CN101024742B - Nano coating with photochromic and sunlight control characteristics, its preparing method and use - Google Patents
Nano coating with photochromic and sunlight control characteristics, its preparing method and use Download PDFInfo
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- CN101024742B CN101024742B CN200610008288A CN200610008288A CN101024742B CN 101024742 B CN101024742 B CN 101024742B CN 200610008288 A CN200610008288 A CN 200610008288A CN 200610008288 A CN200610008288 A CN 200610008288A CN 101024742 B CN101024742 B CN 101024742B
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Abstract
The invention relates to nanometer coating material that has photochromism and sunshine controlled capability, and the manufacturing method and the application. It includes the following steps: addingaqueous solution of adulterated stannic oxide tin oxide nanometer to container, whisking and adding the solution of IB series transition metal nanometer partical and/ or adding the compound of IB series metal to gain the aqueous solution nanometer coating with photochromism and sunshine controlled capability. The mol ratio of doped chemical in stannic oxide and the tin is 0.1-20:100. The mol ratio of stannic oxide and the IB series metal element is 200:1-5:1. The invention could be coated onto surface of glass or organic material.
Description
Technical field
The invention belongs to the nano paint field, particularly have photochromic and nano paint sunlight control characteristics, and the preparation method of this nano paint and the purposes that is used for aspects such as glass coating.
Background technology
The sunlight feed glass is meant the glass with certain control action kou that sees through to sunlight.Simple glass is that not optionally the sunlight feed glass does not have the acceptable transmitance to visible light to seeing through of sunlight, simultaneously to the sunlight ultraviolet or/and Sunshine Red has screening performance outward.The sunlight feed glass generally is the method preparation by magnetron sputtering, CVD and thermal spray, and for example Chinese patent publication number CN1263874A discloses a kind of antisun band coating glass, is the method preparation by thermal spray; Chinese patent publication number CN1350990A discloses a kind of band coating glass of sunlight control, and being needs could realize by the method for thermal spray or PVD or CVD.
Photochromic glass is meant the glass that visible light is had the acceptable transmitance, be subjected to the irradiation of certain wavelength light after, its visible light see through or variation has taken place in absorption spectrum; The performance of under the effect of the light of another wavelength, recovering again.Photochromic material can be divided into organic, inorganic and hybrid material by its Chemical Composition.Generally, the organic photochromic material responsiveness is very fast, be easy to add and be dispersed in the macromolecular material, China Patent No. for example: 02129913.7 discloses and has a kind ofly prepared the manufacture method of photochromic sunglasses with organic photochromic material, but the more inorganic photochromic material of the thermostability of organic photochromic material and ageing-resistant performance is poor.The hybrid system is the characteristics of comprehensive these two kinds of materials normally, to adapt to certain application conditions.The inorganic photochromic material that is used to prepare photochromic coating is silver halide or metal oxide normally.
Eighties of last century sixties, people have just found to contain silver halide and Cu
+Glass have photochromic performance, this discovery be used in the preparation various photochromic materials in, such as U.S. Pat 4049567 (1978); U.S. Pat 4134853 (1979) discloses a kind of composition that does not have the photochromic material of silver, is made up of titanium oxide, ferric oxide and lead nitrate; U.S. Pat 4556605 (1985) discloses a kind of silver halide and metallic compound and organic photochromic material compound photochromic material, and be applied to eyeglass and can improve its photochromic effect, but the composition of not mentioned composite tin oxide; U.S. Pat 5256337 (1993) discloses a kind of photochromic film, and wherein photochromic material is that nano-silver halide adds cobalt, chromium, manganese, magnesium and rare earth element to improve photochromic properties.
So-called aqueous solution is meant that solution or dispersion medium are water and water miscible solvent, and wherein the content of volatile solvent meets limiting the quantity of of state compulsion standard, promptly less than 200 grams per liters.Chinese patent publication number CN1696221A discloses the method for a kind of use formulations prepared from solutions solar control coating and glass, the present invention still adopts the method for aqueous solution to prepare film, on the basis of above-mentioned coating, increased photochromic properties, to improve the energy-conservation and comfortable effect of building glass.
The not mentioned method preparation with the aqueous solution coating of the combination of above document or document has concurrently photochromic and coating and glass solar control coating, simultaneously also not mentioned composition with water-thinned nanometer paint solution involved in the present invention.
Summary of the invention
A purpose of the present invention provides a kind of photochromic and aqueous solution nano paint sunlight control characteristics of having.
Another object of the present invention provides the preparation method of the aqueous solution nano paint with photochromic and sunlight control characteristics.
A present invention also purpose provides and has the purposes that photochromic and aqueous solution nano paint sunlight control characteristics is used for aspects such as glass coating.
It is on glass that coating of the present invention is that the method by aqueous solution coating is coated in, and comprises a kind of adulterated tin oxide nano particle and at least a metal nanoparticle of periodic table of elements transition metal IB family and/or the compound and the aqueous dispersion medium of IB group 4 transition metal of being positioned in the described aqueous solution nano paint at least.The glass that has this coating has sunlight control and photochromic properties simultaneously, is applied to building glass, can reach energy-conservation and comfortable effect.
Of the present invention have a compound that photochromic and aqueous solution nano paint sunlight control characteristics comprises adulterated tin oxide nano particle, IB group 4 transition metal nanoparticle and/or IB group 4 transition metal; Wherein: the mol ratio of doped element and tin element is 0.1～20: 100 in the adulterated stannic oxide, the mol ratio of stannic oxide and transition metal IB family metallic element is 200: 1～5: 1, and the compound of adulterated stannic oxide, metal nanoparticle and/or metal accounts for 1～15% of aqueous solution nano paint gross weight.
In order to improve the over-all properties of coating, can further in coating, add macromolecule film former and/or auxiliary agent, the consumption of macromolecule film former and auxiliary agent is respectively 0～5% of aqueous solution nano paint gross weight.
Preparation method with aqueous solution nano paint of photochromic and sunlight control characteristics of the present invention is:
The aqueous solution of adulterated tin oxide nano particle is joined in the container that whipping appts is installed, under agitation add the aqueous solution of worker B group 4 transition metal nanoparticle and/or the compound of adding IB group 4 transition metal, obtain having photochromic and aqueous solution nano paint sunlight control characteristics; Wherein: in the adulterated stannic oxide in doped element and the stannic oxide mol ratio of tin be 0.1～20: 100, the mol ratio of stannic oxide and transition metal IB family metallic element is 200: 1～5: 1, and the compound of adulterated stannic oxide, metal nanoparticle and/or metal accounts for 1～15% of aqueous solution nano paint gross weight.
In preparation method's process, can further in coating, add macromolecule film former and/or auxiliary agent, obtain uniform aqueous solution system.The consumption of macromolecule film former and auxiliary agent is respectively 0～5% of aqueous solution nano paint gross weight.
Described adulterated stannic oxide is adulterated stannic oxide of fluorine and/or the adulterated stannic oxide of antimony.
Described worker B group 4 transition metal nanoparticle is selected from one or more the mixture in copper, silver, the gold.
Described IB group transition metal compound is selected from one or more the mixture in muriate, bromide, iodide, nitrate, carbonate, vitriol, sulfonate, phosphoric acid salt or the perchlorate.
The mean sizes of described nanoparticle is less than 200 nanometers, and preferred mean sizes is less than 100 nanometers.
Described macromolecule film former is selected from one or both in water miscible acrylic ester emulsion, benzene-acrylic emulsion, organosilicon-modified acrylic emulsion, polyaminoester emulsion, acrylate-urethane copolymer emulsion, epoxy emulsion, the polyester emulsion.
Described auxiliary agent is selected from ethanol, ethylene glycol, Virahol, n-propyl alcohol, propylene glycol, propylene glycol monomethyl ether, Propylene Glycol Dimethyl Ether, propylene-glycol ethyl ether, propylene glycol methyl ethyl ether, propyl carbinol, epoxy six rings, acetone, pimelinketone, acetic acid, lactic acid, tartrate, ammoniacal liquor, trolamine, diethanolamine, in diisopropanolamine (DIPA), tween 80, triton x-100, polyvinyl alcohol, polyvinylpyrrolidone, the polyoxyethylene glycol 1～5 kind.
The content of the volatile solvent in the described auxiliary agent meets limiting the quantity of of state compulsion standard: less than 200 grams per liters.
Of the present invention have a coating that photochromic and aqueous solution nano paint sunlight control characteristics can be used for glass or organic materials surface, obtains having photochromic and glass or organic materials sunlight control characteristics.
Have photochromic and aqueous solution nano paint sunlight control characteristics with what obtain, method by even glue, impregnation, spraying or roller coating is applied to glass or organic materials surface, drying and forming-film just can obtain having photochromic and glass or organic materials sunlight control characteristics.
The thickness of described coating is 0.05～50 micron, preferred 0.1～10 micron.
The glass that has this coating has acceptable visible light transmissivity, outer to Sunshine Red or/and ultraviolet has bridging effect, and under UV-light or intensive solar radiation, visible light transmissivity reduces, visually show as the glass colour deepening, be applied to building and vehicle glass, energy-conservation comfortable effect is arranged.Preparation input of the present invention and the more various sputtering methods of cost or CVD method are low, adopt aqueous solution to have the characteristics of low toxicity, environmental protection.
For being engaged in the use in the various environment, the glass of band coating involved in the present invention or organic materials can compound other coatings or be prepared into hollow or vacuum subassembly.
The spectrogram of coating is to measure by UV-4100 HITACHI SPECTROPHOTMETER.
Below in conjunction with drawings and Examples technical scheme of the present invention is described in detail.Light transmission rate in the accompanying drawing is that the transmitance with air is a baseline, and promptly the transmitance of air is 100%.
Description of drawings
Fig. 1. the sample of the embodiment of the invention 1 is the Optical transmission spectrum figure of 250～2700 nanometers in the ultraviolet lighting front and back at wavelength.
Fig. 2. the sample of the embodiment of the invention 5 is the Optical transmission spectrum figure of 250～2700 nanometers in the ultraviolet lighting front and back at wavelength.
Fig. 3. the sample of the embodiment of the invention 8 is the Optical transmission spectrum figure of 250～2700 nanometers at wavelength behind the sunburst pre-irradiation.
Embodiment
Embodiment 1
In the reactor that whipping appts is housed, add weight percent concentration and be 1 kilogram of the aqueous dispersion of 5% antimony-doped tin oxide (ATO) nano powder, wherein the median size of ATO nano particle is 20 nanometers, under agitation add 1 kilogram of the nano-silver water solution that median size is 10 nanometers (wherein Yin concentration is 0.5 milligram/kilogram) again, stir after 30 minutes, get 50 milliliters of this solution, under the rotating speed of 800 rev/mins of sol evenning machines, be spin-coated on the glass substrate, then obtain the glass of band coating azury, the thickness of coating is 5 microns, this glass is 54～67% in the transmitance of visible-range (400～800 nanometer), sunlight ultraviolet and infrared percent of pass have been reduced simultaneously, have bridging effect, (curve a) in the accompanying drawing 1.
Is after 280～450 nano-ultraviolet lights shine 2 minutes with glass through wavelength, colour-darkening, and measuring its transmitance spectrogram is curve b in the accompanying drawing 1.From the transmitance spectrogram relatively, can see that the transmitance of 550 nano wave lengths has reduced by 7%, reduce for sunlight ultraviolet and infrared not covering.After one day, recover again by the color of glass in indoor placement for sample, and its spectrogram is curve c in the accompanying drawing 1.
Embodiment 2
Employing Chinese patent publication number is that the method for CN1696221A prepares antimony-doped tin oxide (ATO) slurries and fluorine-doped tin oxide (FTO) slurries, their weight percent concentration is respectively 20% and 5%, median size is respectively 30 nanometers and 50 nanometers, the FTO slurries of 0.5 kilogram ATO slurries and 0.5 kilogram are joined in the container that whipping appts is housed, the adding weight percent concentration is 2.5% 1 kilogram of polyvinyl alcohol water solution and Virahol 50 grams, add ammoniacal liquor then, the pH value that makes solution is 9, add weight percent concentration again and be 0.5 kilogram of the nano-silver water solution that 0.5% 1 kilogram of silver nitrate aqueous solution and concentration is 0.5 milligram/kilogram, wherein the median size of nanometer silver is 40 nanometers. after stirring, on the sheet glass with 3 mm thick of solution spraying to 1.2 meter * 1.2 meters, obtaining having the glass of light grey coating. the thickness of coating is 0.5 micron, has sunlight control and photochromic performance.
Embodiment 3
With 1 kilogram weight of percentage concentration is that 10% fluorine-doped tin oxide (FTO) slurries join in the container that stirring is housed, the median size of FTO nanoparticle is 100 nanometers, the adding weight percent concentration is 2.5% 1 kilogram of aqueous emulsion of polyurethane and Virahol 50 grams, add weight percent concentration again and be 0.5 kilogram of the nano-silver water solution that 0.5% 1 kilogram of the Sulfuric acid disilver salt aqueous solution and concentration is 0.02 milligram/kilogram, wherein the median size of nanometer silver is 50 nanometers.After stirring, solution is brushed on the substrate of transparent polymethylmethacrylate, obtain having the eyeglass of light grey coating, the thickness of coating is 3 microns.Can cover outside 45% the Sunshine Red, transmitance in visible light 550 nanometers is 81%, and it shines this coating 5 minutes under the UV-light of 365～450 nanometers, and its transmitance in visible light 550 nanometers has reduced by 8%, stop ultra violet lamp after 1 hour, its light transmission rate spectrogram recovers as before.
Embodiment 4
With 1.5 kilogram weights of percentage concentrations is that 8% antimony-doped tin oxide (ATO) slurries join in the container that stirring is housed, the median size of ATO nanoparticle is 180 nanometers, add weight percent concentration and be 1 kilogram of 2.5% polyvinyl alcohol water solution, add ammoniacal liquor then, the pH value that makes solution is 10, add weight percent concentration again and be 1 kilogram of 1% the silver chloride aqueous solution, after stirring, with solution spraying to sheet glass, obtain having the glass of light grey coating, have the sunlight control action kou, the thickness of coating is 5 microns.The outer transmitance of sunlight ultraviolet and Sunshine Red on average hangs down 30% than the transmitance at visible light respectively, this glass is shone 10 seconds kinds under the UV-light of 365～450 nanometers, its transmitance in visible light 550 nanometers has reduced by 10%, and the outer transmitance of sunlight ultraviolet and Sunshine Red does not change.After stopping ultra violet lamp, its light transmission rate spectrogram recovers as before.
Embodiment 5
Employing Chinese patent publication number is that the method for CN1696221A prepares antimony-doped tin oxide (ATO) slurries and fluorine-doped tin oxide (FTO) slurries, their weight percent concentration is 10%, median size is respectively 50 nanometers and 150 nanometers, the FTO slurries of 1.5 kilograms ATO slurries and 0.5 kilogram are joined in the container that whipping appts is housed, add trolamine 2 grams then, add weight percent concentration again and be 0.5 kilogram of the nanometer gold aqueous solution that 0.5% 1 kilogram of silver nitrate aqueous solution and concentration is 0.3 milligram/kilogram, wherein the median size of nanometer gold is 20 nanometers, after stirring, with solution spraying to sheet glass, obtain having the glass of light grey coating, this glass has sunlight control and photochromic properties concurrently.Before its UV-irradiation and postradiation spectrogram respectively as accompanying drawing 2a and Fig. 2 b.
Embodiment 6
With weight percent concentration is that 10% antimony-doped tin oxide (ATO) slurries join in the container that whipping appts is housed for 5 kilograms, wherein the median size of nano ATO is 20 nanometers, add diethanolamine 2 grams, add weight percent concentration again and be 0.5 kilogram of 0.5% the Silver monobromide aqueous solution, concentration is that 0.3 milligram/kilogram 1.5 kilograms of the nanometer gold aqueous solution and weight percent concentration are 0.1% CuSO
4The aqueous solution, wherein the median size of nanometer gold is 40 nanometers.After stirring, the method by impregnation prepares coating at glass surface, obtains the glass of coating, and the thickness of its floating coat is 15 microns, and its light average transmittances is 78%, and sunlight ultraviolet and infrared transmitance are respectively 64% and 52%.This glass has the sunlight control action kou, and this glass exposure was shone 15 minutes under intensive sunlight, and its visible light transmissive reduces by 6.7%.
Embodiment 7
With weight percent concentration is that 25% antimony-doped tin oxide (ATO) slurries join in the container that whipping appts is housed for 5 kilograms, wherein the median size of nano ATO is 30 nanometers, add diethanolamine 450 grams, add weight percent concentration again and be 0.5 kilogram of 0.5% the Silver monobromide aqueous solution, weight percent concentration is 2.5 kilograms of 0.2% nanometer copper liquor, the median size of nano copper particle is respectively 25 nanometers. add weight percent concentration again and be 2.5 kilograms of 2% polymethylmethacrylate water miscible liquids, after stirring, method by even glue, prepare coating at glass surface, obtain the glass of coating, the sunlight ultraviolet, as seen be respectively 60%, 76% and 52% with infrared average transmittances, this glass exposure was shone 15 minutes under intensive sunlight, its colour-darkening, the thickness of its floating coat are 15 microns.
Embodiment 8
With weight percent concentration is that 21% antimony-doped tin oxide (ATO) slurries join in the container that whipping appts is housed for 10 kilograms, wherein the median size of ATO nanoparticle is 10 nanometers, to wherein adding diethanolamine 5 grams, polyoxyethylene glycol 5 grams, add weight percent concentration again and be 0.5 kilogram of 3% the silver carbonate aqueous solution, concentration is 0.3 milligram/kilogram 1.5 kilograms in nanometer gold colloidal solution, and wherein the median size of nanometer gold is 6 nanometers, adds weight percent concentration and be 0.2% CuSO
42.5 kilograms of the aqueous solution, after stirring, method by spraying prepares coating at glass surface, obtain the glass of coating, it is packaged into the double glazing window assembly of (glass of 6 millimeters band coatings+12 millimeter air+6 millimeters white glass), its light transmission rate spectrogram is accompanying drawing 3a, and this glass exposure was shone 15 minutes under intensive sunlight again, its colour-darkening, light transmission rate spectrogram are accompanying drawing 3b.The thickness of its floating coat is 6 microns.
Embodiment 9
With weight percent concentration is that 25% antimony-doped tin oxide (ATO) slurries join in the container that whipping appts is housed for 5 kilograms, and wherein the median size of ATO nanoparticle is 150 nanometers, and to wherein adding diethanolamine 2 grams, polyoxyethylene glycol 5 grams add and contain Au
+10 kilograms of perchloric acid Jinsui River solution of 0.8%, concentration is 0.3 milligram/kilogram 1.5 kilograms in nanometer gold colloidal solution, wherein the median size of nanometer gold is 6 nanometers, after stirring, method by spraying prepares coating at glass surface, obtain the glass of coating, again it is packaged into the double glazing window assembly of (glass of 6 millimeters band coatings+6 millimeter air+6 millimeters white glass), demonstrate sunlight control and photochromic performance.
Claims (9)
1. one kind has photochromic and aqueous solution nano paint sunlight control characteristics, and it is characterized in that: this coating comprises
Adulterated tin oxide nano particle and
The compound of IB group 4 transition metal nanoparticle and/or IB group 4 transition metal;
Wherein: in the adulterated tin oxide nano particle in doped element and the stannic oxide mol ratio of tin be 0.1～20: 100, adulterated tin oxide nano particle be 200: 1～5: 1 from the mol ratio of the IB group 4 transition metal element in the compound of IB group 4 transition metal nanoparticle and/or IB group 4 transition metal, the compound of adulterated tin oxide nano particle and IB group 4 transition metal nanoparticle and/or IB group 4 transition metal accounts for 1～15% of aqueous solution nano paint gross weight;
Described adulterated tin oxide nano particle is adulterated stannic oxide of fluorine and/or the adulterated stannic oxide of antimony;
Described IB group 4 transition metal nanoparticle is selected from one or more the mixture in copper, silver, the gold; The compound of described IB group 4 transition metal is selected from one or more the mixture in muriate, bromide, iodide, nitrate, carbonate, vitriol, sulfonate, phosphoric acid salt or the perchlorate.
2. coating according to claim 1 is characterized in that: be added with macromolecule film former and/or auxiliary agent in the described coating, wherein the consumption of macromolecule film former and auxiliary agent is respectively 0～5% of aqueous solution nano paint gross weight.
3. coating according to claim 1 is characterized in that: the mean sizes of described nanoparticle is less than 200 nanometers.
4. coating according to claim 2 is characterized in that: described macromolecule film former is selected from one or both in water miscible acrylic ester emulsion, benzene-acrylic emulsion, organosilicon-modified acrylic emulsion, polyaminoester emulsion, acrylate-urethane copolymer emulsion, epoxy emulsion, the polyester emulsion.
5. coating according to claim 2, it is characterized in that: described auxiliary agent is selected from ethanol, ethylene glycol, Virahol, n-propyl alcohol, propylene glycol, propylene glycol monomethyl ether, Propylene Glycol Dimethyl Ether, propylene-glycol ethyl ether, propylene glycol methyl ethyl ether, propyl carbinol, epoxy six rings, acetone, pimelinketone, acetic acid, lactic acid, tartrate, ammoniacal liquor, trolamine, diethanolamine, in diisopropanolamine (DIPA), tween 80, triton x-100 polyvinyl alcohol, polyvinylpyrrolidone, the polyoxyethylene glycol 1～5 kind.
6. one kind according to each described preparation method with aqueous solution nano paint of photochromic and sunlight control characteristics of claim 1～5, it is characterized in that:
The aqueous solution of adulterated tin oxide nano particle is joined in the container, under agitation add the aqueous solution of IB group 4 transition metal nanoparticle and/or the compound of adding IB group 4 transition metal, obtain having photochromic and aqueous solution nano paint sunlight control characteristics; Wherein: in the adulterated stannic oxide in doped element and the stannic oxide mol ratio of tin be 0.1～20: 100, the mol ratio of stannic oxide and transition metal IB family metallic element is 200: 1～5: 1, and the compound of adulterated stannic oxide, metal nanoparticle and/or metal accounts for 1～15% of aqueous solution nano paint gross weight.
7. method according to claim 6, it is characterized in that: in preparation method's process, add macromolecule film former and/or auxiliary agent in coating, obtain uniform aqueous solution system, the consumption of macromolecule film former and auxiliary agent is respectively 0～5% of aqueous solution nano paint gross weight.
8. one kind according to each described purposes with aqueous solution nano paint of photochromic and sunlight control characteristics of claim 1～5, it is characterized in that: this coating is used for the coating on glass or organic materials surface, obtains having photochromic and glass or organic materials sunlight control characteristics.
9. purposes according to claim 8 is characterized in that: the thickness of described coating is 0.05～50 micron.
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| CN101024742B true CN101024742B (en) | 2010-05-12 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9864118B2 (en) | 2014-12-31 | 2018-01-09 | Saint-Gobain Performance Plastics Corporation | Photochromic solar control films |
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| CN115353701B (en) * | 2022-07-05 | 2023-09-29 | 北京仿生界面科学未来技术研究院 | Preparation method and application of intelligent window foil capable of self-adapting to illumination intensity |
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| US4556605A (en) * | 1982-09-09 | 1985-12-03 | Kabushiki Kaisha Suwa Seikosha | Photochromic coating composition and photochromic synthetic resin ophthalmic lens |
| US5256337A (en) * | 1988-06-20 | 1993-10-26 | Reid Jerome L | Photochromic polymer membrane |
| CN1263874A (en) * | 1998-08-21 | 2000-08-23 | 北美埃尔夫爱托化学股份有限公司 | Glass with coating and preventing sunlight |
| JP2000239044A (en) * | 1999-02-17 | 2000-09-05 | Matsushita Electric Ind Co Ltd | Production of electronic rube with black membrane |
| CN1350990A (en) * | 2000-10-30 | 2002-05-29 | 阿托费纳化学股份有限公司 | Sunshine controlled coated glass |
| CN1696221A (en) * | 2004-05-11 | 2005-11-16 | 中科纳米技术工程中心有限公司 | Sunlight controlled coating solution in low radiation, preparation method and application |
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|---|---|---|---|---|
| US4556605A (en) * | 1982-09-09 | 1985-12-03 | Kabushiki Kaisha Suwa Seikosha | Photochromic coating composition and photochromic synthetic resin ophthalmic lens |
| US5256337A (en) * | 1988-06-20 | 1993-10-26 | Reid Jerome L | Photochromic polymer membrane |
| CN1263874A (en) * | 1998-08-21 | 2000-08-23 | 北美埃尔夫爱托化学股份有限公司 | Glass with coating and preventing sunlight |
| JP2000239044A (en) * | 1999-02-17 | 2000-09-05 | Matsushita Electric Ind Co Ltd | Production of electronic rube with black membrane |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US9864118B2 (en) | 2014-12-31 | 2018-01-09 | Saint-Gobain Performance Plastics Corporation | Photochromic solar control films |
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