CN110196465B - Silver-plated mirror and preparation method thereof - Google Patents
Silver-plated mirror and preparation method thereof Download PDFInfo
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- CN110196465B CN110196465B CN201910514455.8A CN201910514455A CN110196465B CN 110196465 B CN110196465 B CN 110196465B CN 201910514455 A CN201910514455 A CN 201910514455A CN 110196465 B CN110196465 B CN 110196465B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1689—After-treatment
- C23C18/1692—Heat-treatment
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
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- 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
- G02B1/11—Anti-reflection coatings
- G02B1/118—Anti-reflection coatings having sub-optical wavelength surface structures designed to provide an enhanced transmittance, e.g. moth-eye structures
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/08—Mirrors
- G02B5/0808—Mirrors having a single reflecting layer
Abstract
The invention discloses a silver-plated mirror and a preparation method thereof, and the silver-plated mirror comprises a transparent substrate photochromic substrate, wherein a nano anti-reflection layer is formed on the upper surface of the transparent substrate photochromic substrate by etching, a silver mirror layer is formed on the lower surface of the transparent substrate photochromic substrate by chemical silver plating, and a paint layer is coated on the silver mirror layer; when the silver-plated mirror prepared by the invention is used under strong light, the light incidence amount and the light reflection amount of the silver mirror layer are reduced, and the phenomena of dazzling and dazzling are prevented; when the mirror is used under dark light, the optical effect of the mirror is similar to that of a common mirror, Fresnel reflection is obviously reduced, the visual angle of the mirror surface is wider, and reflection shadow is prevented from being generated to influence the optical performance. The preparation steps of the nanometer anti-reflection layer can not only prevent Fresnel reflection, but also properly coarsen the lower surface of the base material before secondary silver plating, improve the adhesion of the silver mirror layer on the lower surface and prevent the stripping phenomenon of the silver plating layer.
Description
Technical Field
The invention relates to the technical field of silver mirror preparation, in particular to a silver-plated mirror and a preparation method thereof.
Background
The fresnel reflection on the surface of an object often causes the photoelectric performance of the device to be reduced, the reflectivity of each air-glass interface is nearly 4% in an optical system, and the generated ghost image causes the image contrast to be reduced, and even causes the safety problem in an automobile instrument panel. Therefore, the development of a surface antireflection structure with large angle and broadband characteristics is more significant, and the surface reflection can be effectively reduced by forming an irregular nano concave-convex structure with the characteristic size of less than 200nm on the surface of an object, which is equivalent to a graded refractive index interface.
The method for etching on a substrate by using nano metal particles (silver, gold, nickel and the like) as a mask combines the naturalness of a bottom-up method and the controllability of a top-down method, is a method for effectively preparing a nano anti-reflection structure.
The photochromic phenomenon means that a certain compound A undergoes a specific chemical reaction when being irradiated by light with certain wavelength and intensity to obtain another product B, and the absorption spectrum of the product B is obviously changed (the color of the product B is changed) due to the difference of the structure of the product B. And under the irradiation of light with another wavelength or under the action of heat, the product B can be restored to the form of the compound A. Such compounds, which undergo a reversible colour change under the action of light, are known as photochromic materials.
The photochromic material can be classified into an inorganic photochromic material and an organic photochromic material according to the properties of the material. The photochromic substance can be divided into a film-layer photochromic substrate and a substrate photochromic substrate according to the distribution type of the photochromic substance. The film layer discoloring base material is formed by wrapping a film layer containing photochromic particles on the surface of a substrate with excellent mechanical property, the film layer discoloring base material has excellent mechanical property and excellent discoloring property, but the discoloring film layer is abraded to a certain degree in daily use, so that the base material has low durability in outdoor production activities. The substrate discoloration base material is prepared by uniformly dispersing spiropyran discoloration particles into a monomer for polymerization. The shock resistance and the fast fading characteristic of the base material are considered in the proportioning design process of the base material with color change.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: aiming at the problems that the lower surface of a silver-plated mirror surface is easy to generate Fresnel reflection to cause narrow visual field and generate reflection shadow and the defects that the mirror surface reflection light is dazzling and dazzling under strong light, the invention provides the silver-plated mirror and the preparation method thereof.
In order to solve the technical problems, the invention provides the following technical scheme:
a silver-plated mirror comprises a transparent substrate photochromic substrate, wherein a nano anti-reflection layer is formed on the upper surface of the transparent substrate photochromic substrate through etching, a silver mirror layer is formed on the lower surface of the transparent substrate photochromic substrate through chemical silver plating, and a paint layer is coated on the silver mirror layer;
the thickness of the transparent substrate photochromic base material is more than or equal to 1mm, the etching depth of the nano anti-reflection layer is 97-186 nm, the thickness of the silver mirror layer is 21-94 mu m, and the thickness of the paint layer is 113-459 mu m.
Preferably, the transparent substrate photochromic substrate is a transparent substrate photochromic organic material or a transparent substrate photochromic glass.
Preferably, the photochromic organic material of the transparent substrate is an optical resin polymer in which spiropyran photochromic particles or diarylethene photochromic compounds are dispersed; the photochromic glass is high borosilicate glass with a silver halide color-changing system in solid solution.
Preferably, the diarylethene-based photochromic compound is 1, 2-bis (2-methyl-5- (4-N, N-dimethylaminophenyl) thiophen-3-yl) perfluorocyclopentene or 1, 2-bis (2-methyl-5-naphthylthiophen-3-yl) perfluorocyclopentene.
The preparation method of the silver-plated mirror comprises the following specific steps:
(1) cleaning the upper surface and the lower surface of the transparent substrate photochromic base material serving as a surface to be plated by using a KOH solution or a chromic acid washing solution until a residual water layer on the surface is uniform, then adding concentrated hydrochloric acid with the volume of 8-12% of that of a stannous chloride aqueous solution into 20g/L of the stannous chloride aqueous solution to obtain a sensitizing solution, adjusting the flow rate of a spray gun to be 2-6 mL/s, uniformly spraying the sensitizing solution onto the upper surface and the lower surface of the transparent substrate photochromic base material for 3 times, and sensitizing for 13-18 s each time;
(2) completely immersing the substrate into a container capable of containing a first silver plating solution immediately after sensitization, adding the first silver plating solution which is uniformly mixed, slightly shaking the transparent substrate photochromic substrate for 20-30 s, and then washing with water and drying; forming a metal silver film on the surface of the photochromic substrate of the transparent substrate, and preparing a silver film with the thickness of 10-40 nm;
(3) self-agglomerating the silver film into nano silver particles which are randomly distributed after the rapid annealing treatment in the nitrogen environment of 2L/min, and then utilizing a reactive ion etching system to perform SF treatment6Etching gas under the condition of 200W of power supply power; subsequently, the silver nanoparticles remained on the surface of the substrate are cleaned by 3M nitric acid to form a nano anti-reflection layer;
(4) cleaning and sensitizing only the lower surface of the photochromic base material of the transparent substrate according to the method in the step (1), and after sensitization, silver plating is carried out on the lower surface by adopting a second silver plating solution for reaction for 30-60 s; and after 5 minutes, re-plating once according to the operation method, finally washing redundant second silver plating solution with water, airing the silver mirror layer in a ventilated place to obtain a silver mirror layer, drying the silver mirror layer in the shade, then brushing a paint layer on the silver mirror layer, and drying the silver mirror layer to obtain the silver-plated mirror.
Preferably, the preparation method of the first silver plating solution comprises the following steps: preparing a silver ammonia solution from 0.02wt% silver nitrate aqueous solution, 0.01wt% potassium hydroxide aqueous solution and 0.1wt% ammonia water according to a volume ratio of 1:1:1, and mixing 0.02wt% glucose aqueous solution with the same volume as the silver ammonia solution to obtain a first silver plating solution;
the preparation method of the second silver plating solution comprises the following steps: according to 1.5wt% AgNO3Aqueous solution: 1.5wt% aqueous KOH solution: mixing 0.75wt% glucose water solution at a volume ratio of 1:1:1, and adding AgNO3Mixing the aqueous solution and KOH aqueous solution, adding concentrated ammonia water under continuous stirring until the precipitate is just completely dissolved to obtain solution A, uniformly mixing the solution A and glucose aqueous solution, and preparing the solution before film coating.
Preferably, the sensitizing step in the steps (1) and (4) further comprises an activating step: adding concentrated hydrochloric acid with the volume of 1-5% of that of the palladium chloride aqueous solution into 0.2-0.5 g/L of the palladium chloride aqueous solution to obtain an activation solution, uniformly spraying the activation solution on a surface to be plated, wherein the flow rate of a spray gun is 2-6 mL/s, spraying is carried out for 2 times, 30-60 s each time, and immediately carrying out a silver plating step after activation.
The invention has the following beneficial effects:
1. when the silver-plated mirror prepared by the invention is used under strong light, the photochromic substrate of the transparent substrate is changed from colorless transparency to dark transparency, so that the light incidence and the light reflection of the silver mirror layer are reduced, and the phenomena of dazzling and dazzling are prevented; when the mirror is used under dark light, the transparent substrate photochromic base material is colorless and transparent, does not influence the incident quantity and the reflection quantity of light, and has similar optical effect with a common mirror.
2. The preparation steps of the nanometer anti-reflection layer can not only prevent Fresnel reflection, but also properly coarsen the lower surface of the base material before secondary silver plating, improve the adhesion of the silver mirror layer on the lower surface and prevent the stripping phenomenon of the silver plating layer.
3. The first silver plating layer is thinner and is mainly used as a mask for etching to generate an irregular concave-convex structure and cannot be too thick, otherwise, the irregular concave-convex structure is not easy to condense and shrink to form nano silver particles, the second silver plating layer is mainly used for generating a high-reflection compact silver mirror layer and needs a thick and stable deposited silver mirror layer, and due to different purposes, the preparation of different silver plating solutions is carried out according to needs, so that the formation of a functional microstructure of a silver-plated mirror is facilitated.
4. The sensitizing and activating steps are beneficial to the stable deposition of the silver metal particles on the surface of the photoinduced variable base material made of different materials to form a silver mirror layer, the quality of the mirror surface is improved, and the silver mirror layer is prevented from being peeled off.
Detailed Description
The following examples are included to provide further detailed description of the present invention and to provide those skilled in the art with a more complete, concise, and exact understanding of the principles and spirit of the invention.
Example 1: a silver-plated mirror was prepared as follows:
firstly, preparation of raw materials
The paint layer coating formula comprises: 15 parts of oil-based varnish, 80 parts of red lead powder and 15 parts of No. 20 solvent gasoline by weight are mixed uniformly and then brushed;
the transparent substrate photochromic base material is high borosilicate glass with a silver halide color-changing system (containing 0.142 wt% of Ag, 0.12 wt% of Br, 0.31 wt% of Cl and 0.014 wt% of CuO) in solid solution, and the thickness of the transparent substrate photochromic base material is 1 mm;
the preparation method of the first silver plating solution comprises the following steps: preparing a silver ammonia solution from 0.02wt% silver nitrate aqueous solution, 0.01wt% potassium hydroxide aqueous solution and 0.1wt% ammonia water according to a volume ratio of 1:1:1, and mixing 0.02wt% glucose aqueous solution with the same volume as the silver ammonia solution to obtain a first silver plating solution;
the preparation method of the second silver plating solution comprises the following steps: according to 1.5wt% AgNO3Aqueous solution: 1.5wt% aqueous KOH solution: 0.75wt% glucosePreparing the AgNO with the volume ratio of the aqueous solution of 1:1:13Mixing the aqueous solution and KOH aqueous solution, adding concentrated ammonia water under continuous stirring until the precipitate is just completely dissolved to obtain solution A, uniformly mixing the solution A and glucose aqueous solution, and preparing the solution before film coating.
Secondly, preparing the silver-plated mirror:
(1) cleaning the upper surface and the lower surface of the transparent substrate photochromic substrate serving as a surface to be plated by using a KOH solution or a chromic acid washing solution until a residual water layer on the surface is uniform, then adding concentrated hydrochloric acid with the volume of 8% of that of a stannous chloride aqueous solution into 20g/L of the stannous chloride aqueous solution to obtain a sensitizing solution, adjusting the flow rate of a spray gun to be 2mL/s, uniformly spraying the sensitizing solution onto the upper surface and the lower surface of the transparent substrate photochromic substrate for 3 times, and sensitizing for 13s each time;
(2) completely immersing the substrate into a container capable of containing a first silver plating solution immediately after sensitization, adding the first silver plating solution which is uniformly mixed, slightly shaking the transparent substrate photochromic substrate for 20s, and then washing with water and drying; forming a metal silver film on the surface of the photochromic substrate of the transparent substrate to prepare a silver film with the thickness of 10 nm;
(3) rapidly annealing at 300 deg.C for 30s (RTP-500, Beijing Dongdong institute of Physics) in nitrogen atmosphere of 2L/min to self-aggregate the silver film into randomly distributed nano silver particles, and etching with SF by using reactive ion etching system6Etching for 5min under the condition of 200W of power supply power for etching gas (tegal 903e, REFURSEHED); subsequently, the silver nanoparticles remained on the surface of the substrate are cleaned by 3M nitric acid to form a nano anti-reflection layer; the characterization of the nano anti-reflection layer is measured by a scanning electron microscope (FE-SEM: FEI Quanta 400FEG), and the etching depth of the nano anti-reflection layer in the embodiment is measured to be 97 nm;
(4) cleaning and sensitizing only the lower surface of the photochromic base material of the transparent substrate according to the method in the step (1), and after sensitization, carrying out silver plating on the lower surface by adopting a second silver plating solution for reaction for 30 s; and after 5 minutes, re-plating once according to the operation method, finally washing redundant second silver plating solution with water, airing the silver mirror layer at a ventilated place to prepare a silver mirror layer, drying the silver mirror layer in the shade, then coating a paint layer on the silver mirror layer, and drying the silver mirror layer to obtain the silver-plated mirror, wherein the thickness of the silver mirror layer of the silver-plated mirror is measured to be 21 microns by an ultrasonic coating thickness gauge, and the thickness of the paint layer is measured to be 113 microns.
Example 2: a silver-plated mirror was prepared as follows:
firstly, preparation of raw materials
The paint layer coating formula comprises: 15 parts of oil-based varnish, 80 parts of red lead powder and 20 parts of No. 20 solvent gasoline by weight, and the three are mixed uniformly and then can be brushed;
the transparent substrate photochromic base material is a transparent substrate photochromic organic material and has the thickness of 3 mm;
in this embodiment, the transparent substrate photochromic organic material is an optical resin polymer dispersed with spiropyran color-changing particles (weight ratio: 0.5 wt%); the optical resin polymer is prepared by mixing styrene, trimethylolpropane triacrylate vinegar and ethoxylated bisphenol A diacrylate in the weight ratio of 1:1:2, controlling the total mass ratio of polyoxyethylene polyoxypropylene ether block copolymer ((F127) to methacrylic acid to be not more than 2.5 wt%, and preparing the photochromic organic material with the refractive index of 1.5171 by using azodiisoheptonitrile as an initiator and diisooctylphthalate as a plasticizer.
The first and second silver plating solutions were prepared in the same manner as in example 1.
Concentrated hydrochloric acid of 1% by volume of the aqueous palladium chloride solution was added to 0.2g/L of the aqueous palladium chloride solution to obtain an activated solution.
Secondly, preparing the silver-plated mirror:
(1) cleaning the upper surface and the lower surface of the transparent substrate photochromic substrate serving as a surface to be plated by using a KOH solution or a chromic acid washing solution until a residual water layer on the surface is uniform, then adding concentrated hydrochloric acid with the volume of 12% of that of a stannous chloride aqueous solution into 20g/L of the stannous chloride aqueous solution to obtain a sensitizing solution, adjusting the flow rate of a spray gun to be 6mL/s, uniformly spraying the sensitizing solution onto the upper surface and the lower surface of the transparent substrate photochromic substrate for 3 times, and sensitizing for 18s each time;
(2) after sensitization, uniformly spraying the activating solution on a surface to be plated, wherein the flow rate of a spray gun is 6mL/s, spraying is carried out for 2 times, 60s each time, after activation, the surface is immediately and completely immersed into a container capable of containing the first silver plating solution, the first silver plating solution is added and uniformly mixed, the transparent substrate photochromic base material is slightly shaken for 30s, and then the transparent substrate photochromic base material is washed by water and dried; forming a metal silver film on the surface of the photochromic substrate of the transparent substrate to prepare a silver film with the thickness of 40 nm;
(3) rapidly annealing at 220 deg.C under 2L/min nitrogen for 3min (RTP-500, Beijing Dongdong's institute of Physics), self-agglomerating the silver film into randomly distributed nano silver particles, and etching with SF by using reactive ion etching system6For etching gas, etching treatment is carried out for 6min under the condition that the power supply power is 200W (tegal 903e, REFURSEHED); subsequently, the silver nanoparticles remained on the surface of the substrate are cleaned by 3M nitric acid to form a nano anti-reflection layer; the characterization of the nanometer anti-reflection layer is measured by a scanning electron microscope (FE-SEM: FEI Quanta 400FEG), and the etching depth of the nanometer anti-reflection layer in the embodiment is 186 nm;
(4) cleaning and sensitizing only the lower surface of the photochromic base material of the transparent substrate according to the method in the step (1), uniformly spraying the activating solution on the surface to be plated after sensitization, spraying for 2 times and 60s each time at the flow speed of 6mL/s by using a spray gun, and after activation, silvering the lower surface by using a second silvering solution for reaction for 60 s; and after 5 minutes, re-plating once according to the operation method, finally washing redundant second silver plating solution with water, airing the silver mirror layer at a ventilated place to prepare a silver mirror layer, drying the silver mirror layer in the shade, then coating a paint layer on the silver mirror layer, and drying the silver mirror layer to obtain the silver-plated mirror, wherein the thickness of the silver mirror layer of the silver-plated mirror is measured to be 94 microns by an ultrasonic coating thickness meter, and the thickness of the paint layer is 459 microns.
Example 3: a silver-plated mirror was prepared as follows:
firstly, preparation of raw materials
The paint layer coating formula comprises: 15 parts of oil-based varnish, 60 parts of red lead powder and 17 parts of No. 20 solvent gasoline by weight, and the three are mixed uniformly and then can be brushed;
the transparent substrate photochromic base material is a transparent substrate photochromic organic material and is 10mm thick;
the photochromic organic material of the transparent substrate is an optical resin polymer dispersed with 1,2 bis (2-methyl-5- (4-N, N-dimethylaminophenyl) thiophene-3-yl) perfluorocyclopentene with the total weight of 1.1 wt%; the optical resin polymer was the same as in example 2.
The first and second silver plating solutions were prepared as in example 1.
Concentrated hydrochloric acid of 5 vol% of the aqueous palladium chloride solution was added to 0.5g/L of the aqueous palladium chloride solution to obtain an activated solution.
Secondly, preparing the silver-plated mirror:
(1) cleaning the upper surface and the lower surface of the transparent substrate photochromic substrate serving as a surface to be plated by using a KOH solution or a chromic acid washing solution until a residual water layer on the surface is uniform, then adding concentrated hydrochloric acid with the volume of 10% of that of a stannous chloride aqueous solution into 20g/L of the stannous chloride aqueous solution to obtain a sensitizing solution, adjusting the flow rate of a spray gun to be 4mL/s, uniformly spraying the sensitizing solution onto the upper surface and the lower surface of the transparent substrate photochromic substrate for 3 times, and sensitizing for 15s each time;
(2) after sensitization, uniformly spraying the activating solution on a surface to be plated, wherein the flow rate of a spray gun is 4mL/s, spraying is carried out for 2 times, each time is 45s, after activation, the activating solution is immediately and completely immersed into a container capable of containing the first silver plating solution, the first silver plating solution is added and uniformly mixed, the transparent substrate photochromic base material is slightly shaken for 25s, and then the transparent substrate photochromic base material is washed by water and dried; forming a metal silver film on the surface of the photochromic substrate of the transparent substrate to prepare a silver film with the thickness of 25 nm;
(3) rapidly annealing at 270 deg.C for 45s (RTP-500, Beijing Dongdong institute of Physics) in nitrogen atmosphere of 2L/min to self-aggregate the silver film into randomly distributed nano silver particles, and etching with SF by using reactive ion etching system6For etching gas, etching treatment is carried out for 4min under the condition of 200W of power supply power (tegal 903e, REFURSEHED); subsequently, the silver nanoparticles remained on the surface of the substrate are cleaned by 3M nitric acid to form a nano anti-reflection layer; the characterization of the nanometer anti-reflection layer is measured by a scanning electron microscope (FE-SEM: FEI Quanta 400FEG), and the etching depth of the nanometer anti-reflection layer in the embodiment is 137 nm;
(4) cleaning and sensitizing only the lower surface of the photochromic base material of the transparent substrate according to the method in the step (1), uniformly spraying the activating solution on the surface to be plated after sensitization, spraying for 2 times and 45s each time at the flow speed of 4mL/s by using a spray gun, and after activation, silvering the lower surface by using a second silvering solution for reacting for 45 s; and after 5 minutes, re-plating once according to the operation method, finally washing redundant second silver plating solution with water, airing the silver mirror layer at a ventilated place to prepare a silver mirror layer, drying the silver mirror layer in the shade, then coating a paint layer on the silver mirror layer, and drying the silver mirror layer to obtain the silver-plated mirror, wherein the thickness of the silver mirror layer of the silver-plated mirror is measured to be 59 micrometers by an ultrasonic coating thickness meter, and the thickness of the paint layer is measured to be 284 micrometers.
Example 4: a silver-plated mirror was prepared as follows:
firstly, preparation of raw materials
The paint layer coating formula comprises: 18 parts of oil-based varnish, 80 parts of red lead powder and 16 parts of No. 20 solvent gasoline by weight, and the three are mixed uniformly and then can be brushed;
the transparent substrate photochromic base material is a transparent substrate photochromic organic material, and the thickness of the transparent substrate photochromic base material is 15 mm;
the transparent substrate photochromic organic material is an optical resin polymer in which 1, 2-bis (2-methyl-5-naphthylthiophen-3-yl) perfluorocyclopentene is dispersed in an amount of 0.31 wt% based on the total weight; the optical resin polymer was the same as in example 2.
The first and second silver plating solutions were prepared in the same manner as in example 1.
Concentrated hydrochloric acid of 3% by volume of the aqueous palladium chloride solution was added to 0.35g/L of the aqueous palladium chloride solution to obtain an activated solution.
Secondly, preparing the silver-plated mirror:
(1) cleaning the upper surface and the lower surface of the transparent substrate photochromic substrate serving as a surface to be plated by using a KOH solution or a chromic acid washing solution until a residual water layer on the surface is uniform, then adding concentrated hydrochloric acid with the volume of 9% of that of a stannous chloride aqueous solution into 20g/L of the stannous chloride aqueous solution to obtain a sensitizing solution, adjusting the flow rate of a spray gun to be 5mL/s, uniformly spraying the sensitizing solution onto the upper surface and the lower surface of the transparent substrate photochromic substrate for 3 times, and sensitizing 17s each time;
(2) after sensitization, uniformly spraying the activating solution on a surface to be plated, wherein the flow rate of a spray gun is 3mL/s, spraying is carried out for 2 times, each time is 40s, after activation, the activating solution is immediately and completely immersed into a container capable of containing the first silver plating solution, the first silver plating solution which is uniformly mixed is added, the transparent substrate photochromic base material is slightly shaken for 23s, and then the transparent substrate photochromic base material is washed with water and dried; forming a metal silver film on the surface of the photochromic base material of the transparent substrate to prepare a silver film with the thickness of 34 nm;
(3) in a 2L/min nitrogen environmentPerforming rapid annealing treatment at 240 deg.C for 15s (RTP-500, Beijing Dongtong institute of Physics), self-agglomerating the silver film into randomly distributed nano silver particles, and performing SF etching by using a reactive ion etching system6For etching gas, etching treatment is carried out for 2min under the condition of 200W of power supply power (tegal 903e, REFURSEHED); subsequently, the silver nanoparticles remained on the surface of the substrate are cleaned by 3M nitric acid to form a nano anti-reflection layer; the characterization of the nano anti-reflection layer is measured by a scanning electron microscope (FE-SEM: FEI Quanta 400FEG), and the etching depth of the nano anti-reflection layer in the embodiment is measured to be 105 nm;
(4) cleaning and sensitizing only the lower surface of the photochromic base material of the transparent substrate according to the method in the step (1), uniformly spraying the activating solution on the surface to be plated after sensitization, spraying for 2 times and 45s each time at the flow speed of a spray gun of 3mL/s, and after activation, silver plating the lower surface by adopting a second silver plating solution for reaction for 45 s; and after 5 minutes, re-plating once according to the operation method, finally washing redundant second silver plating solution with water, airing the silver mirror layer at a ventilated place to prepare a silver mirror layer, drying the silver mirror layer in the shade, then coating a paint layer on the silver mirror layer, and drying the silver mirror layer to obtain the silver-plated mirror, wherein the thickness of the silver mirror layer of the silver-plated mirror is measured to be 73 microns by an ultrasonic coating thickness gauge, and the thickness of the paint layer is measured to be 226 microns.
Comparative example: the mirror containing the silver-plated modification layer is prepared by adopting the method provided in Chinese patent CN103858026B and is used for a subsequent performance comparison test;
1. to test the optical properties of the present invention, the following tests were performed:
under the environment of 200Lx illumination intensity, taking the etched non-silver-plated transparent substrate photochromic base material as each group of samples, and measuring the transmittance and the reflectance in the wavelength range of 200-2500nm by using a UV-VIS-NIR spectrophotometer (UV-3600, SHIMADZU) and combining an integrating sphere, wherein the results are as follows;
TABLE 1 light reflectance (%) of silver-plated mirror surface at different wavelengths
The results in table 1 show that in a low light environment, the nano anti-reflection layer can significantly reduce the reflectivity of the upper surface of the substrate, thereby reducing the fresnel reflection phenomenon on the surface of the substrate, and thus increasing the visual field of the mirror, while the surface of the comparative example is a smooth mirror surface, and therefore has a higher reflectivity.
TABLE 2 light transmittance (%) at different wavelengths on the surface of the silver-plated mirror
The results in table 2 show that the transmittance of 200nm ultraviolet light is low due to weak penetrating power, while the light with the wavelength of more than 400nm has high light penetration and less loss in a weak light environment, because the photochromic substrate of the substrate is in a transparent state in the weak light environment, the photochromic substrate has no capability of blocking light penetration basically, and the photochromic substrate is beneficial to light reflection imaging of the silver mirror layer of the mirror in the weak light environment.
2. Detection of reflectivity of silver-plated mirror
The silver-plated mirror samples were irradiated with 3500Lx intensity and 200Lx white light at 60 degree angle, respectively, and the reflectivity was measured, the results are shown in table 3:
TABLE 3 reflectance of silver-plated mirrors at different light intensities
Under the irradiation of 3500Lx strong light, the base material is subjected to photochromic development and darkened, so that the transmission of light is blocked, the light transmittance of the photochromic base material of the transparent substrate is obviously reduced compared with that of the comparative example, the integral reflectivity of the mirror in the examples 1-4 under strong light is obviously reduced compared with that of the comparative example, and the phenomena of dazzling and dazzling caused by over-strong light reflection are prevented; when the mirror is irradiated by 200Lx weak light, the base material does not generate photochromic color, the whole reflectivity of the mirror is similar to that of a common mirror, and the contrast embodiment comprises the coloring layer, so that the whole reflectivity is reduced, and the dark light imaging of the mirror is not facilitated.
3. Bond strength detection for silver mirror layers
The test of the adhesive force of the silver mirror layer refers to the GB9286-88 standard, the silver-plated mirror prepared in the embodiment 1-4 is used as a sample, the lower surface of the photochromic base material of the transparent substrate is subjected to lattice drawing to prepare a sample, the number of the lattices is 5 multiplied by 5, and the side length of each lattice is 2 mm. And manual scratching is adopted for scratching, force is uniformly applied, the scratching speed is about 50mm/s, and the scratching is stable and free of vibration. And after cutting, using a 3M adhesive tape to bond the surface of the scribed silver mirror layer, using the 3M adhesive tape to bond for 5 times, and observing the number of the remaining coating squares on the surface of the aluminum foil paper to represent the adhesive force of the silver mirror layer to the base paper in a grading way, wherein the adhesive force of 0 grade is the best, the adhesive force of 5 grades is the worst, and the adhesive force of 0 grade, 1 grade and 2 grades can meet the common application.
TABLE 4 determination of the curing adhesion rating of silver mirror layers
| Group of | Region 1 | Region 2 | Region 3 |
| Example 1 | 1 | 1 | 1 |
| Example 2 | 0～1 | 0～1 | 0～1 |
| Example 3 | 0～1 | 1 | 0～1 |
| Example 4 | 1 | 0 | 0 |
| Comparative example | 2 | 2 | 2 |
| Common silver-plated mirror | 2 | 3 | 2 |
The results show that the adhesive force between the silver mirror layer and the base material is obviously better than that between the silver mirror layer and the base material in the comparison example and the common silver mirror, and the silver particles are deposited more uniformly and compactly and are adhered more tightly mainly due to the micro-roughening effect of the nano anti-reflection layer on the lower surface. After the activation step was added, the silver mirror layer of the optical resin material also had a better adhesion effect, similar to or better than that of example 1.
In conclusion, when the silver-plated mirror prepared by the invention is used under strong light, the photochromic substrate of the transparent substrate is changed from colorless transparency to dark transparency, so that the light incidence and the light reflection of the silver mirror layer are reduced, and the phenomena of dazzling and dazzling are prevented; when the mirror is used under dark light, the transparent substrate photochromic base material is colorless and transparent, does not influence the incident quantity and the reflection quantity of light, and has similar optical effect with a common mirror. The preparation steps of the nanometer anti-reflection layer can not only prevent Fresnel reflection, but also properly coarsen the lower surface of the base material before secondary silver plating, improve the adhesion of the silver mirror layer on the lower surface and prevent the stripping phenomenon of the silver plating layer. The first silver plating layer is thinner and is mainly used as a mask for etching to generate an irregular concave-convex structure and cannot be too thick, otherwise, the irregular concave-convex structure is not easy to condense and shrink to form nano silver particles, the second silver plating layer is mainly used for generating a high-reflection compact silver mirror layer and needs a thick and stable deposited silver mirror layer, and due to different purposes, the preparation of different silver plating solutions is carried out according to needs, so that the formation of a functional microstructure of a silver-plated mirror is facilitated. The sensitizing and activating steps are beneficial to the stable deposition of the silver metal particles on the surface of the photoinduced variable base material made of different materials to form a silver mirror layer, the quality of the mirror surface is improved, and the silver mirror layer is prevented from being peeled off.
The above embodiments are only for illustrating the technical idea of the present invention, and the protection scope of the present invention cannot be limited thereby, and any modification made on the basis of the technical scheme according to the technical idea proposed by the present invention falls within the protection scope of the present invention; the technology not related to the invention can be realized by the prior art.
Claims (6)
1. A silver-plated mirror characterized by: the transparent substrate is etched on the upper surface of the photochromic substrate to form a nano anti-reflection layer, the lower surface of the photochromic substrate is chemically plated with silver to form a silver mirror layer, and the silver mirror layer is coated with a paint layer;
the thickness of the transparent substrate photochromic base material is more than or equal to 1mm, the etching depth of the nano anti-reflection layer is 97-186 nm, the thickness of the silver mirror layer is 21-94 mu m, and the thickness of the paint layer is 113-459 mu m;
the specific preparation steps of the silver-plated mirror are as follows:
(1) cleaning the upper surface and the lower surface of the transparent substrate photochromic base material serving as a surface to be plated by using a KOH solution or a chromic acid washing solution until a residual water layer on the surface is uniform, then adding concentrated hydrochloric acid with the volume of 8-12% of that of a stannous chloride aqueous solution into 20g/L of the stannous chloride aqueous solution to obtain a sensitizing solution, adjusting the flow rate of a spray gun to be 2-6 mL/s, uniformly spraying the sensitizing solution onto the upper surface and the lower surface of the transparent substrate photochromic base material for 3 times, and sensitizing for 13-18 s each time;
(2) completely immersing the substrate into a container capable of containing a first silver plating solution immediately after sensitization, adding the first silver plating solution which is uniformly mixed, slightly shaking the transparent substrate photochromic substrate for 20-30 s, and then washing with water and drying; forming a metal silver film on the surface of the photochromic substrate of the transparent substrate, and preparing a silver film with the thickness of 10-40 nm;
(3) self-agglomerating the silver film into nano silver particles which are randomly distributed after the rapid annealing treatment in the nitrogen environment of 2L/min, and then utilizing a reactive ion etching system to perform SF treatment6Etching gas under the condition of 200W of power supply power; subsequently, the silver nanoparticles remained on the surface of the substrate are cleaned by 3M nitric acid to form a nano anti-reflection layer;
(4) cleaning and sensitizing only the lower surface of the photochromic base material of the transparent substrate according to the method in the step (1), and after sensitization, silver plating is carried out on the lower surface by adopting a second silver plating solution for reaction for 30-60 s;
(5) and (5) after 5 minutes, re-plating once according to the method in the step (4), finally washing redundant second silver plating solution with water, airing the silver plating solution in a ventilated place to prepare a silver mirror layer, drying the silver mirror layer in the shade, then coating a paint layer on the silver mirror layer, and drying the silver mirror layer to obtain the silver-plated mirror.
2. A silver-coated mirror according to claim 1, wherein: the transparent substrate photochromic base material is a transparent substrate photochromic organic material or transparent substrate photochromic glass.
3. A silver-coated mirror according to claim 2, wherein: the photochromic organic material of the transparent substrate is an optical resin polymer dispersed with spiropyran photochromic particles or diarylethene photochromic compounds; the transparent substrate photochromic glass is high borosilicate glass with a silver halide color-changing system in solid solution.
4. A silver-coated mirror according to claim 3, wherein: the diaryl ethylene photochromic compound is 1, 2-bis (2-methyl-5- (4-N, N-dimethylamino phenyl) thiophene-3-yl) perfluor cyclopentene or 1, 2-bis (2-methyl-5-naphthyl thiophene-3-yl) perfluor cyclopentene.
5. A silver-coated mirror according to claim 1, wherein: the preparation method of the first silver plating solution comprises the following steps: preparing a silver ammonia solution from 0.02wt% silver nitrate aqueous solution, 0.01wt% potassium hydroxide aqueous solution and 0.1wt% ammonia water according to a volume ratio of 1:1:1, and mixing 0.02wt% glucose aqueous solution with the same volume as the silver ammonia solution to obtain a first silver plating solution;
the preparation method of the second silver plating solution comprises the following steps: according to 1.5wt% AgNO3Aqueous solution: 1.5wt% aqueous KOH solution: mixing 0.75wt% glucose water solution at a volume ratio of 1:1:1, and adding AgNO3 Mixing the aqueous solution and KOH aqueous solution, adding concentrated ammonia water under continuous stirring until the precipitate is just completely dissolved to obtain solution A, uniformly mixing the solution A and glucose aqueous solution, and preparing the solution before film coating.
6. A silver-coated mirror according to claim 1, wherein: the step (1) and the step (4) further comprise an activation step after the sensitization step: adding concentrated hydrochloric acid with the volume of 1-5% of that of the palladium chloride aqueous solution into 0.2-0.5 g/L of the palladium chloride aqueous solution to obtain an activation solution, uniformly spraying the activation solution on a surface to be plated, wherein the flow rate of a spray gun is 2-6 mL/s, spraying is carried out for 2 times, 30-60 s each time, and a silver plating step is carried out immediately after activation.
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Citations (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63128318A (en) * | 1986-11-19 | 1988-05-31 | Seiko Epson Corp | Photochromic optical modulating element |
| EP0404599A2 (en) * | 1989-06-22 | 1990-12-27 | Sharp Kabushiki Kaisha | Optical memory device |
| TW203123B (en) * | 1990-04-17 | 1993-04-01 | Wasserman Nelson | |
| CN1944710A (en) * | 2006-10-11 | 2007-04-11 | 方宏亮 | Nano mirror spray coating |
| CN101398618A (en) * | 2008-10-30 | 2009-04-01 | 上海交通大学 | Method for producing antireflection film of subwavelength structure |
| JP2012009336A (en) * | 2010-06-25 | 2012-01-12 | Panasonic Electric Works Co Ltd | Organic electroluminescent element |
| CN103038671A (en) * | 2010-07-30 | 2013-04-10 | 光州科学技术院 | Micro/nano combined structure, manufacturing method of micro/nano combined structure, and manufacturing method of an optical device |
| CN103562151A (en) * | 2011-05-27 | 2014-02-05 | 康宁股份有限公司 | Transparent glass substrate having antiglare surface |
| CN103858026A (en) * | 2011-10-12 | 2014-06-11 | 法国圣戈班玻璃厂 | Mirror comprising a silvering-modifying layer |
| CN203800059U (en) * | 2014-04-03 | 2014-08-27 | 苏州北鹏光电科技有限公司 | Wide-angle photoelectric detector |
| CN104049295A (en) * | 2013-03-14 | 2014-09-17 | 松下电器产业株式会社 | Guided light diffuser panel and method of manufacturing guided light diffuser panel |
| JP2015130386A (en) * | 2014-01-07 | 2015-07-16 | パナソニックＩｐマネジメント株式会社 | Ultraviolet light-emitting element |
| CN105034969A (en) * | 2014-04-16 | 2015-11-11 | 福特全球技术公司 | Method for reducing reflectance of bright decorative trim under high ambient light conditions |
| CN105417965A (en) * | 2015-12-11 | 2016-03-23 | 潍坊玉晶玻璃科技有限公司 | Preparation method of tempered silver mirror |
| CN105487319A (en) * | 2002-04-03 | 2016-04-13 | 金泰克斯公司 | Electrochromic rearview mirror assembly incorporating a display/signal light |
| CN205246991U (en) * | 2015-12-03 | 2016-05-18 | 丹阳市特洛依眼镜有限公司 | Shading light -sensitive sunglasses |
| CN107632479A (en) * | 2017-11-07 | 2018-01-26 | 宁波祢若电子科技有限公司 | A kind of modified electrochromism automobile rear view mirror lens |
| CN109581777A (en) * | 2019-01-12 | 2019-04-05 | Oppo广东移动通信有限公司 | Electronic equipment, housing unit, electrochromism mould group and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10739589B2 (en) * | 2017-12-01 | 2020-08-11 | Doron Koren | Vehicle window adapted for augmented reality projection |
-
2019
- 2019-06-14 CN CN201910514455.8A patent/CN110196465B/en active Active
Patent Citations (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63128318A (en) * | 1986-11-19 | 1988-05-31 | Seiko Epson Corp | Photochromic optical modulating element |
| EP0404599A2 (en) * | 1989-06-22 | 1990-12-27 | Sharp Kabushiki Kaisha | Optical memory device |
| TW203123B (en) * | 1990-04-17 | 1993-04-01 | Wasserman Nelson | |
| CN105487319A (en) * | 2002-04-03 | 2016-04-13 | 金泰克斯公司 | Electrochromic rearview mirror assembly incorporating a display/signal light |
| CN1944710A (en) * | 2006-10-11 | 2007-04-11 | 方宏亮 | Nano mirror spray coating |
| CN101398618A (en) * | 2008-10-30 | 2009-04-01 | 上海交通大学 | Method for producing antireflection film of subwavelength structure |
| JP2012009336A (en) * | 2010-06-25 | 2012-01-12 | Panasonic Electric Works Co Ltd | Organic electroluminescent element |
| CN103038671A (en) * | 2010-07-30 | 2013-04-10 | 光州科学技术院 | Micro/nano combined structure, manufacturing method of micro/nano combined structure, and manufacturing method of an optical device |
| CN103562151A (en) * | 2011-05-27 | 2014-02-05 | 康宁股份有限公司 | Transparent glass substrate having antiglare surface |
| CN103858026A (en) * | 2011-10-12 | 2014-06-11 | 法国圣戈班玻璃厂 | Mirror comprising a silvering-modifying layer |
| CN104049295A (en) * | 2013-03-14 | 2014-09-17 | 松下电器产业株式会社 | Guided light diffuser panel and method of manufacturing guided light diffuser panel |
| JP2015130386A (en) * | 2014-01-07 | 2015-07-16 | パナソニックＩｐマネジメント株式会社 | Ultraviolet light-emitting element |
| CN203800059U (en) * | 2014-04-03 | 2014-08-27 | 苏州北鹏光电科技有限公司 | Wide-angle photoelectric detector |
| CN105034969A (en) * | 2014-04-16 | 2015-11-11 | 福特全球技术公司 | Method for reducing reflectance of bright decorative trim under high ambient light conditions |
| CN205246991U (en) * | 2015-12-03 | 2016-05-18 | 丹阳市特洛依眼镜有限公司 | Shading light -sensitive sunglasses |
| CN105417965A (en) * | 2015-12-11 | 2016-03-23 | 潍坊玉晶玻璃科技有限公司 | Preparation method of tempered silver mirror |
| CN107632479A (en) * | 2017-11-07 | 2018-01-26 | 宁波祢若电子科技有限公司 | A kind of modified electrochromism automobile rear view mirror lens |
| CN109581777A (en) * | 2019-01-12 | 2019-04-05 | Oppo广东移动通信有限公司 | Electronic equipment, housing unit, electrochromism mould group and preparation method thereof |
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