CN1111216A - Heat ray-reflecting glass - Google Patents
Heat ray-reflecting glass Download PDFInfo
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- CN1111216A CN1111216A CN94113361A CN94113361A CN1111216A CN 1111216 A CN1111216 A CN 1111216A CN 94113361 A CN94113361 A CN 94113361A CN 94113361 A CN94113361 A CN 94113361A CN 1111216 A CN1111216 A CN 1111216A
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- Prior art keywords
- plated film
- heat ray
- reflecting glass
- glass
- nickel
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
- C03C17/25—Oxides by deposition from the liquid phase
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/217—FeOx, CoOx, NiOx
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/23—Mixtures
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/112—Deposition methods from solutions or suspensions by spraying
Abstract
The present invention relates to a heat ray-reflecting glass comprises a glass substrate having on the surface thereof a coating film comprising cobalt oxide and nickel oxide. The said coating film has a surface resistivity of not less than 10<4> OMEGA /square and a thickness of not less than 10 nm, the content of cobalt in the coating film based on the total metal content per unit area is from 60 to 90% by weight, and the content of nickel in the coating film based on the total metal content per unit area is from 10 to 40% by weight. In a second aspect the coating film further comprises at least one metal selected from titanium, vanadium, chromium, manganese, copper, and zirconium from 1 to 39% by weight, and the content of iron in the coating film based on the total metal content per unit area is from 1.0 to 4.5% by weight. The reflecting color tone is green series color.
Description
The present invention relates to be used for building, automobile and other haulageman and have heat ray-reflecting glass.
In recent years, have the heat ray-reflecting glass of the transmissivity of low visible light and solar radiation, expanded to as building and the glass port of automobile, reduce the burden of air regulator to reduce straight heat according to daylight, secret and improve outward appearance.The manufacturing of heat ray-reflecting glass is to use physical unit, as sputter, on substrate of glass, form metallic membrane or metal nitride films, or be sprayed on the glass basic surface that is heated to more than the metallic compound heat decomposition temperature by the film-forming soln that will contain metallic compound and form metal oxide film.From the considerations such as weather resistance of production cost, plated film, a kind of method in back is more superior than preceding a kind of method.But the heat ray-reflecting glass that is obtained by this method is difficult to make transmission of visible light and solar radiation loss of transmission below certain level, and this level depends on the plated film composition.
In these cases, mean through the Japanese Patent of examination open as JP-B-63-3273(term used herein " JP-B ") describe, the known plated film that contains the metal oxide of cobalt and nickel can suitably reduce transmission of visible light etc. as plated film.
Yet, among the JP-B-63-32736 disclosed in conductive articles the surface resistivity of used plated film little, thereby reflection of electromagnetic wave height is when as the heat ray-reflecting glass window of building, cause the ghost image of contiguous house TV image, especially when cities and towns and urban district practical application, have shortcoming.
According to these situations, the purpose of this invention is to provide heat ray-reflecting glass, the reflection of electromagnetic wave that its coatings has is reduced to the level that can not cause problem in use, keep containing the optical characteristics of the certain limit that plated film had of cobalt oxide and nickel oxide simultaneously, also presented fabulous weather resistance.
The heat ray-reflecting glass that the present invention relates to comprises substrate of glass, has one deck to contain the plated film of cobalt oxide and nickel oxide on the surface of substrate of glass.
Coatings has following feature:
(1) a first aspect of the present invention, the surface resistivity of plated film is not less than 10
4Ω/side, thickness is not less than 10nm, the cobalt contents in the plated film is counted 60～90%(weight by the total metal contents in soil of per unit area) and plated film in nickel content count 10～40%(weight by the total metal contents in soil of per unit area).
(2) a second aspect of the present invention, plated film also contain at least a metal oxide that is selected from titanium, vanadium, chromium, manganese, copper and the zirconium, and its surface resistivity is not less than 10
4Ω/side, thickness is not less than 10nm, cobalt contents in the plated film is counted 60～89%(weight by the total metal contents in soil of per unit area), nickel content in the plated film is counted 10～39%(weight by the total metal contents in soil of per unit area), and the content that is selected from least a metal in titanium, vanadium, chromium, manganese, copper and the zirconium in the plated film is counted 1～30%(weight by the total metal contents in soil of per unit area).
(3) a third aspect of the present invention, plated film also contain ferric oxide, and its surface resistivity is not less than 10
4Ω/side, thickness is not less than 10nm, the iron level in the plated film is counted 1.0～4.5%(weight by the total metal contents in soil of per unit area).
(4) a fourth aspect of the present invention, the surface resistivity of plated film is not less than 10
4Ω/side, thickness are 10～70nm, mainly are made up of the oxide compound with spinel structure that contains cobalt oxide and nickel oxide, and the reflection tone simultaneously sees it is green from described plated film described invisible heat glass on the contrary.
Relation curve between the cobalt contents that Fig. 1 is illustrated in the per unit area total metal contents in soil of pressing plated film before and after the acid resistance test and the transmission of visible light variation.
Fig. 2 represents the schematic cross-sectional according to heat ray-reflecting glass of the present invention, and wherein numeral 1 is represented substrate of glass, numeral 2 expression plated films.
Heat ray-reflecting glass of the present invention can be pressed method production, the method comprises film forming solution is applied on the substrate of glass, film forming solution contains and is useful on cobalt compound, nickel compound and other compound that consists of the plated film component, the temperature of substrate of glass remain on be not less than these metallic compounds heat decomposition temperature to form metal oxide film. More particularly, the method can be by being sprayed to maintenance on glass realization the at high temperature with film forming solution behind the melt-shaping of the glass production line of float glass.
The temperature that is applied to the substrate of glass of coating solution is preferably 350～800 ℃.
The example of cobalt compound comprises acetylacetonate, cobalt acetate, cobalt chloride, cobalt borate, cobaltous sulfate, cobalt benzoate, cobaltous bromide, cobalt nitrate, cobaltous fluoride, cobaltous iodide, cobalt oxalate, cobalt phosphate, phosphorous acid cobalt and the cobaltous octadecanate of cobalt (II) or (III).
The example of nickel compound comprises two propionyl methyl nickel, two propionyl acetone nickel, nickel acetylacetonate, nickel acetate, nickelous bromide, nickel chloride, nickel fluoride, nickelous fluosilicate, nickel nitrate, nickel formate, nickel hydroxide, nickel iodide, nickel stearate, nickel sulfamic acid and nickelous sulfate.
In these nickel compounds, preferably two propionyl methyl nickel and/or two propionyl acetone nickel, the plated film that it provides has gratifying outward appearance and have gratifying solubility in organic solvent such as alcohols, toluene and dimethylbenzene.
The plated film that nickel acetylacetonate forms has the outward appearance of further improvement, also can be preferably used for the present invention. Because the solubility of nickel acetylacetonate in organic solvent such as alcohols, toluene and dimethylbenzene is little, so it is preferably on probation with the form of suspension in the organic solvent.
The example of titanium compound comprise titanium tetrachloride, tetrem titanium oxide, acetylacetone,2,4-pentanedione oxygen titanium, titanium sulfate (III), titanium sulfate (IV), titanium tetrabutoxide, isopropyl titanium oxide, first titanium oxide, Two octene glycosides (glycoxide) titaniums of diisopropoxy, the two octene glycosides titaniums of two-just-propoxyl group, diisopropoxy list octene glycosyloxy (glycoxy) titanium acetylacetone, two-just-butoxy list octene glycosyloxy titanium acetylacetone, four octene glycosides titaniums and two-just-propoxyl group bis-acetylacetonate titanium.
The example of vanadium compound comprises vanadium acetylacetonate, methyl ethyl diketone vanadyl, vanadium trichloride, vanadyl dichloride, vanadylic chloride, nitric acid vanadyl, oxalic acid vanadyl and vanadylic sulfate.
The example of chromium cpd comprises chromium acetylacetonate, chromium acetate (III), chromium chloride (II), chromic formate (III), chromium fluoride (III), ammonium chromic sulfate, chromium hydroxide, chromium nitrate (III), Plessy's green, potassium chromium sulfate and chromium sulphate (III).
The example of manganic compound comprises manganese acetylacetonate (I), manganese acetylacetonate (II), manganous acetate, ammonium manganous sulfate, manganese borate, Manganese dibromide, manganous carbonate, Manganous chloride tetrahydrate, manganous fluoride, manganese fluosilicate, formic acid manganese, manganese iodide, manganous lactate, manganous nitrate, manganous oxalate, phosphate dihydrogen manganese, manganese hydrogen phosphate, manganous sulfate and manganous tartrate.
The copper compound example comprises acetylacetone copper, cuprous bromide, cupric bromide, cuprous chloride, cupric chloride, cupric ammonium chloride, Cuprocitrol, cupric cyanide, cupric fluoborate, cupric fluoride, cuprichexafluorosilicate, Tubercuprose, copper hydroxide, cuprous iodide, cupric nitrate, cupric oleate, cupric oxalate, cupric phosphate and copper sulfate.
The example of zirconium compounds comprises methyl ethyl diketone zirconium, zirconium hydroxide, zirconium nitrate, nitrous acid zirconium, zirconyl chloride, phosphoric acid zirconium white, zirconium sulfate, zirconium tetrachloride and zirconium acetate.
The example of iron cpd comprises ferric acetyl acetonade, iron protochloride, iron(ic) chloride, ironic citrate, ferric ammonium oxalate, ferric ammonium sulfate, ferric fluoborate, ferric fluoride, silicofluoric acid iron, iron lactate, iron nitrate, Ferrox, ferrous phosphate, tertiary iron phosphate, ferrous sulfate, ferric sulfate and ferrous tartrate.
As the solvent that dissolves or disperse above-mentioned metallic compound, generally can be with an organic solvent as aromatic species solvent, esters solvent, ketones solvent, alcoholic solvent, ether solvent.
The example of substrate of glass generally comprises water white soda-lime glass substrate, but is not limited thereto.In order to regulate the tone of transmission of visible light or transmitted light, also can use the coloured soda-lime glass that contains a small amount of tinting material.
In order to reduce reflectance, plated film can also contain silicon or aluminium.In order to regulate tone, plated film also can contain zinc, tin, antimony, indium etc.The content that is used to reduce reflectance or regulates these metals of tone is preferably counted 3%(weight by the total metal contents in soil of per unit area) or 3% below.
In plated film according to first aspect present invention, weather resistance viewpoint according to plated film, the content of cobalt is preferably 68～87%(weight by the total metal contents in soil of per unit area in the plated film), the content of nickel is preferably 13～32%(weight by the total metal contents in soil of per unit area in the plated film).
According to the plated film of the present invention first and second aspects, preferred thickness is not more than 130nm, and this is because if thickness is too big, depends on that the surface resistivity of its composition can be less than 10
4Ω/side considers that according to the productivity of heat ray-reflecting glass the thickness of plated film more preferably is to be not more than 100nm, considers according to visible light transmittance, then is most preferably and is not more than 45nm.
Coating film thickness according to all aspects of the invention preferably still is 20～45nm, and this is to have fabulous outward appearance because have the plated film of this ranges of thicknesses.Thickness preferably still is 20～40nm.Have the heat ray-reflecting glass of the plated film that is used for building window glass of this thickness by use, can eliminate the discomfort that causes owing to the interior lighting reflection at night, this is because the reflected colour modulation monochromatizing of plated film one side is transferred; Also can get rid of because of the catoptrical pollution of skin, this is because all can be lowered in plated film one side with at the reflectance of the heat ray-reflecting glass on the two sides of the reverse side of plated film.
In plated film, consider that by transmittance of regulating visible light and the weather resistance of improving plated film the nickel content in the plated film is preferably 5～40%(weight by the per unit area total metal contents in soil) according to third aspect present invention.
The transmission tone that heat ray-reflecting glass of the present invention had preferably drops in the following scope according to JIS Z8722-1982 regulation:
-4.5≤a
＊≤4.5
3.0≤b
＊≤12.5
From the viewpoint of the value of the product of heat ray-reflecting glass outward appearance, the transmission tone of afore mentioned rules preferably falls in the following scope:
-0.5≤a
＊≤0.5
5.0≤b
＊≤8.5
The reflection tone that shows from the reflect visible light of the heat ray-reflecting glass unilateral observation of plated film reverse side preferably drops in the following scope by JIS Z8722-1982 regulation:
-7.0≤a
＊≤-3.0
-5.0≤b
＊≤4.0
The employed a of this paper
*And b
*Be L according to JIS Z8729-1980 regulation
*a
*b
*Chroma index than color system.
Surface resistivity according to the heat ray-reflecting glass of first aspect present invention is 10
4Ω/or 10
4Ω/more than the side, make it can not bring problem in fact in actual applications so that suppress reflection of electromagnetic wave.When surface resistivity reduces and increases along with the thickness of film, when the composition of film was identical, then the following 10nm that is limited to of first aspect present invention plated film was essential optical characteristics to keep heat ray-reflecting glass.In addition, the content by restriction cobalt oxide and nickel oxide is controlled at the transmission of visible light and the solar radiation transmissivity of first aspect present invention heat ray-reflecting glass in the suitable basically scope.Promptly in the plated film that comprises cobalt oxide and nickel oxide, the dzhulukulite with spinel structure has reduced surface resistivity.Therefore, when the stoichiometric ratio (Ni/Co=1/2) that is different from dzhulukulite by the ratio that makes nickel and cobalt widely increases the resistivity of plated film, if be used for increasing ratio that the method for resistivity is applied to cobalt oxide less than 60% situation, then just might make visible light transmittance surpass 50%.On the other hand, when ratio that this method is applied to nickel oxide less than 10% situation in, then the solar radiation transmissivity of glass can not be lowered to the degree of transmission of visible light.In both of these case, the feature of plated film does not all have to show.Therefore, in a first aspect of the present invention, account for the weight percent of plated film per unit area total metal contents in soil, make it to drop on respectively and avoid this class problem in 60～90% and 10～40% the scope by determining cobalt and nickel.
Have the feature of the invention described above first aspect according to the heat ray-reflecting glass of second aspect present invention,, thereby further improved weather resistance because the plated film of second aspect present invention contains at least a metal that is selected from titanium, vanadium, chromium, manganese, copper and zirconium.
The surface resistivity that has according to the heat ray-reflecting glass of third aspect present invention also is 10
4Ω/side, or 10
4Ω/more than the side, make it can not bring problem in fact in actual applications so that suppress reflection of electromagnetic wave.In the plated film of third aspect present invention, the following 10nm that is defined as of thickness so that keep for the necessary optical characteristics of heat ray-reflecting glass, and its thickness on be defined as 70nm so that when not using, make surface resistivity remain on 10 than relatively large iron
4Ω/side or 10
4Ω/more than the side.Therefore, can will be reduced to 4.5%(weight according to the iron level in the plated film of third aspect present invention) or lower, so that improve weather resistance, the especially acid resistance of plated film.
The surface resistivity that has according to the heat ray-reflecting glass of fourth aspect present invention also is 10
4Ω/side or 10
4Ω/more than the side, make it can not bring problem in fact in actual applications to suppress reflection of electromagnetic wave.In the heat ray-reflecting glass of fourth aspect present invention, from the reflection tone of plated film unilateral observation on the contrary be green be color.Thereby can be with it as heat ray-reflecting glass, from color harmony this satisfied requirement that is used for building window glass of viewpoint of scenery on every side of buildings with green reflection tone.It is open to mean uncensored Japanese Patent as JP-A-63-190742(term used herein " JP-A ") describe, the traditional heat ray-reflecting glass with green reflection tone has the glass of the trilamellar membrane of being made up of titanium oxide and titanium nitride.Owing to the production of traditional heat ray-reflecting glass is to form plated film with physical vapor deposition, therefore, its productivity is lower than the heat ray-reflecting glass of fourth aspect present invention, the plated film that the present invention can the low cost production high-durability.A kind of have as the identical spinel structure of fourth aspect present invention but can be produced by the method for thermolysis film-forming soln by the oxide film that cobalt, chromium and iron are formed.But, regulated its thickness and can not present green reflection tone even have the plated film of this composition.In this case, even can obtain tone, still, be to be difficult to obtain uniform color tone by on big area, forming even plated film near green area.
The heat-reflecting glass of the present invention first, second and the third aspect is by regulating plated film, and the thickness that especially makes plated film is 70nm or can be similar to a fourth aspect of the present invention below the 70nm and presents green reflection tone.
The present invention will be described in greater detail in conjunction with the following examples and comparative example, but the invention is not restricted to these embodiment.
The soda-lime-silica glass plate of one block length 150mm, wide 150mm, thick 4mm washed and dry to make substrate.With a suspension bracket this substrate is fixed in 650 ℃ the electric furnace and kept 5 minutes.Be sprayed in the substrate of taking out from electric furnace by being dissolved in the coated solution that 5.13g acetylacetone cobalt (III) in the 100CC toluene and 1.18g two propionyl methyl nickel (II) form a kind of, spraying is that to adopt commercially available spray gun be 3.0kg/cm in air pressure
2, air velocity is under the 90 l/ branch conditions, the spraying plated film speed of dividing with 20ml/ is carried out about 10 seconds and is implemented.
The transmission of visible light of the heat ray-reflecting glass that records by JIS R 3106-1985, visible light reflectance, solar radiation transmissivity and solar radiation reflectance.With in the radio frequency plasma emission spectrometry plated film by the cobalt contents of total metal contents in soil.Measure the surface resistivity and the thickness of plated film.What obtain the results are shown in the following table 1.
Same procedure by embodiment 1 prepares heat ray-reflecting glass, and just the consumption with acetylacetone cobalt (III) changes 4.27g into, and the consumption of two propionyl methyl nickel (II) changes 1.96g into, and spray time changes about 15 seconds into, and spraying plated film speed changes the 24ml/ branch into.Same procedure by embodiment 1 detects the invisible heat reflection glass coloured glaze that obtains.What obtain the results are shown in table 1.
Embodiment 3
Same procedure by embodiment 1 prepares heat ray-reflecting glass, and just the consumption with acetylacetone cobalt (III) changes 3.21g into, and the consumption of two propionyl methyl nickel (II) changes 2.94g into, and spray time changes about 20 seconds into, and spraying plated film speed changes the 28ml/ branch into.Same procedure by embodiment 1 detects the heat ray-reflecting glass that obtains.What obtain the results are shown in table 1.
Comparative example 1
For relatively, form the plated film formed by the metal oxide of chromium, iron and cobalt to prepare heat ray-reflecting glass.Identical method by embodiment 1 prepares heat ray-reflecting glass, just the consumption of acetylacetone cobalt (III) changes 6.55g into, the nickel (II) with 1.90g second propionyl ketone iron (III) and 5.00g chromium acetylacetonate (III) to replace two propionyl methyl, spray time changes about 30 seconds into, and spraying plated film speed changes the 35ml/ branch into.Identical method by embodiment 1 detects the invisible heat reflection glass coloured glaze that obtains.What obtain the results are shown in table 1.
By the result of table 1 as can be seen, the surface resistivity of the heat ray-reflecting glass of embodiment 1～3 is 10
4Ω/side or 10
4Ω/more than the side, transmission of visible light is below 50% or 50%, and the value that the solar radiation transmissivity is higher than transmission of visible light is no more than 2.5%.In the heat ray-reflecting glass of comparative example 1, transmission of visible light is suppressed to below 50% or 50%, but the solar radiation transmissivity exceeds nearly 5% than transmission of visible light.Therefore, compare with comparative example 1, the protection of solar radiation characteristic of the heat ray-reflecting glass of embodiment 1～3 is fabulous.
Measure embodiment 2 and 3 and the chroma index a of the transmitted light of the heat ray-reflecting glass of comparative example 1 gained
*And b
*The results are shown in as in the following table 2.
Table 2
a
*b
*
Embodiment 3-0.13 8.41
Comparative example 1-0.72 13.80
Embodiment 4～8 and comparative example 2 and 3
Same procedure by embodiment 1 except the composition that changes coated solution prepares heat ray-reflecting glass.Measure transmission of visible light, visible light reflectance, solar radiation transmissivity and the solar radiation reflectance of the heat ray-reflecting glass that obtains by JIS R 3106-1985.In addition, it is according to JIS R 3221-1990 that chemical-resistant is measured, and glass is immersed reach 3 days in the chemical substance and carry out.
What obtain the results are shown among table 3 and Fig. 1.
The acid resistance of plated film is 68～87%(weight at cobalt contents as seen from Figure 1) the zone in be good especially.
By the result of table 3 as can be seen, 50%(weight is arranged) transmission of visible light of the metal oxide plated film of cobalt contents is higher than 50%, but containing 100%(weight) the solar radiation transmissivity that has of the metal oxide plated film of cobalt is high more about 5% than transmission of visible light, can control characteristic so do not reach enough transmissions.
In whole embodiment 1～8, the plated film of acquisition all has uniform outward appearance.
When in embodiment 1～8, when using water white soda-lime glass, can suitably regulate transmission of visible light, solar radiation transmissivity and the transparent tone of the heat ray-reflecting glass that obtains by adopting colored soda-lime glass to do substrate as substrate of glass.
Comparative example 4
Same procedure by embodiment 1 prepares heat ray-reflecting glass, just the consumption of acetylacetone cobalt (III) changes 7.12g into, and the consumption of two propionyl methyl nickel (II) changes 3.13g into, and the consumption of toluene changes 200CC into, spray time changes about 50 seconds into, and spraying plated film speed becomes the 100ml/ branch.The coating film thickness of the heat ray-reflecting glass that obtains is 150nm, and transmission of visible light is 8.5%, but expression resistivity is 1100 Ω/sides.
Embodiment 9
The soda-lime-silica glass plate of one block length 150mm, wide 150mm and thick 4mm washed and dry with the preparation substrate.With suspension bracket this substrate is fixed in 650 ℃ the electric furnace and kept 5 minutes.A kind of coated solution of being made up of the 5.13g acetylacetone cobalt (III), 1.18g two propionyl methyl nickel (II) and the 0.65g vanadium acetylacetonate that are dissolved in the 100 CC toluene is sprayed to in the substrate of taking out in the electric furnace, and spraying is that the commercially available spray gun of employing is 3.0kg/cm in air pressure
2, air velocity is under the 90l/ condition of dividing, the spraying plated film speed of dividing by 20ml/ was carried out 20 seconds and was implemented.
Measure the transmission of visible light of the heat ray-reflecting glass that obtains by JIS R 3106-1985.With in the radio frequency plasma emission spectrometry plated film by the cobalt contents of total metal contents in soil.Measure the surface resistivity and the thickness of plated film.What obtain the results are shown in the following table 4.
Same procedure by embodiment 9 prepares heat ray-reflecting glass, just replaces vanadium acetylacetonate with the 0.66g chromium acetylacetonate, and presses the same procedure detection of embodiment 9.What obtain the results are shown in table 4.
Embodiment 11
Same procedure by embodiment 9 prepares heat ray-reflecting glass, just replaces vanadium acetylacetonate with the 0.66g manganese acetylacetonate, and presses the same procedure detection of embodiment 9.What obtain the results are shown in table 4.
Embodiment 12
Same procedure by embodiment 9 prepares heat ray-reflecting glass, just replaces vanadium acetylacetonate with the 0.66g acetylacetone copper, and presses the same procedure detection of embodiment 9.What obtain the results are shown in table 4.
Embodiment 13
Same procedure by embodiment 9 prepares heat ray-reflecting glass, just replaces vanadium acetylacetonate with 0.66g methyl ethyl diketone zirconium, and presses the same procedure detection of embodiment 9.What obtain the results are shown in table 4.
Comparative example 5
Same procedure by embodiment 9 prepares heat ray-reflecting glass, does not just use vanadium acetylacetonate, and presses the same procedure detection of embodiment 9.What obtain the results are shown in table 4.
By the result of table 4 as can be seen, the surface resistivity of the heat ray-reflecting glass of embodiment 9～13 is 10
4Ω/side or 10
4Ω/more than the side, transmission of visible light is below 50% or 50%, and when having added the metal oxide of vanadium, chromium, manganese or zirconium in plated film, the surface resistivity increase is very big.
Embodiment 14
The mixed in molar ratio that acetylacetone cobalt (II), acetylacetonate nickel (II) and titanium acetylacetone are pressed 78.4/19.6/2, the mixture that 15g is obtained joins 100 CC and contains in polyoxyethylene glycol and the toluene of polydimethylsiloxane as dispersion agent.Adopt coating wobbler (producing) to stir this mixture and obtain coated solution 10 seconds by Eishin company.
The soda-lime-silica glass plate of one block length 300mm, wide 300mm, thick 4mm washed and dry to make substrate.With a suspension bracket this substrate is fixed in 650 ℃ the electric furnace and kept 5 minutes.Adopting commercially available spray gun is 4kg/cm in air pressure
2, air velocity is under the 140 l/ branch conditions the above-mentioned coated solution of 15g to be sprayed in the substrate of taking out from electric furnace, forming thickness is the metal oxide plated film of 50nm.
Measure the transmission of visible light and the solar radiation transmissivity of the heat ray-reflecting glass that obtains by JIS R 3106-1985.Measure the surface resistivity of plated film.What obtain the results are shown in the following table 5.
Same procedure by embodiment 14 makes heat ray-reflecting glass, and just vanadium acetylacetonate, chromium acetylacetonate, manganese acetylacetonate, acetylacetone copper or the methyl ethyl diketone zirconium with same amount replaces titanium acetylacetone.Detect the heat ray-reflecting glass that obtains by embodiment 14 identical methods.What obtain the results are shown in table 5.
Comparative example 6
Make heat ray-reflecting glass except not using the titanium acetylacetone by embodiment 14 identical methods.Detect the heat ray-reflecting glass that obtains by embodiment 14 identical methods.What obtain the results are shown in table 5.
By the result of table 5 as can be seen, can improve the acid resistance of the heat ray-reflecting glass of the plated film that contains cobalt and nickel oxide by the metal oxide that in plated film, adds titanium, vanadium, chromium, manganese, copper or zirconium.Under the situation of vanadium, chromium, manganese, copper or zirconium, acid proof improvement effect is significant.By the embodiment 15～19 that has added oxide compounds such as titanium with do not add relatively it can also be seen that between the comparative example 6 of metal oxide, the heat ray-reflecting glass of embodiment 15～19 has improved the weather resistance of plated film, especially acid resistance, and transmission of visible light and solar radiation transmissivity are remained within certain scope.
In whole embodiment 9～19, the plated film of acquisition has uniform outward appearance.
In embodiment 9～19, use water white soda-lime glass as substrate of glass, can suitably regulate the transmission of visible light of the heat ray-reflecting glass that obtains, solar radiation transmissivity and transparent tone by using colored soda-lime glass.
The soda-lime-silica glass plate of one block length 150mm, wide 150mm, thick 6mm washed and dry to make substrate.With a suspension bracket this substrate is fixed in one 650 ℃ the electric furnace and kept 5 minutes.The coated solution that a kind of 5.3g acetylacetone cobalt (III), 1.2g two propionyl methyl nickel (II) and 0.3g ferric acetyl acetonade (III) that has been dissolved in the 200 CC toluene formed is sprayed in the substrate of taking out from electric furnace, and spraying is that the commercially available spray gun of employing is 1.5kg/cm in air pressure
2, air velocity is under the 50l/ branch condition, carries out about 10 seconds by the spraying plated film speed of 100ml/ branch and implements.
Measure the transmission of visible light of the heat ray-reflecting glass that obtains by JIS R 3106-1985.With in the radio frequency plasma emission spectrometry plated film by the iron level and the nickel content of total metal contents in soil.Determine the crystalline structure of plated film with X-ray diffraction spectrum.The method of measuring coated surface resistivity is that heat ray-reflecting glass is cut into 5 * 4cm, the silver slurry is coated in the width formation electrode of the longer edges of 5cm to 0.5cm, measures resistivity with digital multimeter.The method of measuring wear resistance is by JIS R 3221-1990, Taber wheel rotation 200 changeed, and the difference of the haze values before and after the mensuration processing.The chemical-resistant measuring method is with heat ray-reflecting glass dipping 24 hours in 40 ℃ 1N sulfuric acid or 1N aqueous sodium hydroxide solution, the damage intensity of assessment plated film, observe do not damage in fact be the A level, that observes tangible damage is the B level.What obtain the results are shown in as in the following table 6.
Embodiment 21
Prepare heat ray-reflecting glass by embodiment 20 identical methods, just will change 12mm into as the thickness of the soda-lime-silica glass of substrate.Detect the heat ray-reflecting glass that obtains by embodiment 20 identical methods.What obtain the results are shown in table 6.
Embodiment 22
Same procedure by embodiment 20 prepares heat ray-reflecting glass, and just the consumption with acetylacetone cobalt (III) changes 8.2g into, and the consumption of two propionyl methyl nickel (II) changes 1.2g into, and the consumption of ferric acetyl acetonade (II) changes 0.4g into.Detect the heat ray-reflecting glass that obtains by embodiment 20 identical methods.What obtain the results are shown in the table 6.
Embodiment 23
Same procedure by embodiment 20 prepares heat ray-reflecting glass, and just the consumption with acetylacetone cobalt (III) changes 4.5g into, and the consumption of two propionyl methyl nickel (II) changes 1.2g into, and the consumption of ferric acetyl acetonade (III) changes 0.3g into.Detect the heat ray-reflecting glass that obtains by embodiment 20 identical methods.What obtain the results are shown in the table 6.
Comparative example 7
Same procedure by embodiment 20 prepares heat ray-reflecting glass, and just the consumption with acetylacetone cobalt (III) changes 5.3g into, and the consumption of two propionyl methyl nickel (II) changes 1.2g into, and the consumption of ferric acetyl acetonade (III) changes 0.7g into.Detect the heat ray-reflecting glass that obtains by embodiment 20 identical methods.What obtain the results are shown in the table 6.
Comparative example 8
Same procedure by embodiment 20 prepares heat ray-reflecting glass, just the consumption with acetylacetone cobalt (III) changes 5.3g into, the consumption of two propionyl methyl nickel (II) changes 1.2g into, and the consumption of ferric acetyl acetonade (III) changes 0.7g into, and spray time changes the twice of embodiment 20 into.Detect the heat ray-reflecting glass that obtains by embodiment 20 identical methods.What obtain the results are shown in the table 6.
Comparative example 9
Same procedure by embodiment 20 prepares heat ray-reflecting glass, and just the consumption with acetylacetone cobalt changes 3.3g into, and the consumption of two propionyl methyl nickel (II) changes 2.9g into, and the consumption of ferric acetyl acetonade (III) changes 0.1g into.Detect the heat ray-reflecting glass that obtains by embodiment 20 identical methods.What obtain the results are shown in the table 6.
From the result of table 6 as can be seen, iron level in the plated film is preferably 1.0%(weight) or it is 1.0% above being used to suppress the specific conductivity of plated film, if but iron level is too big, and the weather resistance of then destroying plated film is acid resistance especially, therefore, iron level is preferably 4.5%(weight) or 4.5% below.If nickel content is too big, then the crystalline structure of metal oxide can not become spinel structure in the plated film, will cause the problem as high transmission of visible light.Therefore, also consider that from the weather resistance of plated film the content of nickel is preferably 5～40%(weight).
Embodiment 24
The soda-lime-silica glass plate of one block length 150mm, wide 150mm, thick 6mm washed and dry to make substrate.With a suspension bracket this substrate is fixed in 650 ℃ the electric furnace and kept 5 minutes.Be dissolved in the coated solution that 8.2g acetylacetone cobalt (III) in the 200 CC toluene and 1.2g two propionyl methyl nickel (II) form and be sprayed in the substrate of taking out from electric furnace a kind of, spraying is that to adopt commercially available spray gun be 1.5kg/cm in air pressure
2, air velocity is under the 50 l/ branch conditions, the spraying plated film speed of dividing by 120ml/ was carried out 5 seconds and was implemented.
Measure the transmission of visible light of the heat ray-reflecting glass that obtains according to JIS R 3106-1985.Be determined at the L of JIS Z 8729-1980 regulation according to JIS R 3106-1985
*a
*b
*Chroma index a than color system
*And b
*Determine the crystalline structure of plated film with X-ray diffraction spectrum.The method of measuring the surface resistivity of plated film is that heat ray-reflecting glass is cut into 5 * 4cm, the longer edges that the silver slurry is coated in 5cm to the width of 0.5cm to form electrode, measure resistivity with digital multimeter.The method of measuring wear resistance is according to JIS R 3221-1990 Taber wheel rotation 200 to be changeed, and measures the difference of the turbidity before and after handling.It is with heat ray-reflecting glass dipping 24 hours in the acid solution of JIS R 3221 regulations or alkaline solution that chemical-resistant is measured, and the damage intensity of assessment plated film is not wherein observed the damaged A level that is in fact, and that observes tangible breakage is the B level.What obtain the results are shown in as in the following table 7.
Same procedure by embodiment 24 prepares heat ray-reflecting glass, only is to use the coated solution of being made up of 8.2g acetylacetone cobalt (III), 1.2g two propionyl methyl nickel (II) and 0.7g ferric acetyl acetonade (III) that is dissolved in the 200 CC toluene.Same procedure by embodiment 24 detects the heat ray-reflecting glass that obtains.What obtain the results are shown in the table 7.
Embodiment 26
Same procedure by embodiment 24 prepares heat ray-reflecting glass, the thickness that just is used as the soda-lime-silica glass of substrate of glass is 12mm, and the coated solution of use is to be dissolved in being made up of 8.2g acetylacetone cobalt (III), 1.2g two propionyl methyl nickel (II) and 0.7g ferric acetyl acetonade (III) in the 200 CC toluene.Same procedure by embodiment 24 detects the heat ray-reflecting glass that obtains.What obtain the results are shown in table 7.
Embodiment 27
Same procedure by embodiment 24 prepares heat ray-reflecting glass, and just used thickness is that 6mm, transmitted colour are adjusted to blue soda-lime-silica glass as substrate of glass.Same procedure by embodiment 24 detects the heat ray-reflecting glass that obtains.What obtain the results are shown in the table 7.
Embodiment 28
Same procedure by embodiment 24 prepares heat ray-reflecting glass, and just used thickness is that 5mm, transmitted colour are adjusted to green soda-lime-silica glass as substrate of glass.Same procedure by embodiment 24 detects the heat ray-reflecting glass that obtains.What obtain the results are shown in the table 7.
Comparative example 10
Same procedure by embodiment 24 prepares heat ray-reflecting glass, only is to use the coated solution of being made up of 3.6g acetylacetone cobalt (III) and 1.8g chromium acetylacetonate (III) that is dissolved in the 200 CC toluene.Same procedure by embodiment 24 detects the heat ray-reflecting glass that obtains.What obtain the results are shown in the table 7.
From the result of table 7 as can be seen, adopting soda-lime glass to do to press L among the embodiment 24～26 of substrate
*a
*b
*Chroma index a than color system
*And b
*Drop in the following scope:
-7.0≤a
＊≤-0.3
-5.0≤b
＊≤4.0
The reflected light that tone falls into above-mentioned scope is a green hue, generally has good surface appearance.
Heat ray-reflecting glass of the present invention is to produce by the pyrolysated method based on coated solution, and this method has fabulous productivity.The present invention has improved the weather resistance and the catoptrical tone of electromagnetic reflection, plated film; these are in actual use in the serious problems of considering that environment protection can bring, and the characteristic of heat ray-reflecting glass that therefore keeps containing the plated film of cobalt oxide and nickel oxide can be controlled at transmission of visible light and solar radiation transmissivity below the certain level.
Claims (11)
1, heat ray-reflecting glass contains substrate of glass, and the plated film that contains cobalt oxide and nickel oxide is arranged on the surface of substrate,
The surface resistivity that described plated film has is not less than 10
4Ω/side, thickness is not less than 10nm,
Cobalt contents in the described plated film is counted 60～90% (weight) by the per unit area total metal contents in soil,
Nickel content in the described plated film is counted 10～40% (weight) by the per unit area total metal contents in soil.
2, according to the heat ray-reflecting glass of claim 1, the cobalt contents in the wherein said plated film is counted 68～87%(weight by the per unit area total metal contents in soil), the nickel content in the described plated film is counted 13～32%(weight by the per unit area total metal contents in soil).
3, heat ray-reflecting glass contains substrate of glass, and the plated film that contains cobalt oxide and nickel oxide is arranged on the surface of substrate,
Described plated film also contains at least a metal oxide that is selected from titanium, vanadium, chromium, manganese, copper and the zirconium, and the surface resistivity that has is not less than 10
4Ω/side, thickness is not less than 10nm,
Cobalt contents in the described plated film is counted 60～89%(weight by the per unit area total metal contents in soil),
Nickel content in the described plated film is counted 10～39%(weight by the per unit area total metal contents in soil),
The content that is selected from least a metal of titanium, vanadium, chromium, manganese, copper and zirconium in the described plated film is counted 1～30%(weight by the total metal contents in soil of per unit area).
4, according to the heat ray-reflecting glass of one of claim 1～3, the thickness of wherein said plated film is not more than 130nm.
5, heat ray-reflecting glass contains substrate of glass, and the plated film that contains cobalt oxide and nickel oxide is arranged on the surface of substrate,
Described plated film also contains ferric oxide, and the surface resistivity that has is not less than 10
4Ω/side, thickness are 10～70nm,
Iron level in the described plated film is counted 1.0～4.5%(weight by the per unit area total metal contents in soil).
6, according to the heat ray-reflecting glass of claim 5, the content of nickel is counted 5～40%(weight by the total metal contents in soil of per unit area in the wherein said plated film).
7, according to the heat ray-reflecting glass of one of claim 1～6, wherein from the reflection tone of the unilateral observation of the described heat ray-reflecting glass of described plated film reverse side be green be color.
8, according to the heat ray-reflecting glass of one of claim 1～7, wherein said plated film mainly is made of the oxide compound with spinel structure.
9, according to the heat ray-reflecting glass of one of claim 1～8, wherein the transmission tone of the visible light of transmission demonstration drops on following scope:
-4.5≤a
＊≤4.5
3.0≤b
＊≤12.5
A wherein
*And b
*Represent the chroma index.
10, according to the heat ray-reflecting glass of one of claim 1～9, wherein from the described heat ray-reflecting glass unilateral observation of described plated film reverse side to the reflection that shows of reflect visible light transfer and drop in the following scope:
-7.0≤a
＊≤-0.3
-5.0≤b
＊≤4.0
A wherein
*And b
*Represent the chroma index.
11, heat ray-reflecting glass contains substrate of glass, and the plated film that contains cobalt oxide and nickel oxide is arranged on the surface of substrate,
Described plated film mainly is made of the oxide compound with spinel structure that contains cobalt oxide and nickel oxide, and its surface resistivity is not less than 10
4Ω/side, thickness are 10～70nm,
From the described heat ray-reflecting glass unilateral observation of described plated film reverse side to the reflection tone be green be color.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP335868/93 | 1993-12-28 | ||
| JP335868/1993 | 1993-12-28 | ||
| JP335123/93 | 1993-12-28 | ||
| JP33586893 | 1993-12-28 | ||
| JP335123/1993 | 1993-12-28 | ||
| JP33512393 | 1993-12-28 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1111216A true CN1111216A (en) | 1995-11-08 |
| CN1101354C CN1101354C (en) | 2003-02-12 |
Family
ID=26575066
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94113361A Expired - Fee Related CN1101354C (en) | 1993-12-28 | 1994-12-28 | Heat ray-reflecting glass |
Country Status (5)
| Country | Link |
|---|---|
| KR (1) | KR950017792A (en) |
| CN (1) | CN1101354C (en) |
| GB (1) | GB2285634A (en) |
| SG (1) | SG81880A1 (en) |
| TW (1) | TW293005B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1106357C (en) * | 1997-05-22 | 2003-04-23 | 日本电气硝子株式会社 | Solar reflective glass block and method of producing the same |
| CN102127326A (en) * | 2010-12-28 | 2011-07-20 | 中国科学院上海硅酸盐研究所 | Vanadium dioxide-based composite coating liquid and composite film and preparation methods and applications of coating liquid and composite film |
| CN107586039A (en) * | 2017-11-02 | 2018-01-16 | 北京工业大学 | A kind of low-temperature leadless sealed glass |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001083392A1 (en) | 2000-04-28 | 2001-11-08 | Asahi Glass Company, Limited | Glass coated with heat reflecting colored film and method for manufacturing the same |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2688565A (en) * | 1949-07-01 | 1954-09-07 | Pittsburgh Plate Glass Co | Refractory base containing a low reflection coating and method of making same |
| US2975076A (en) * | 1957-11-12 | 1961-03-14 | Pittsburgh Plate Glass Co | Preparing glass coating compositions |
| GB1002024A (en) * | 1961-02-14 | 1965-08-18 | Libbey Owens Ford Glass Co | Glazing closure |
| US3185586A (en) * | 1961-02-28 | 1965-05-25 | Pittsburgh Plate Glass Co | Coated glass sheets |
| BE785764A (en) * | 1971-07-08 | 1973-01-03 | Glaverbel | |
| US3850665A (en) * | 1971-07-08 | 1974-11-26 | Glaverbel | Process for forming a metal oxide coating on a substrate and resulting products |
| US4160061A (en) * | 1975-03-29 | 1979-07-03 | Central Glass Company, Limited | Heat-reflecting glass plate and method of producing same |
| US4204028A (en) * | 1978-03-16 | 1980-05-20 | Ppg Industries, Inc. | Conductive metal oxide film for solar energy control |
| JPS57149848A (en) * | 1981-03-06 | 1982-09-16 | Asahi Glass Co Ltd | Metallic oxide coated glass |
| CN1029734C (en) * | 1992-04-07 | 1995-09-13 | 林启雄 | Hot-line reflecting glass |
| JPH0859299A (en) * | 1994-08-18 | 1996-03-05 | Nippon Sheet Glass Co Ltd | Heat radiation-reflecting glass and its production |
-
1993
- 1993-12-28 SG SG9605348A patent/SG81880A1/en unknown
-
1994
- 1994-12-22 GB GB9426370A patent/GB2285634A/en not_active Withdrawn
- 1994-12-27 KR KR1019940037114A patent/KR950017792A/en not_active Application Discontinuation
- 1994-12-28 TW TW083112249A patent/TW293005B/zh active
- 1994-12-28 CN CN94113361A patent/CN1101354C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1106357C (en) * | 1997-05-22 | 2003-04-23 | 日本电气硝子株式会社 | Solar reflective glass block and method of producing the same |
| CN102127326A (en) * | 2010-12-28 | 2011-07-20 | 中国科学院上海硅酸盐研究所 | Vanadium dioxide-based composite coating liquid and composite film and preparation methods and applications of coating liquid and composite film |
| CN102127326B (en) * | 2010-12-28 | 2012-10-31 | 中国科学院上海硅酸盐研究所 | Vanadium dioxide-based composite coating liquid and composite film and preparation methods and applications of coating liquid and composite film |
| CN107586039A (en) * | 2017-11-02 | 2018-01-16 | 北京工业大学 | A kind of low-temperature leadless sealed glass |
Also Published As
| Publication number | Publication date |
|---|---|
| GB9426370D0 (en) | 1995-03-01 |
| CN1101354C (en) | 2003-02-12 |
| GB2285634A (en) | 1995-07-19 |
| KR950017792A (en) | 1995-07-20 |
| TW293005B (en) | 1996-12-11 |
| SG81880A1 (en) | 2001-07-24 |
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