CN102239221B - Undercoating layers providing improved topcoat functionality - Google Patents
Undercoating layers providing improved topcoat functionality Download PDFInfo
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- CN102239221B CN102239221B CN200980148470.XA CN200980148470A CN102239221B CN 102239221 B CN102239221 B CN 102239221B CN 200980148470 A CN200980148470 A CN 200980148470A CN 102239221 B CN102239221 B CN 102239221B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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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
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide coatings
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1693—Antifouling paints; Underwater paints as part of a multilayer system
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
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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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/401—Oxides containing silicon
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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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/405—Oxides of refractory metals or yttrium
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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
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/71—Photocatalytic coatings
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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
- C03C2217/00—Coatings on glass
- C03C2217/90—Other aspects of coatings
- C03C2217/91—Coatings containing at least one layer having a composition gradient through its thickness
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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
- C03C2217/00—Coatings on glass
- C03C2217/90—Other aspects of coatings
- C03C2217/94—Transparent conductive oxide layers [TCO] being part of a multilayer coating
Abstract
A coated article includes a substrate and a first coating formed over at least a portion of the substrate. The first coating includes a mixture of oxides including oxides of at least two of P, Si, Ti, Al and Zr. A functional coating is formed over at least a portion of the first coating. The functional coating is selected from an electrically conductive coating and a photoactive coating. In one embodiment, the functional coating includes fluorine doped tin oxide. In another embodiment, the functional coating includes titania.
Description
The cross reference of related application
The coexist right of priority of the U. S. application that the application number submitted on November 19th, 2008 is 12/273,617,12/273,623 and 12/273,641 of the application's request, and all three applications are all introduced the application as a reference.
Background technology
1. technical field
Present invention relates in general to the goods that apply and, relate in particular to the goods of the multiple coating with functional external coating (EC) and at least one undercoat.
2. technical discussion
There are the goods of laminated coating for various application.An example is in field of thin film solar cells.Typical solar cell comprises base material, and such as sheet glass, it has transparent conductive film (the first electrode).Semiconductor film with photoelectric conversion material is deposited on this transparent conductive film.This battery comprises the other base material with transparent conductive film (the second electrode).Comprise ionogen between these two electrodes.When this photoelectric conversion material be adsorbed on this semiconductor film is subject to irradiation, the inside that the electronics produced by this irradiation moves through this semiconductor film and enters one of this transparent conductive film.For example, this electronics can move through the first electrode, pass electrical lead, and the electrode that arrives other.With regard to solar cell, with regard to photoelectric transformation efficiency, importantly electronics moves the electrode to other by the first conductive film as far as possible fast.Namely, if the transparent conductive film surface resistivity is low, cater to the need.If this electronics is quick travel not, compound (being commonly referred to " reversible circulation " or " the anti-electric current that flows ") of this electronics and this photoelectric conversion material may occur.In addition, if this conductive film is highly transparent and allow the solar radiation quantity maximum value to be delivered to this photoelectric conversion material, be desirable.Therefore, the desirable goods that are to provide for the coating of solar cell, it strengthens by the stream of electrons of transparent conductive film.Namely, transparent conductive film has low surface resistivity.
Utilizing the example in the other field of the goods that apply is photocatalyst product fields.Knownly apply photocatalysis coating such as titanium dioxide so that the goods of the coating with self-cleaning property to be provided on base material.Once, to some electromagnetic radiation exposure such as uv-radiation, the organic pollutant on this photocatalysis coating and coatingsurface interacts so that this organic pollutant degradation or decomposition.Yet conventional photocatalyst product has higher visible reflectance and therefore, may not be suitable for the application of some construction applicationies.In addition, conventional photocatalysis coating may experience usually said " sodium-ion poisoning " and degrade, and " sodium-ion poisoning " results within sodium ion breaks away from and enter this photocatalysis coating from this lower floor glass baseplate.In addition, conventional photocatalysis coating tends to show rainbow effect, and it impairs the aesthetic appearance of coated goods.
Therefore, the desirable goods that are to provide coating, it has the undercoat be positioned between base material and functional external coating (EC) (for example but be not limited to conduct conductive coating or the photocatalysis coating that photovoltaic is transparent), and it is not only with doing the obstruct of sodium ion diffusion but also having improved the performance of coated goods.The reflectivity of the goods that for example, this performance can be by reducing this coating and/or provide color suppress and/or improve the functional of this external coating (EC) and improve to these goods.For example, in the photovoltaic application, this undercoat can reduce the surface resistivity of this external coating (EC) (for example transparency conducting layer) to increase stream of electrons.In photocatalytic applications, this undercoat can increase the photocatalytic activity of photocatalysis coating.
Summary of the invention
A kind of goods of coating comprise base material and are formed at the first coating on this base material at least a portion.This first coating comprises P, Si, Ti, the oxide compound of at least two kinds in Al and Zr.Functional coat is formed on this first coating at least a portion.In a kind of unrestricted embodiment, this first coating at least comprises the oxide compound of Ti and Si.In another non-limiting embodiments, this first coating at least comprises Ti, the oxide compound of Si and P.In another non-limiting embodiments, this first coating at least comprises Ti, the oxide compound of Si and Al.Other embodiment can comprise in these materials the combination of two or more.The example of functional coat includes but are not limited to, photolytic activity coating (such as photocatalysis coating and/or light hydrophilic coating), and conductive coating.This functional coat can be coated on the first coating with any combination of said components.
The goods of another coating comprise glass baseplate and are formed at the first coating on this base material at least a portion.This coating comprises P, Si, Ti, the oxide compound of at least two kinds in Al and Zr.Functional coat is formed on this first coating at least a portion.This functional coat is selected the stannic oxide of titanium dioxide and fluorine doping.
The method of the goods that preparation applies comprises provides glass baseplate; By the first coating composition is formed on glass baseplate at least a portion to the first coating through CVD towards the glass baseplate orientation, this first coating composition comprises silica precursor, titanium dioxide precursor and silicon-dioxide promotor, this silicon-dioxide promotor comprises at least one promoter material, this promoter material has P, Al, and at least one in Zr; And by the second coating composition is formed to functional coat through CVD towards the glass baseplate orientation on this first coating at least a portion, stannic oxide precursor composition or titanium dioxide precursor composition that this second layer coating compositions comprises the fluorine doping.
The another kind of goods that apply comprise base material and are formed at the first coating on this base material at least a portion.This first coating comprises oxide mixture, and it comprises P, Si, Ti, the oxide compound of at least two kinds in Al and Zr.Conductive coating is formed on this first coating at least a portion.This conductive coating comprises Zn, Fe, Mn, Al, Ce, Sn, Sb, Hf, Zr, Ni, Zn, Bi, Ti, Co, Cr, the alloy of two or more in one or more oxide compound or these materials in Si or In.
The method that reduces the conductive coating surface resistivity comprises provides base material; Form the first coating on this base material at least a portion, this first coating comprises P, Si, Ti, the oxide compound of at least two kinds in Al and Zr; And form conductive coating on this first coating at least a portion.
The method of the mist degree of the goods that raising applies and/or raising visible ray transparence comprises provides base material; Form the first coating on this base material at least a portion, this first coating comprises P, Si, Ti, the oxide compound of at least two kinds in Al and Zr; And form functional coat on this first coating at least a portion.
The another kind of goods that apply comprise base material and are formed at the first coating on this base material at least a portion.This first coating comprises oxide mixture, and it comprises P, Si, Ti, the oxide compound of at least two kinds in Al and Zr.The photolytic activity coating is formed on this first coating at least a portion.
The goods that photolytic activity applies comprise glass baseplate and are formed at the first coating on this base material at least a portion.The mixture that this first coating comprises silicon-dioxide, titanium dioxide and aluminum oxide.The photolytic activity functional coat that comprises titanium dioxide is formed on this first coating at least a portion.
The method that improves the photocatalytic activity of photolytic activity coating comprises provides base material; Form the first coating on this base material at least a portion, this first coating comprises P, Si, Ti, the oxide compound of at least two kinds in Al and Zr; And form the photolytic activity coating on this first coating at least a portion.
The method for preparing the photolytic activity goods comprises provides glass baseplate; By the first coating composition is formed on this glass baseplate at least a portion to the first coating through CVD towards the glass baseplate orientation, this first coating ingredients comprises tetraethyl orthosilicate, titanium isopropoxide and dimethyl aluminum isopropoxide; And, by the second coating composition is formed on this first coating at least a portion to the photolytic activity coating through CVD towards the glass baseplate orientation, this photolytic activity coating comprises titanium dioxide.
The accompanying drawing explanation
If graphic extension by reference to the accompanying drawings, can realize complete understanding of the present invention from following explanation.
Fig. 1 is side-looking, the sectional view (not in scale) of goods that comprises the coating of feature of the present invention;
Fig. 2 is the curve of the surface resistivity of the direct doped tin oxide coatings in fluorine doping on glass or that form on undercoat of the present invention to [Sn];
Fig. 3 is the curve of the transparence percentage of the direct doped tin oxide coatings in fluorine doping on glass or that form on undercoat of the present invention to wavelength;
Fig. 4 is the curve of the reflectivity of the goods that apply of embodiment 5 to titanium dioxide thickness; And
Fig. 5 is the curve of the colour-change of the goods that apply of embodiment 6.
The preferred embodiment explanation
As used herein, relevant to the present invention " left side ", " right side ", " inside ", " outside ", " going up ", " under " etc. space or directional terminology as shown in drawn accompanying drawing.Yet, be appreciated that the present invention can present various alternative orientations, and therefore restriction do not thought in these terms.In addition, as used herein, the numerical value of all expression sizes, physical property, processing parameter, composition quantity, reaction conditions etc. is used and be considered to use in all cases word " approximately " to modify in specification sheets and claims.Therefore, unless the phase antirepresentation arranged, the desired properties that the numerical value of enumerating in following specification sheets and appended claims can be looked for according to the present invention acquisition changes.At least, and be not to attempt to limit the application of doctrine of equivalents in the claim scope, each numerical parameter at least should and be explained by applying the common technology of rounding up according to the number of reported significant figure.And all scopes disclosed herein should be believed to comprise the value range that starts and finish and all and any subrange comprised therein.For example, the described scope of " 1 to 10 " should be believed to comprise all and any subrange (comprising end value) between the maximum value of 1 minimum value and 10; That is to say, all subranges that start and finish to be equal to or less than maximum value 10 to be equal to or greater than minimum value 1, for example, 1 to 3.3,4.7 to 7.5, and 5.5 to 10 etc.In addition, as used herein, this term " on being formed at ", " on being deposited on ", or " on provide " but meaning forms, deposition or be provided on surface may not directly contact this surface.For example, coating " is formed at " on base material and does not get rid of one or more same or different other coating or films that form and be present between formed coating and this base material.As used herein, this term " polymkeric substance " or " polymer-type " comprise oligopolymer, homopolymer, multipolymer and terpolymer, for example, and by the polymkeric substance of two or more monomers or polymer formation.This term " visible region " or " visible ray " refer to the electromagnetic radiation of wavelength in the 380nm-760nm scope.This term " infrared region " or " ir radiation " refer to that wavelength is being greater than 760nm to 100, the electromagnetic radiation in the 000nm scope.This term " ultraviolet region " or " uv-radiation " refer to wavelength at 300nm to the electromagnetic energy be less than in the 380nm scope.This term " microwave region " or " microwave radiation " refer to the electromagnetic radiation of frequency in 300 megahertz to 300 mega hertz scopes.In addition, all documents, for example be not limited to granted patent and patent application, mentioned in the application, all be considered to " all being incorporated herein by reference ".In discussing hereinafter, this refractive index numerical value is those for reference wavelength is 550 nanometers (nm).This term " film " refer to have require or the zone of the coating of selected composition." layer " comprise one or more " film "." coating " or " coating stack " " layer " forms by one or more.
In Fig. 1, graphic extension comprises the goods 10 of the coating of feature of the present invention.These goods 10 comprise base material 12, and it has at least one major surfaces.The first coating of the present invention (undercoat) 14 is formed on this major surfaces at least a portion.The second coating (functional coat) 16 is formed on first coating 14 at least a portion.It although now disclosed, is specific exemplary embodiment, should understand feature one or more of the present invention that these embodiments comprise can with one or more characteristics combination of other embodiment, and the present invention is not limited to specific exemplary embodiment as described below.
In broad practice of the present invention, this base material 12 can comprise any required material, and it has any required feature.For example, this base material 12 can be transparent, translucent or opaque for visible ray.With regard to " transparent ", meaning visible ray transparence is greater than 0% until 100%.Alternatively, this base material 12 can be translucent or opaque.With regard to " translucent ", mean allow electromagnetic energy (for example visible ray) through but spread this energy so that object can't be clearly visible back to viewer's one side.With regard to " opaque ", meaning visible ray transparence is 0%.Applicable examples of materials includes but are not limited to, and plastic basis material is (such as acrylic polymers, such as polyacrylic ester; Polyalkyl methacrylate, such as polymethylmethacrylate, polyethyl methacrylate, polypropylmethacryla,es etc.; Urethane; Polycarbonate; Polyalkylterephthalaor, such as polyethylene terephthalate (PET), Poly(Trimethylene Terephthalate), polybutylene terephthalate etc.; Polymkeric substance containing polysiloxane; Perhaps for the preparation of these multipolymer or any its mixture of arbitrary monomer); Metal base, be such as but not limited to galvanized steel, stainless steel and aluminium; Ceramic base material; Tile substrate; Glass baseplate; The perhaps mixture of above-mentioned any one or combination.For example, this base material can comprise conventional soda-lime-silicate glass, borosilicate glass or lead glass.This glass can be transparent glass." transparent glass " refers to non-dyeing or non-staining glass.Alternatively, glass can be dyeing or other tinted shade.This glass can be annealing or through the glass of heat treated.As used herein, this term " heat treated " meaning tempering or tempering at least in part.This glass can be arbitrary type, such as conventional float glass, and can have any composition, this composition has any optical property, for example, the visible light transmissivity of any numerical value, ultraviolet ray transmissivity, infrared transmittivity and/or total solar energy transmitance." float glass " refers to that glass is formed by conventional float glass process, and wherein molten glass deposits on bath of molten metal and be controlled cooling to form float glass belt.Although do not limit the present invention, the glass examples that is applicable to this base material is disclosed in United States Patent (USP) 4,746,347; 4,792,536; 5,030,593; 5,030,594; 5,240,886; 5,385,872; With 5,393,593.Can comprise for the limiting examples of implementing glass of the present invention
gL-35
tM,
solarphire
and
glass, all be purchased the Inc. from PPG Industries, Pittsburgh, Pennsylvania.This glass has smooth surface, or alternatively, has the surface of roughening or veining.In a kind of unrestricted embodiment, this glass surface surfaceness (RMS) is 100nm-5mm.
This base material 12 can have size, for example length, width, shape or the thickness of any requirement.For example, this base material 12 can be plane, bending or there is plane with curved part.In a kind of unrestricted embodiment, these base material 12 thickness can be between 1 millimeter to 10 millimeters, such as 1 millimeter to 5 millimeters, such as 2 millimeters to 4 millimeters, such as 3 millimeters to 4 millimeters.
In a kind of unrestricted embodiment, this base material 12 has high visible light transmissivity under 550 nanometers (nm) reference wavelength." high visible light transmissivity " means transmission of visible light under 550 nanometers and is greater than or equal to 85%, such as being greater than or equal to 87%, such as being greater than or equal to 90%, such as being greater than or equal to 91%, such as being greater than or equal to 92%.
The goods 10 that the first coating (undercoat) 14 is this coating provide various performance advantages, as described in detail further below.In a kind of unrestricted embodiment of the present invention, the first coating 14 can be uniform coating." uniform coating " refers to a kind of coating, and wherein this material is to be distributed in randomly this coating everywhere.Alternatively, the first coating 14 can comprise a plurality of coatings or film, (such as two or more coated membrane independently).Also alternatively, the first coating 14 can be gradient layer." gradient layer " meaning layer there is two or more component and make this concentration of component with the variable in distance apart from this base material continuously (or segmentation) change.
In a kind of unrestricted embodiment, the first coating 14 comprises two or more oxide mixtures, and these two or more oxide compounds are selected from the oxide compound of silicon, titanium, aluminium, zirconium and/or phosphorus.This oxide compound can exist by the ratio of any requirement.In a kind of unrestricted embodiment, the mixture that the first coating 14 comprises silicon-dioxide and titanium dioxide, and this dioxide-containing silica scope be 0.1 % by weight (wt.%) to 99.9wt.% and this content of titanium dioxide scope be 99.9wt.%-0.1wt.%.The first coating 14 can be uniform coating.Alternatively, the first coating 14 is gradient claddings, and the ratio that wherein runs through the relative titanium dioxide of silicon-dioxide of this coating changes.For example, the first coating 14 can be rich in this base material adjacent zone silicon-dioxide and be rich in titanium dioxide in these the first coating 14 exterior lateral area.
As discussed above, the first coating 14 can comprise at least two kinds of hopcalites, and these at least two kinds of oxide compounds have the element that is selected from silicon, titanium, aluminium, zirconium and/or phosphorus.Said mixture includes but are not limited to, titanium dioxide and phosphorous oxides; Silicon-dioxide and aluminum oxide; Titanium dioxide and aluminum oxide; Silicon-dioxide and phosphorous oxides; Titanium dioxide and phosphorous oxides; Silicon-dioxide and zirconium white; Titanium dioxide and zirconium white; Aluminum oxide and zirconium white; Aluminum oxide and phosphorous oxides; Zirconium white and phosphorous oxides; Perhaps any combination of above-mentioned materials.This oxide compound relative proportion can be the quantity that exists of any requirement, such as a kind of material is 0.1wt.%-99.9wt.% and another material is 99.9wt.%-0.1wt.%.
In addition, the first coating 14 can comprise at least three kinds of hopcalites, such as rather than be limited to three kinds or more kinds of hopcalite, these three kinds or more kinds of oxide compound have the element that is selected from silicon, titanium, aluminium, zirconium and/or phosphorus.Mixture examples includes but are not limited to, the mixture that comprises following material: silicon-dioxide, titanium dioxide and phosphorous oxides; Silicon-dioxide, titanium dioxide and aluminum oxide; And silicon-dioxide, titanium dioxide and zirconium white.In a kind of unrestricted embodiment, the first coating 14 comprises other hopcalite that silicon-dioxide and titanium dioxide and at least one are selected from aluminum oxide, zirconium white and phosphorous oxides.This oxide compound relative proportion can be the quantity that exists of any requirement, and such as a kind of material is that 0.1wt.%-99.9wt.%, the second material are 99.9wt.%-0.1wt.%, and the 3rd material is 0.1wt.%-99.9wt.%.
The mixture that a kind of specific the first coating 14 of the present invention comprises silicon-dioxide, titanium dioxide and phosphorous oxides.This dioxide-containing silica scope is 30 percent by volumes (vol.%)-80vol.%.This content of titanium dioxide scope is 5vol.%-69vol.%.This phosphorous oxides content range is 1vol.%-15vol.%.
The first coating 14 can have any requirement thickness, such as and be not limited to 10nm-120nm, such as 30nm-80nm, such as 40nm-80nm, such as 30nm-70nm.
The second coating (external coating (EC)) 16 comprises functional coat.Can be used for functional coat example of the present invention and include but are not limited to, control coating, low emissivity coatings and photolytic activity coating at conductive coating, sunshine.
In a kind of unrestricted embodiment, the second coating 16 comprises at least one conductive oxide layer, such as doped oxide layer.For example, the second coating 16 can comprise one or more oxide materials, be such as but not limited to Zn, Fe, Mn, Al, Ce, Sn, Sb, Hf, Zr, Ni, Zn, Bi, Ti, Co, Cr, the alloy of two or more in one or more one or more oxide compounds or these materials such as zinc in Si or In.The second coating 16 can also comprise one or more dopant materials, such as and be not limited to F, In, Al, and/or Sb.In a kind of unrestricted embodiment, the second coating 16 is doped tin oxide coatings of fluorine doping, and in this coating precursor material, fluorine content is for being less than 20wt.%, based on this precursor material gross weight, such as being less than 15 % by weight, such as being less than 13wt.%, such as being less than 10wt.%, such as being less than 5wt.%.The second coating 16 can be amorphous, crystallization or crystallization at least partly.
In a kind of unrestricted embodiment, the stannic oxide that the second coating 16 comprises fluorine doping, its thickness is greater than 200nm, such as being greater than 250nm, such as being greater than 350nm, such as being greater than 380nm, such as being greater than 400nm, such as being greater than 420nm.In a kind of unrestricted embodiment, this thickness range is 350nm-420nm.
The surface resistivity that undercoat of the present invention 14 for example, provides for external coating (EC) 16 (stannic oxide of fluorine doping) is less than 15 ohm-sq (Ω/), such as being less than 14 Ω/, such as being less than 13.5 Ω/, such as being less than 13 Ω/, such as being less than 12 Ω/, such as being less than 11 Ω/, such as being less than 10 Ω/.
In another non-limiting embodiments, the second coating 16 can be the photolytic activity coating.This term " photolytic activity " or " photolytic activity ground " refer to when through the CF radiation irradiation time such as ultraviolet (" UV ") light, producing hole-electron pair.This photolytic activity coating can be light-catalysed, photolytic activity is hydrophilic or the two has." photochemical catalysis " mean coating and have self-cleaning property, be coating when some electromagnetic radiation be exposed to such as UV, just with organic pollutant on this coatingsurface, interact to degrade or decompose this organic pollutant." photolytic activity wetting ability " means a kind of coating, and for it, because coating is exposed to the electromagnetic radiation within this material optical absorption band, on this coating, the water droplet contact angle reduces in time.For example, be at coatingsurface that to be exposed to intensity within this material optical absorption band be 24W/m
2radiation after 60 minutes, this contact angle can reduce to numerical value be less than 15 °, such as being less than 10 °, and the super hydrophilic that can become, for example, be reduced to less than 5 °.Although be photoactive, it is light-catalysed to the automatically cleaning degree that this coating can need not to be, and can need not to be enough light-catalysed with reasonable or available period makes the organic materials decomposition of similar dust and dirt on this coatingsurface economically.For example, this photocatalytic activity can be less than 4x10
-3every centimetre minute (cm
-1min
-1), such as being less than 3x10
-3cm
-1min
-1, such as being less than 2x10
-3cm
-1min
-1, such as being less than 1x10
-3cm
-1min
-1.
This photolytic activity coating can comprise at least one Photoactive coating layer material and optionally at least one additive or doping agent, its configuration so that this coating with coating without this dopant material compared with the photolytic activity effect.This Photoactive coating layer material can comprise at least one oxide compound, such as rather than be limited to one or more oxide compounds or oxide semiconductor, such as titanium oxide, silicon oxide, aluminum oxide, ferric oxide, silver suboxide, cobalt oxide, chromic oxide, cupric oxide, Tungsten oxide 99.999, zinc oxide, zinc/tin-oxide, strontium titanate, and composition thereof.This oxide compound can comprise oxide compound, super-oxide or the suboxide of this element.This oxide compound can be crystalline or at least part of crystallization.In exemplary coating of the present invention, this Photoactive coating layer material is titanium dioxide (titanium dioxide).Titanium dioxide exists with amorphous form and three kinds of crystal habits, namely this anatase octahedrite, rutile and brookite crystal habit.This anatase phase titanium dioxide is particularly useful, because it demonstrates the high light activity, also has fabulous chemical resistance and fabulous physical durability simultaneously.Yet the combination of this Rutile Type or this anatase octahedrite and/or rutile and this brookite and/or amorphous phase also is applicable to the present invention.
The doping agent example that can be used for photolytic activity coating of the present invention comprises, but be not limited to, be the chromium (Cr) of element or ionic state, vanadium (V), manganese (Mn), copper (Cu), iron (Fe), magnesium (Mg), scandium (Sc), yttrium (Y), niobium (Nb), molybdenum (Mo), ruthenium (Ru), tungsten (W), silver (Ag), plumbous (Pb), nickel (Ni), rhenium (Re), tin (Sn), and/or one or more in any mixture or its combination.
In a kind of unrestricted embodiment, the titanium dioxide thickness that the second coating 16 comprises is greater than 10nm, such as being greater than 20nm, such as being greater than 30nm, such as being greater than 40nm, such as being greater than 50nm, such as being greater than 60nm, such as being greater than 70nm, such as being greater than 80nm, such as being greater than 90nm, such as being greater than 100nm, such as in the 10nm-150nm scope.
In a kind of unrestricted embodiment, the first coating 14 of the present invention can be less than for the reflectivity in visible region that these goods 10 with titanium dioxide second coating 16 provide 23%, such as being less than 20%, such as being less than 19%, such as being less than 18%, such as being less than 17%, such as being less than 16%, such as being less than 15%, such as being less than 14%, such as being less than 12%, such as being less than 11%, such as being less than 10%.
The first coating 14 and/or the second coating 16 by any ordinary method, such as rather than be limited to and spray pyrolytic decomposition, chemical vapour deposition (CVD) or magnetron sputtering vacuum moulding machine (MSVD) and be formed on base material 12 at least a portion.At this, spray in pyrolysis method, for example there is the precursor composition that comprises organism or metal for one or more oxide precursor materials of titanium dioxide and/or silicon-dioxide and/or aluminum oxide and/or phosphorous oxides and/or zirconic precursor material, in moisture or suspension non-aqueous solution for example, transport and focus on the surface of this base material simultaneously this base material in sufficiently high temperature to cause this precursor composition decompose and form coating on this base material.Said composition can comprise one or more dopant materials.In the CVD method, precursor composition transports in the carrier gas such as nitrogen, and focuses on this heated substrate.In this MSVD method, in atmosphere inertia or oxygen containing, under reduced pressure sputter contains the cathode target of one or more metals to deposit splash coating on base material.This base material is during applying or heat afterwards to cause this splash coating crystallization to form this coating.
In a kind of unrestricted practice of the present invention, one or more CVD coating units can be used the one or more positions in conventional float glass belt manufacturing process.Pass this annealing furnace or break away from this annealing furnace at it for example, when, the CVD coating unit can be worked as this float glass belt through this tin bath, after it breaks away from this tin bath, before it enters this annealing furnace, when it and use later.Because this CVD method can apply mobile float glass belt, still bear with this float glass belt and prepare relevant severe environment, so this CVD method especially is very suitable in molten tin bath deposited coatings on float glass belt.The patent No. is 4,853,257; 4,971,843; 5,536,718; 5,464,657; 5,714,199; With 5,599,387 United States Patent (USP) has been described CVD coating unit and method, and it can be used for the present invention's practice to apply float glass belt in molten tin bath.
In a kind of unrestricted embodiment, one or more CVD coating machines can be located among the tin bath on this melting tin tank.When this float glass belt passes this tin bath, the precursor composition of this evaporation can add to carrier gas and concentrate on the upper surface of this band.This precursor composition decomposition forms coating (for example the first coating 14 and/or the second coating 16) to be with at this.In a kind of unrestricted embodiment, this coating composition is deposited on this and is with on a position, and the temperature of this position band is less than 1300 °F (704 ℃), such as being less than 1250 °F (677 ℃), such as being less than 1200 °F (649 ℃), such as being less than 1190 °F (643 ℃), such as being less than 1150 °F (621 ℃), such as being less than 1130 °F (610 ℃), such as in 1190 °F-1200 °F (643 ℃-649 ℃) scopes.It is useful that this has to deposition the second coating 16 (for example stannic oxide of fluorine doping) that reduces surface resistivity especially, because the surface resistivity that this depositing temperature is lower, produce is lower.
For example, be the first coating 14 that formation comprises silicon-dioxide and titanium dioxide, said composition comprise silica precursor and titanium dioxide precursor the two.A unrestricted example of silica precursor is tetraethyl orthosilicate (TEOS).
The titanium dioxide precursor example includes but are not limited to, titanyl compound, suboxide or super-oxide.In one embodiment, this titanium dioxide precursor material can comprise alkoxide, the methylate such as titanium, ethylate, propylate, butanolate of one or more titaniums etc.; Perhaps its isomer, such as, titanium isopropoxide, purity titanium tetraethoxide etc.The exemplary precursor material that is applicable to the present invention's practice includes but are not limited to, tetra isopropyl titanate (TPT).Alternatively, this titanium dioxide precursor material can be titanium tetrachloride.The example of alumina precursor includes but are not limited to, three second month in a season of dimethyl aluminium isopropoxide (DMAP) and aluminium-butanolate (ATSB).In a kind of unrestricted embodiment, by the isopropoxide that at room temperature rate 2: 1 is mixed trimethyl aluminium and aluminium in molar ratio in inert atmosphere, prepare this dimethyl aluminium isopropoxide.The example of phosphorous oxides precursor includes but are not limited to, triethyl phosphorite.The example of zirconium oxide precursor includes but are not limited to, zirconium alkoxide.
The first coating 14 with silicon-dioxide and titanium dioxide combination provides the advantage with respect to above-mentioned combination of oxides.For example, the combination of the low refractive index material such as silicon-dioxide (refractive index is 1.5 under 550nm) and the high refractive index material such as titanium dioxide (refractive index is 2.4 under 550nm) changes this refractive index of the first coating 14 by the quantity that changes silicon-dioxide and titanium dioxide between these two kinds of end values.This is particularly useful for color or iris rejection are provided for the first coating 14.
Yet titanium dioxide deposition speed is generally faster than silicon-dioxide.Under general mode of deposition, the quantity of this restriction silicon-dioxide is to no more than approximately 50 % by weight, and it limits the refractive index lower limit of the earth silicon/titanic oxide coating of synthesized successively.Therefore, dopant material can add this silicon-dioxide and titanium dioxide precursor composition so that the acceleration of silica deposit speed.This doping agent forms the part and therefore of the oxide mixture of synthesized, can be selected the performance that the coating of thinking synthesized provides improvement.Can be used for functional coat example of the present invention and include but are not limited to, comprise in phosphorus, aluminium and zirconium one or more material to form the oxide compound of these materials in the coating of synthesized.The example of phosphorous oxides precursor material comprises triethyl phosphorite.The alumina precursor examples of materials comprises tri sec-butoxy aluminum (ATSB) and dimethyl aluminium isopropoxide (DMAP).The example of zirconium oxide precursor comprises zirconium alkoxide.
Embodiment
This embodiment explanation is known clearly by utilizing undercoat of the present invention to suppress layer for the titanium dioxide external coating (EC) as color.This undercoat is the combination of silicon-dioxide, titanium dioxide and phosphorous oxides.
Use the laboratory coating machine to make this primer depo-sition on glass baseplate by chemical gaseous phase depositing process.Then coating of titanium dioxide is deposited on this undercoat.Table 1 shows the coating structure (forming and thickness) for sample 1-4.This primer depo-sition is a plurality of retes with three kinds of primary coat tunics; The first undercoat is on glass baseplate, and the second primary coat tunic is on the first primary coat tunic, and the 3rd undercoat is on the second primary coat tunic.This multilayered structure simulation level undercoat.
Table 1
| |
|
Sample 3 | |
|
| The first primer thickness [nm] | 13 | 11 | 29 | 13 |
| The volume % of phosphorous oxides in the first undercoat | 5 | 10 | 5 | 5 |
| The volume % of silicon-dioxide in the first undercoat | 75 | 80 | 70 | 75 |
| The volume % of titanium dioxide in the |
20 | 10 | 25 | 20 |
| The second primer thickness [nm] | 23 | 33 | 21 | 27 |
| The volume % of phosphorous oxides in the |
2 | 2 | 2 | 2 |
| The volume % of silicon-dioxide in the second undercoat | 49 | 58 | 48 | 62 |
| The volume % of titanium dioxide in the second undercoat | 49 | 40 | 50 | 36 |
| The 3rd primer thickness [nm] | 21 | 18 | 15 | 23 |
| The volume % of phosphorous oxides in the 3rd undercoat | 5 | 11 | 5 | 5 |
| The volume % of silicon-dioxide in the 3rd undercoat | 75 | 80 | 70 | 70 |
| The volume % of titanium dioxide in the |
20 | 9 | 25 | 25 |
| The thickness of external coating (EC) titanium dioxide [nm] | 115 | 121 | 113 | 118 |
The reflection color characteristic data of table 2 show sample 1-4 and comparative sample (glass sheet of titanium dioxide-coated is without this undercoat).For the coated side of this base material, use conventional
software is at D65, and 10 ° of viewers locate to simulate this color data.
Table 2
With regard to this sample, with the goods without this undercoat, to compare, the existence of this undercoat provides lower generally (more negative sense) a* and higher (corrigendum to) b*.
This embodiment has illustrated by utilizing undercoat of the present invention so that the photolytic activity of enhancing is provided to the titanium dioxide external coating (EC).This first coating comprises silicon-dioxide, titanium dioxide and phosphorous oxides.
The two is formed this undercoat and this external coating (EC) (titanium dioxide) by chemical gaseous phase depositing process.This phosphorous oxides precursor is triethyl phosphorite (TEP).This silica precursor is tetraethyl orthosilicate (TEOS).Not only in this undercoat but also the precursor of the titanium dioxide in this external coating (EC) be titanium isopropylate (TPT).Table 3 shows this sample 5-9 deposition parameter.
Table 3
Table 4 shows the layer thickness of this sample 5-9.
Table 4
| Sample 5 | |
Sample 7 | Sample 8 | Sample 9 | |
| Phosphorous oxides [microgram/cm 2] | 1.5 | 2.1 | 1.5 | 1.2 | N/A |
| Titanium dioxide [microgram/cm 2] | 34.4 | 38.4 | 36.0 | 37.0 | 30.2 |
| This primer thickness [nm] | 37.4 | 98.9 | 52.5 | 83.3 | 0 |
| This titania functional coat-thickness [nm] | 132 | 132 | 129 | 121 | 129 |
The conventional stearic acid test result of table 5 show sample 5-9.This stearic acid test is disclosed in U.S. Pat 6,027, in 766, is incorporated herein by reference.As what can see, the goods with undercoat of the present invention have more highlight catalytic active than the goods that do not have this undercoat (sample 9).
Table 5
| PCA(×10 -3cm -1min -1) | |
| Sample 5 | 121 |
| |
121 |
| Sample 7 | 112 |
| Sample 8 | 92 |
| Sample 9 | 61 |
Embodiment 3
The present embodiment has illustrated by utilizing the surface resistivity of undercoat of the present invention with the stannic oxide external coating (EC) of reduction fluorine doping.
This undercoat is silicon-dioxide, titanium dioxide, the phosphorous oxides undercoat that CVD deposits.The precursor used is TEOS (silicon-dioxide), TPT (titanium dioxide), and TEP (phosphorous oxides).On this undercoat and the stannic oxide external coating (EC) that deposits the fluorine doping of various thickness in uncoated (as a comparison sample) on glass.Two coatings are by by being purchased the Market from Electronic Design To, and the surface resistivity of the R-Chek+ 4 point instrumentation amount of Inc. compares.The quantity of [Sn] is measured by x-ray fluorescence, and it is corresponding to the thickness of the doped tin oxide coatings of fluorine doping.Fig. 2 is presented at the stannic oxide layer low 1-3 ohm-sq of the surface resistivity average specific of the doped tin oxide coatings of fluorine doping on undercoat of the present invention in the fluorine doping of same thickness on glass.In Fig. 2, empty square and dotted line are illustrated in the stannic oxide of fluorine doping on glass.Closed circular and solid line are illustrated in the doped tin oxide coatings of the fluorine doping on undercoat of the present invention.This undercoat (forming and thickness) is identical to each sample.
Use the CVD method to use precursor as mentioned above to apply (12 inches * 24 inches of a slice transparent glasses; 30cm * 61cm).Half glass surface is directly at the doped tin oxide coatings of coating fluorine doping on glass and the stannic oxide external coating (EC) of second half coating silicon dioxide of this glass, titanium dioxide, phosphorus undercoat and fluorine doping.Cut sample and as described below the analysis from the glass sheet various piece.
(1) x-ray fluorescence (XRF) data
The amount (in the situation that the FTO/UL coating is stacked slightly higher) of similar [Sn] of this XRF data presentation for two coatings in table 6.
Table 6
| FTO only | FTO/UL | Blank | |
| [P] | 0.09 | 0.56 | 0.09 |
| [Ti] | 0 | 1.87 | 0 |
| [Sn] | 145.8 | 147 | 0.2 |
(2) mist degree and transparence
The mist degree of test sample and transparence in addition.The results are shown in table 7.Transparence spectrum is presented in Fig. 4.With directly comparing at the doped tin oxide coatings (FTO) of fluorine doping on glass, the stacked mist degree of the stannic oxide (FTO) of this fluorine doping/undercoat (UL) coating is higher and transparence is also higher.Therefore, the goods mist degree that undercoat of the present invention also provides raising to apply and the method for transparence.This can be used for area of solar cell, and the mist degree that wherein improved increases the electromagnetic absorption path, its successively, for the absorption of electromagnetic energy provides more multimachine meeting.
Table 7
| FTO only | FTO/UL | |
| Mist degree | 0.89％ | 1.77％ |
| Transparence | 80.78％ | 81.37％ |
(3) surface resistivity
The surface resistivity data presentation is in table 8.This FTO/UL coatingsurface resistance ratio is at low 1.5 Ω of FTO coating on glass/sq.
Table 8
| FTO only | FTO/UL |
| 13.55Ω/sq | 12.05Ω/sq |
(4) coat-thickness
By this etching method, measure, with this FTO on UL (FTO external coating (EC) 334nm) relatively, in the situation that the FTO coating is at (356nm) on glass, this FTO coat-thickness is bigger.
(5) coating porosity
Use scanning electron microscopy (SEM) to watch this coating.Directly in this FTO coating on glass, see a lot of apertures.Do not observe hole in this FTO/UL coating is stacked.
(6) surfaceness
For 10 microns (um) * 10um; 5um * 5um; And the area of 1um * 1um is used atomic force microscopy (AFM) analytical table surface roughness.Result is presented in table 9.In the FTO/UL coating stacked situation lower surface roughness higher than directly at FTO on glass.Surfaceness improves to be risen the coating mist degree and therefore, has increased any impact electromagnetic absorption path.
Table 9
| Sample | RMS roughness (nm) | Ra roughness (nm) |
| FTO 10umx10um only | 13.39 | 10.69 |
| FTO/UL 10umx10um | 17.45 | 13.74 |
| FTO 5umx5um only | 12.53 | 9.99 |
| FTO/UL 5umx5um | 18.03 | 14.09 |
| FTO 1umx1um only | 8.99 | 7.18 |
| FTO/UL 1umx1um | 9.96 | 8.03 |
Embodiment 5
The present embodiment has illustrated the impact of undercoat of the present invention for the reflectivity of the goods that apply.
Fig. 4 shows for TiO on transparent glass
2coating 10 nanometers-120 nanometer (empty rhombus and dotted line) and for same TiO on the undercoat of the present invention on transparent glass
2the reflectance varies of layer.Undercoat is 13nm 75% SiO
2-20% TiO
2-5% P
2o
5/ 23nm 49%SiO
2-49%TiO
2-2% P
2o
5/ 21nm 75% SiO
2-20% TiO
2-5% P
2o
5(closed circular and solid line).TiO
2the variation of thickness is that 5 nanometer intervals are from 10 nanometers to 120 nanometers.
If Fig. 4 shows at this TiO on glass
2functional coat thickness increases, this reflectivity mobility scale wide any quantity of 11.7%<R<38.8% (that is, from).Yet, if this TiO
2functional coat is to be deposited on undercoat, this reflectance varies much lower (that is, scope 17.2%-27.4%).This shows along with external coating (EC) thickness changes, and the stacked reflectivity of whole coatings with undercoat does not resemble without sensitive the situation of the first coating.
In some zones, use the present invention's the first coating, this reflectivity can significantly reduce.Table 10 shows that titanium dioxide coarseness is the reflectivity difference under 55nm and 165nm.
Table 10
| Reflectivity without undercoat | Reflectivity with undercoat | |
| 55nm TiO 2 | 38.8％ | 26.4％ |
| 165nm TiO 2 | 35.6％ | 25.5％ |
The present embodiment has illustrated for example, impact for the color (a* and b*) of the goods that apply of undercoat of the present invention.
Fig. 5 shows for 10nm-120nm TiO on transparent glass
2(empty rhombus and dotted line) and for (13nm 75% SiO of the same coating on undercoat on transparent glass
2-20%TiO
2-5% P
2o
5/ 23nm 49% SiO
2-49% TiO
2-2% P
2o
5/ 21nm 75% SiO
2-20%TiO
2-5%P
2o
5) a* of (closed circular and solid line) and the variation of b*.TiO
2the variation of thickness with 5 nanometer intervals from 10 nanometers to 120 nanometers.
If Fig. 5 shows this TiO
2functional coat thickness increases, and this is without the TiO of undercoat
2coating color (a* and b*) intensity of variation very large (from-24<a*<+37, and-any numerical value of 42<b*<+34).Yet, if this TiO
2functional coat is deposited on as mentioned above on undercoat, the only less variation of this a* and b* (scope is-8<a*<+12, and-10<b*<+7).This means along with external coating (EC) thickness changes, the stacked color of whole coatings with undercoat of the present invention does not resemble without sensitivity undercoat.
Embodiment 7
This embodiment has illustrated the impact of the gradient undercoat of silicon-dioxide and titanium dioxide for titanium dioxide external coating (EC) (120nm is thick) photocatalytic activity.
Table 11 shows the composition of two gradient undercoats.
Table 11
Table 12 shows to be compared with the titanium dioxide activity that there is no undercoat, and two undercoats of table 11 are for the photocatalytic activity impact of 120nm thickness titanium dioxide external coating (EC).[Ti] unit is microgram/cm
2.
Table 12
It will be readily appreciated by those skilled in the art that not deviating from the present invention under the disclosed ultimate principle of above-mentioned explanation can be improved.Therefore, the detailed disclosed specific embodiments of the application is only illustrative and do not limit the scope of the invention, scope of the present invention by the whole width of appended claims with and any and all Equivalents provide.
Claims (15)
1. the goods of a coating comprise:
Base material;
The first coating formed on this base material at least a portion, this first coating comprises in P, Si, Ti, Al and Zr the oxide compound of at least two kinds; And
The functional coat formed on this first coating at least a portion, wherein this functional coat is selected from conductive coating and photolytic activity coating, and
Wherein this first coating comprises 30-80 volume % silicon-dioxide, 1-15 volume % phosphorous oxides and 5-69 volume % titanium dioxide.
2. the goods of claim 1, wherein this first coat-thickness is 10nm-120nm.
3. the goods of claim 1, wherein this first coating is gradient cladding.
4. the goods of claim 1, wherein this first coating is laminated coating, it comprises:
Comprise the first layer that 5-10 volume % phosphorous oxides, 70-80 volume % silicon-dioxide and 10-25 volume % titanium dioxide and thickness are 11nm-29nm;
Comprise the second layer that 2 volume % phosphorous oxidess, 48-62 volume % silicon-dioxide and 36-50 volume % titanium dioxide and thickness are 21nm-33nm; And
Comprise the 3rd layer that 5-11 volume % phosphorous oxides, 70-80 volume % silicon-dioxide and 9-25 volume % titanium dioxide and thickness are 15nm-23nm.
5. the goods of claim 1, wherein this functional coat is conductive coating, its comprise in Zn, Fe, Mn, Al, Ce, Sn, Sb, Hf, Zr, Ni, Zn, Bi, Ti, Co, Cr, Si and In one or more oxide compound or these materials in two or more alloy.
6. the goods of claim 5, wherein this functional coat comprises at least one doping agent that is selected from F, In, Al and Sb.
7. the goods of claim 6, the stannic oxide that wherein this functional coat comprises the fluorine doping.
8. the goods of claim 1, wherein this functional coat is the photolytic activity coating that comprises titanium dioxide.
9. the goods of claim 1, the color gamut that wherein these goods have is-10≤a
*≤ 2 and-15≤b
*≤ 0.
10. the goods of claim 1, the wherein a of these goods
*scope is-8 to-4.4, b
*scope is-12.6 to-5.2, and L
*scope is 50.5 to 52.3.
11. the goods of claim 8, wherein the thickness of this titania functional coating is 10nm at least.
12. the goods of claim 1, wherein this functional coat is selected from the stannic oxide of titanium dioxide and fluorine doping.
13. the method for the goods that preparation applies comprises:
Glass baseplate is provided;
By the first coating composition is formed on glass baseplate at least a portion to the first coating through CVD towards the glass baseplate orientation, the silicon-dioxide promotor that the first coating composition comprises silica precursor, titanium dioxide precursor and comprises at least one promoter material, this promoter material has at least one in P, Al and Zr; And
By the second coating composition is formed to functional coat through CVD towards the glass baseplate orientation on first coating at least a portion, stannic oxide precursor composition or titanium dioxide precursor composition that this second coating composition comprises the fluorine doping, and
Wherein this first coating comprises 30-80 volume % silicon-dioxide, 1-15 volume % phosphorous oxides and 5-69 volume % titanium dioxide.
14. the method for claim 13, wherein the first painting is deposited as gradient cladding.
15. the method for claim 13, wherein the first painting is deposited as laminated coating.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US12/273,623 | 2008-11-19 | ||
| US12/273,617 US7998586B2 (en) | 2008-11-19 | 2008-11-19 | Undercoating layers providing improved topcoat functionality |
| US12/273,641 US8133599B2 (en) | 2008-11-19 | 2008-11-19 | Undercoating layers providing improved photoactive topcoat functionality |
| US12/273,623 US20100124642A1 (en) | 2008-11-19 | 2008-11-19 | Undercoating layers providing improved conductive topcoat functionality |
| US12/273,617 | 2008-11-19 | ||
| US12/273,641 | 2008-11-19 | ||
| PCT/US2009/064292 WO2010059507A1 (en) | 2008-11-19 | 2009-11-13 | Undercoating layers providing improved topcoat functionality |
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| CN102239221A CN102239221A (en) | 2011-11-09 |
| CN102239221B true CN102239221B (en) | 2013-12-25 |
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| JP (1) | JP5343133B2 (en) |
| CN (1) | CN102239221B (en) |
| CA (1) | CA2743845A1 (en) |
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| FI116297B (en) * | 2004-01-07 | 2005-10-31 | Kemira Pigments Oy | Method for surface treatment |
| US7431992B2 (en) * | 2004-08-09 | 2008-10-07 | Ppg Industries Ohio, Inc. | Coated substrates that include an undercoating |
| EP1833768B1 (en) * | 2004-12-21 | 2012-06-13 | AGC Glass Europe | Glazing panel with a multilayer coating |
| JP4852526B2 (en) * | 2005-02-07 | 2012-01-11 | 帝人デュポンフィルム株式会社 | Conductive laminated film |
| US8097340B2 (en) * | 2006-02-08 | 2012-01-17 | Ppg Industries Ohio, Inc. | Coated substrates having undercoating layers that exhibit improved photocatalytic activity |
-
2009
- 2009-11-13 DE DE112009003493T patent/DE112009003493T5/en not_active Withdrawn
- 2009-11-13 CN CN200980148470.XA patent/CN102239221B/en not_active Expired - Fee Related
- 2009-11-13 JP JP2011537513A patent/JP5343133B2/en not_active Expired - Fee Related
- 2009-11-13 CA CA2743845A patent/CA2743845A1/en not_active Abandoned
- 2009-11-13 WO PCT/US2009/064292 patent/WO2010059507A1/en active Application Filing
- 2009-11-13 RU RU2011124950/05A patent/RU2481364C2/en not_active IP Right Cessation
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1074890A (en) * | 1991-12-26 | 1993-08-04 | 北美埃尔夫爱托化学股份有限公司 | The method of coating glass substrates |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2010059507A1 (en) | 2010-05-27 |
| CA2743845A1 (en) | 2010-05-27 |
| DE112009003493T5 (en) | 2012-09-06 |
| JP5343133B2 (en) | 2013-11-13 |
| RU2481364C2 (en) | 2013-05-10 |
| CN102239221A (en) | 2011-11-09 |
| RU2011124950A (en) | 2012-12-27 |
| JP2012509214A (en) | 2012-04-19 |
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