 1 an optical element was produced by the same procedure as in example 1, except that no pretreatment was performed.
The surface energy of the antireflection film after the pretreatment was measured (example 1). The measurement is performed before the waterproof film is formed. Also, the surface energy of the antireflection film of comparative example 1 was measured. The surface energy measurement was carried out based on the Owens-Wendt method. Specifically, a test liquid of known surface energy was dropped to measure the contact angle, and the polar component of the surface energy was calculated according to a calculation formula based on Owens-Wendt analysis. Pure water and diiodomethane were used as the test liquid. The measurement results are shown in fig. 4.
Fig. 4 is a graph showing the measurement results of example 1 and comparative example 1. Specifically, fig. 4 shows the polar components of the surface energy of the antireflection film of example 1 and the polar components of the surface energy of the antireflection film of comparative example 1.
In fig. 4, the vertical axis represents the polar component of the surface energy. As shown in FIG. 4, the polar component of example 1 was 47.50mJ/mm2. Thus, the polar component of example 1 was 35mJ/mm2Above 55mJ/mm2Values within the following ranges. On the other hand, the polar component of comparative example 1 was 28.19mJ/mm2. Thus, the polar component of comparative example 1 was 35mJ/mm2Above 55mJ/mm2Values outside the following ranges.
[ weather resistance test]The optical elements of example 1 and comparative example 1 were subjected toAnd (4) weather resistance test. Further, after the weather resistance test, the contact angle of the waterproof film was measured. The weather resistance test was carried out using an "accelerated weather resistance tester (Japanese: スーパーキセノンウェザーメーター) (model: SX 75)" manufactured by SuGA tester (Japanese: スガ (N.K.) test), the test period was 120 minutes (water mist was sprayed for 18 minutes during irradiation of ultraviolet light for 120 minutes), and the illuminance was 180W/m2. The blackboard temperature was 65 °. The results of the contact angle measurements are shown in fig. 5.
Fig. 5 is a graph showing the measurement results of example 1 and comparative example 1. Specifically, fig. 5 shows a contact angle before the start of the weather resistance test, a contact angle after 200 hours from the start of the weather resistance test, a contact angle after 400 hours from the start of the weather resistance test, a contact angle after 600 hours from the start of the weather resistance test, and a contact angle after 1000 hours from the start of the weather resistance test.
In fig. 5, the vertical axis represents the contact angle, and the horizontal axis represents the test time of the weather resistance test. In addition, black circle marks represent the measurement results of the contact angle of example 1, and black triangle marks represent the measurement results of the contact angle of comparative example 1.
As shown in fig. 5, in example 1, the contact angle before the start of the weather resistance test and the contact angle after 1000 hours from the start of the weather resistance test were substantially the same value. The contact angle after 1000 hours from the start of the weather resistance test was 100 ° or more (more specifically, 110 ° or more). In contrast, in comparative example 1, the contact angle was smaller as the test time of the weather resistance test was increased. Further, the contact angle after 600 hours from the start of the weather resistance test was less than 100 °.
[ example 2]An antireflection film (composition: SiO) was coated2、Ta2O5、TiO2) The optical glass lens of (1). The antireflection film is subjected to flame treatment (pretreatment). Thereafter, the polar component of the surface energy of the antireflection film was measured. Flame treatment was carried out using a gas torch (flame temperature: 1000 ℃ C.). Anti-reflection film and gasThe distance between the welding torches is 10mm or less.
Fig. 6 shows the measurement results of the polar component in example 2. Fig. 6 is a graph showing the measurement results of experimental example 2. Specifically, fig. 6 shows the polar components of the surface energy of the antireflection film of example 2.
In fig. 6, the vertical axis represents the polar component of the surface energy. As shown in FIG. 6, the polar component of example 2 was 46.06mJ/mm2. Thus, the polar component of example 2 was 35mJ/mm2Above 55mJ/mm2Values within the following ranges.
Examples 3 to 7 and comparative examples 2 to 4]Optical elements of examples 3 to 7 and comparative examples 2 to 4 were produced by the same procedure as in example 1. As shown in Table 1, examples 3 to 7 and comparative examples 2 to 4 differ in polar component. Specifically, the optical devices of examples 3 to 7 and comparative examples 2 to 4 were produced while changing the treatment time of the pretreatment. In addition, even if the pretreatment time is prolonged by 2 minutes or more, the polar component does not reach 55mJ/mm2The above.
The polar components of the antireflection films of examples 3 to 7 and comparative examples 2 to 4 were measured. The measurement of the polar component is performed after the pretreatment and before the formation of the water-repellent film. The measurement results are shown in table 1.
In addition, the optical elements of examples 3 to 7 and comparative examples 2 to 4 were evaluated for weather resistance, abrasion resistance, chemical resistance and heat resistance. The results are shown in table 1.
[ Table 1]
[ evaluation of weather resistance]The weather resistance was evaluated based on the difference between the contact angle before the weather resistance test (initial contact angle) and the contact angle after the weather resistance test (post-test contact angle). Specifically, it is determined whether or not the contact angle after the test has changed by 10 ° or more from the initial contact angle. The weather resistance test was performed for 1000 hours. In table 1, the "∘" mark means that the contact angle did not change by 10 ° or more from the initial contact angle after the test. "×" markNote that the contact angle after the test changed by 10 ° or more from the initial contact angle. As shown in Table 1, the polar component was 35mJ/mm2In the above case, the weather resistance is good.
[ abrasion resistance]Wear tests were performed using a wear gauge. Specifically, the water-repellent film of the optical element was abraded 1000 times by a car wash brush. In the abrasion operation, a load of 1kg was applied to the waterproof film 1 from the car wash brush. In the same manner as the evaluation of weather resistance, it was judged whether or not the contact angle after the test changed by 10 ° or more from the initial contact angle. In table 1, the "∘" mark means that the contact angle did not change by 10 ° or more from the initial contact angle after the test. The "×" mark indicates that the contact angle after the test changed by 10 ° or more from the initial contact angle. As shown in Table 1, the polar component was 30mJ/mm2In the above case, the wear resistance is good.
[ drug resistance]The optical element was immersed in 0.1N dilute sulfuric acid for 8 hours. In the same manner as the evaluation of weather resistance, it was judged whether or not the contact angle after the test changed by 10 ° or more from the initial contact angle. In table 1, the "∘" mark means that the contact angle did not change by 10 ° or more from the initial contact angle after the test. The "×" mark indicates that the contact angle after the test changed by 10 ° or more from the initial contact angle. As shown in Table 1, the polar component was 25mJ/mm2In the above case, the drug resistance is good.
[ Heat resistance]The heat resistance test was performed using a heating apparatus (WFO-520) manufactured by Tokyo Rickett instruments, Inc. (Japan: imperial Jing instruments Co., Ltd.). Specifically, the optical element was placed in a test chamber, and the temperature in the test chamber was set to 105 ℃. The heat resistance test was performed for 1000 hours. In the same manner as the evaluation of weather resistance, it was judged whether or not the contact angle after the test changed by 10 ° or more from the initial contact angle. In table 1, the "∘" mark means that the contact angle did not change by 10 ° or more from the initial contact angle after the test. The "×" mark indicates that the contact angle after the test changed by 10 ° or more from the initial contact angle. As shown in Table 1, the polar component was 35mJ/mm2In the above case, the heat resistance is good.
[ comprehensive evaluation]The comprehensive evaluation is shown in table 1. In the comprehensive evaluation, ". smallcircle" mark means resistanceAll the results of evaluation of the weatherability, abrasion resistance, chemical resistance and heat resistance were "O". The "x" mark indicates an optical element in which some of the evaluation results of weather resistance, abrasion resistance, chemical resistance, and heat resistance are "x". As shown in Table 1, the polar component was 35mJ/mm2Above 55mJ/mm2In the following cases, the overall evaluation was good.
The present invention is preferably used for a coating method, an optical element, and a lens assembly, for example. The optical element and lens assembly of the present invention are ideal for outdoor use. For example, the optical element and the optical module of the present invention can be preferably used as an in-vehicle monitor for monitoring the surroundings of a vehicle.
(symbol description)
1 an optical element; 6 a holding member; 10a light-transmissive member; 11a lens; 12 functional film coating; 20a waterproof membrane; a 100 lens assembly.
Claims (13)
1. A method of coating, comprising:
a step of performing pretreatment on the surface of a light-transmitting member including a lens; and
a step of forming a water-repellent film on the surface of the light-transmitting member after the pretreatment,
the outermost layer of the light-transmissive member contains silicon oxide,
the number of hydroxyl groups bonded to the surface of the light-transmissive member is increased by the pretreatment,
the waterproof film contains a fluorine-containing organosilicon compound,
the pretreated light-transmitting member has a polar component of surface energy of 35mJ/mm2Above 55mJ/mm2The following.
2. The coating method according to claim 1,
the light-transmissive member further includes a functional coating film formed on the lens.
3. The coating method according to claim 1 or 2,
the pretreatment is at least one of a high-frequency discharge plasma treatment, an electron beam treatment, a corona treatment, an atmospheric pressure glow discharge plasma treatment, and a flame treatment.
4. The coating method according to any one of claims 1 to 3,
the light-transmitting member is used for an in-vehicle camera.
5. The coating method according to claim 4,
the curvature radius of the surface of the light-transmitting member on which the waterproof film is formed is 10mm to 15 mm.
6. An optical element, comprising:
a light-transmissive member including a lens; and
a waterproof film formed on a surface of the light-transmitting member,
the outermost layer of the light-transmissive member contains silicon oxide,
the waterproof film contains a fluorine-containing organosilicon compound,
the contact angle of the waterproof film after the specific weather resistance test is performed for 1000 hours is 100 DEG or more,
the specific weather resistance test is a test in which a first test and a second test are alternately performed,
the first test is a test in which the optical element is irradiated with ultraviolet rays,
the unit test time for the first test was 102 minutes,
the second test is a test in which the optical element is irradiated with ultraviolet rays while being sprayed with water,
the unit test time for the second test was 18 minutes.
7. The optical element of claim 6,
the difference between the contact angle before the specific weather resistance test and the contact angle after the specific weather resistance test is less than 10 °.
8. The optical element according to claim 6 or 7,
the light-transmissive member further includes a functional coating film formed on the lens.
9. The optical element according to any one of claims 6 to 8,
the optical element is used for a vehicle-mounted camera.
10. The optical element of claim 9,
the curvature radius of the surface of the light-transmitting member on which the waterproof film is formed is 10mm to 15 mm.
11. A lens assembly, comprising:
the optical element of any one of claims 6 to 10; and
a holding member that holds the optical element, the waterproof film of the optical element being exposed to the outside from the holding member.
12. The lens assembly of claim 11,
the holding member covers an edge portion of the waterproof film.
13. The lens assembly of claim 12,
the holding member has a protruding portion that holds the first optical element, and the protruding portion covers an edge portion of the waterproof film.
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| JP2018-144166 | 2018-07-31 | ||
| JP2018144166A JP2021177200A (en) | 2018-07-31 | 2018-07-31 | Coating method, optical component and lens assembly |
| PCT/JP2019/029622 WO2020027037A1 (en) | 2018-07-31 | 2019-07-29 | Coating method, optical component, and lens assembly |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115210067A (en) * | 2020-03-04 | 2022-10-18 | 迪睿合株式会社 | Optical laminate, article, and method for producing optical laminate |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP7089610B2 (en) * | 2020-03-04 | 2022-06-22 | デクセリアルズ株式会社 | Manufacturing method of optical laminate |
| JP7089609B2 (en) * | 2020-03-04 | 2022-06-22 | デクセリアルズ株式会社 | Manufacturing method of optical laminate, article, optical laminate |
| EP4116086A4 (en) * | 2020-03-04 | 2024-06-19 | Dexerials Corporation | Method for manufacturing optical laminate |
| JP7101297B2 (en) * | 2020-07-17 | 2022-07-14 | デクセリアルズ株式会社 | Manufacturing method of optical laminate, article, optical laminate |
| JP7248830B2 (en) * | 2020-07-17 | 2023-03-29 | デクセリアルズ株式会社 | Method for manufacturing optical laminate |
| CN115803190A (en) * | 2020-07-17 | 2023-03-14 | 迪睿合株式会社 | Optical laminate, article, and method for producing optical laminate |
| JP7303954B2 (en) * | 2020-07-17 | 2023-07-05 | デクセリアルズ株式会社 | Method for manufacturing optical laminate |
| EP4183573A1 (en) * | 2020-07-17 | 2023-05-24 | Dexerials Corporation | Method for producing optical multilayer body |
| KR20230008883A (en) * | 2020-09-10 | 2023-01-16 | 데쿠세리아루즈 가부시키가이샤 | Manufacturing method of optical laminate |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000147208A (en) * | 1998-11-12 | 2000-05-26 | Tomoegawa Paper Co Ltd | Antireflection material and polarizing film using same |
| JP2000171603A (en) * | 1998-12-04 | 2000-06-23 | Tomoegawa Paper Co Ltd | Antireflection material and polarizing film using the same |
| JP2000187102A (en) * | 1998-10-14 | 2000-07-04 | Tomoegawa Paper Co Ltd | Antireflection material and polarizing film using the same |
| JP2000308846A (en) * | 1999-04-26 | 2000-11-07 | Toppan Printing Co Ltd | Method for formation of antifouling layer |
| JP2001089625A (en) * | 1999-09-24 | 2001-04-03 | Jsr Corp | Curable resin composition and resin cured product |
| JP2005301208A (en) * | 2004-03-17 | 2005-10-27 | Seiko Epson Corp | Method for manufacturing stain proof optical article |
| JP2006309139A (en) * | 2005-03-29 | 2006-11-09 | Seiko Epson Corp | Manufacturing method of stain-proof optical article |
| EP1914210A1 (en) * | 2005-08-08 | 2008-04-23 | Nippon Sheet Glass Company Limited | Water-repellent coating clad article and process for producing the same |
| CN101362815A (en) * | 2008-09-18 | 2009-02-11 | 大连振邦氟涂料股份有限公司 | Hybrid polyurethane-polyacrylacid ester dispersion containing fluorine and/or siloxane and preparation method thereof |
| CN101454411A (en) * | 2006-03-27 | 2009-06-10 | 埃西勒国际通用光学公司 | Edging process of lens using transparent coating layer for protecting lens |
| JP2015040945A (en) * | 2013-08-21 | 2015-03-02 | コニカミノルタ株式会社 | Lens unit for on-vehicle camera |
| CN104977633A (en) * | 2014-04-08 | 2015-10-14 | 株式会社巴川制纸所 | Protective film, film layered product and polarizer |
| JP2015200884A (en) * | 2014-04-02 | 2015-11-12 | ダイキン工業株式会社 | surface treatment method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008062460A (en) * | 2006-09-06 | 2008-03-21 | Konica Minolta Holdings Inc | Optical film and image display element using it |
-
2018
- 2018-07-31 JP JP2018144166A patent/JP2021177200A/en active Pending
-
2019
- 2019-07-29 WO PCT/JP2019/029622 patent/WO2020027037A1/en active Application Filing
- 2019-07-29 CN CN201980050301.6A patent/CN112513682A/en active Pending
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000187102A (en) * | 1998-10-14 | 2000-07-04 | Tomoegawa Paper Co Ltd | Antireflection material and polarizing film using the same |
| JP2000147208A (en) * | 1998-11-12 | 2000-05-26 | Tomoegawa Paper Co Ltd | Antireflection material and polarizing film using same |
| JP2000171603A (en) * | 1998-12-04 | 2000-06-23 | Tomoegawa Paper Co Ltd | Antireflection material and polarizing film using the same |
| JP2000308846A (en) * | 1999-04-26 | 2000-11-07 | Toppan Printing Co Ltd | Method for formation of antifouling layer |
| JP2001089625A (en) * | 1999-09-24 | 2001-04-03 | Jsr Corp | Curable resin composition and resin cured product |
| JP2005301208A (en) * | 2004-03-17 | 2005-10-27 | Seiko Epson Corp | Method for manufacturing stain proof optical article |
| JP2006309139A (en) * | 2005-03-29 | 2006-11-09 | Seiko Epson Corp | Manufacturing method of stain-proof optical article |
| EP1914210A1 (en) * | 2005-08-08 | 2008-04-23 | Nippon Sheet Glass Company Limited | Water-repellent coating clad article and process for producing the same |
| CN101454411A (en) * | 2006-03-27 | 2009-06-10 | 埃西勒国际通用光学公司 | Edging process of lens using transparent coating layer for protecting lens |
| CN101362815A (en) * | 2008-09-18 | 2009-02-11 | 大连振邦氟涂料股份有限公司 | Hybrid polyurethane-polyacrylacid ester dispersion containing fluorine and/or siloxane and preparation method thereof |
| JP2015040945A (en) * | 2013-08-21 | 2015-03-02 | コニカミノルタ株式会社 | Lens unit for on-vehicle camera |
| JP2015200884A (en) * | 2014-04-02 | 2015-11-12 | ダイキン工業株式会社 | surface treatment method |
| CN104977633A (en) * | 2014-04-08 | 2015-10-14 | 株式会社巴川制纸所 | Protective film, film layered product and polarizer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115210067A (en) * | 2020-03-04 | 2022-10-18 | 迪睿合株式会社 | Optical laminate, article, and method for producing optical laminate |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2020027037A1 (en) | 2020-02-06 |
| JP2021177200A (en) | 2021-11-11 |
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