CN102239221A - Undercoating layers providing improved topcoat functionality - Google Patents
Undercoating layers providing improved topcoat functionality Download PDFInfo
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- CN102239221A CN102239221A CN200980148470XA CN200980148470A CN102239221A CN 102239221 A CN102239221 A CN 102239221A CN 200980148470X A CN200980148470X A CN 200980148470XA CN 200980148470 A CN200980148470 A CN 200980148470A CN 102239221 A CN102239221 A CN 102239221A
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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 application number submitted on November 19th, 2008 of the application's request is the right of priority of 12/273,617,12/273,623 and 12/273,641 U. S. application, and all three applications are all introduced the application as a reference.
Background technology
1. technical field
The goods that present invention relates in general to apply and, relate in particular to the goods of multiple coating with functional external coating (EC) and at least one undercoat.
2. technical discussion
Goods with laminated coating are used 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 (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 (second electrode).Between these two electrodes, comprise ionogen.When this photoelectric conversion material that is adsorbed on this semiconductor film is subjected to irradiation, the inside of passing this semiconductor film and entering one of this transparent conductive film by the electron migration that this irradiation produced.For example, this electronics can move through first electrode, pass electrical lead, and the electrode that arrives other.With regard to solar cell, importantly electron migration should be as far as possible fast by the electrode of first conductive film to other with regard to photoelectric transformation efficiency.Just, if the transparent conductive film surface resistivity is low, then 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 then may be taken place.In addition, if this conductive film is a highly transparent and allow the solar radiation quantity maximum value to be delivered to this photoelectric conversion material, then be desirable.Therefore, the desirable goods that provide the coating that is used for solar cell, it strengthens the stream of electrons by transparent conductive film.Just, transparent conductive film has low surface resistivity.
Utilizing the example in the other field of the goods that apply is photocatalyst product fields.Knownly on base material, apply photocatalysis coating such as titanium dioxide so that the goods of the coating with self-cleaning property to be provided.In case to some electromagnetic radiation exposure such as uv-radiation, the organic pollutant on this photocatalysis coating and the coatingsurface interacts so that this organic pollutant degradation or decomposition.Yet conventional photocatalyst product has than 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 from sodium ion and break away from from this lower floor glass baseplate and enter within this photocatalysis coating.In addition, conventional photocatalysis coating tends to show the rainbow effect, and it impairs the aesthetic appearance of coated goods.
Therefore, the desirable goods that provide coating, it has the undercoat that is positioned between base material and the functional external coating (EC) (for example but be not limited to conduct transparent conductive coating of photovoltaic or photocatalysis coating), and it is not only with doing the obstruct of sodium ion diffusion but also having improved the performance of coated goods.For example, the reflectivity of the goods that this performance can be by reducing this coating and/or provide color to suppress and/or improve the functional of this external coating (EC) and improve to these goods.For example, in photovoltaic was used, 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 first coating that is formed on this base material at least a portion.This first coating comprises P, Si, Ti, at least two kinds oxide compound among Al and the Zr.Functional coat is formed on this first coating at least a portion.In a kind of unrestricted embodiment, this first coating comprises the oxide compound of Ti and Si at least.In another non-limiting embodiments, this first coating comprises Ti at least, the oxide compound of Si and P.In another non-limiting embodiments, this first coating comprises Ti at least, 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 first coating with any combination of said components.
The goods of another coating comprise glass baseplate and first coating that is formed on this base material at least a portion.This coating comprises P, Si, Ti, at least two kinds oxide compound among Al and the Zr.Functional coat is formed on this first coating at least a portion.This functional coat is selected titanium dioxide and the adulterated stannic oxide of fluorine for use.
The method of the goods that preparation applies comprises provides glass baseplate; By first coating composition is formed first coating towards the glass baseplate orientation through CVD on glass baseplate at least a portion, this first coating composition comprises silica precursor, titanium dioxide precursor and silicon-dioxide promotor, this silicon-dioxide promotor comprises at least a promoter material, this promoter material has P, Al, and at least a among the Zr; And by second coating composition is formed functional coat through CVD towards the glass baseplate orientation on this first coating at least a portion, this second layer coating compositions comprises adulterated stannic oxide precursor composition of fluorine or titanium dioxide precursor composition.
The another kind of goods that apply comprise base material and first coating that is formed on this base material at least a portion.This first coating comprises oxide mixture, and it comprises P, Si, Ti, at least two kinds oxide compound among Al and the 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 among Si or the In.
The method that reduces the conductive coating surface resistivity comprises provides base material; Form first coating on this base material at least a portion, this first coating comprises P, Si, Ti, at least two kinds oxide compound among Al and the Zr; And on this first coating at least a portion, form conductive coating.
The method of the mist degree of the goods that raising applies and/or raising visible light transparence comprises provides base material; Form first coating on this base material at least a portion, this first coating comprises P, Si, Ti, at least two kinds oxide compound among Al and the Zr; And on this first coating at least a portion, form functional coat.
The another kind of goods that apply comprise base material and first coating that is formed on this base material at least a portion.This first coating comprises oxide mixture, and it comprises P, Si, Ti, at least two kinds oxide compound among Al and the 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 first coating that is formed on this base material at least a portion.This first coating comprises the mixture of 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 first coating on this base material at least a portion, this first coating comprises P, Si, Ti, at least two kinds oxide compound among Al and the Zr; And on this first coating at least a portion, form the photolytic activity coating.
The method for preparing the photolytic activity goods comprises provides glass baseplate; By first coating composition is formed first coating towards the glass baseplate orientation through CVD on this glass baseplate at least a portion, this first coating ingredients comprises tetraethyl orthosilicate, titanium isopropoxide and dimethyl aluminum isopropoxide; And by second coating composition is formed the photolytic activity coating towards the glass baseplate orientation through CVD on this first coating at least a portion, this photolytic activity coating comprises titanium dioxide.
Description of drawings
If graphic extension in conjunction with the accompanying drawings then 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 directly at the surface resistivity of the adulterated doped tin oxide coatings of fluorine on glass or that form on the undercoat of the present invention curve to [Sn];
Fig. 3 is directly at the transparence percentage of the adulterated doped tin oxide coatings of fluorine on glass or that form on the undercoat of the present invention curve 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 ", spaces such as " descending " or directional terminology such as show in the drafting accompanying drawing.Yet, be appreciated that the present invention can present various alternate 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, one-tenth dosis refracta, reaction conditions etc. uses be considered to use in all cases word " approximately " to modify in specification sheets and claims.Therefore, unless the phase antirepresentation is arranged, the desired properties that the numerical value of enumerating in following specification sheets and appended claims can be looked for acquisition according to the present invention changes.At least, and be not to attempt to limit the application of doctrine of equivalents in the claim scope, each numerical parameter should be explained according to the number of the significant figure of being reported and by using the common technology of rounding up at least.And all scopes disclosed herein should be believed to comprise the value range of beginning and end and all and any subrange that comprise 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, to be equal to or greater than minimum value 1 beginning and to be equal to or less than all subranges that maximum value 10 finishes, 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 ", perhaps " on provide " but meaning forms, deposition or be provided on the surface may not directly contact this surface.For example, coating " be formed at " do not get rid of on the base material one or more same or different other coatings of forming or film be present between the coating that forms 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 light " refer to the electromagnetic radiation of wavelength in the 380nm-760nm scope.This term " infrared region " or " ir radiation " refer to wavelength 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 less than the electromagnetic energy 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 " is formed by one or more.
Graphic extension comprises the goods 10 of the coating of feature of the present invention in Fig. 1.These goods 10 comprise base material 12, and it has at least one major surfaces.First coating of the present invention (undercoat) 14 is formed on this major surfaces at least a portion.Second coating (functional coat) 16 is formed on first coating, 14 at least a portion.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 material that requires, and it has any feature that requires.For example, this base material 12 can be transparent, translucent or opaque for visible light.With regard to " transparent " meaning visible light transparence greater than 0% until 100%.Interchangeable is that this base material 12 can be translucent or opaque.With regard to " translucent ", mean and allow that electromagnetic energy (for example visible light) passes but spread this energy so that object can't be clearly visible back to viewer's one side.Meaning visible light transparence is 0% with regard to " opaque ".The examples of materials that is fit to includes but are not limited to, and plastic basis material is (such as acrylic polymers, such as polyacrylic ester; Polyalkyl methacrylate is such as polymethylmethacrylate, polyethyl methacrylate, polypropylmethacryla,es etc.; Urethane; Polycarbonate; Polyalkylterephthalaor, such as polyethylene terephthalate (PET), Poly(Trimethylene Terephthalate), polybutylene terephthalate etc.; The polymkeric substance that contains polysiloxane; Perhaps be used to prepare these arbitrary monomeric multipolymer or any its mixture); Metal base, be such as but not limited to galvanized steel, stainless steel and aluminium; Ceramic base material; Tile substrate; Glass baseplate; Perhaps above-mentioned each mixture 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 " is meant non-dyeing or non-staining glass.Interchangeable is that 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 the float glass of routine, 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 " is meant that glass is formed by the float glass process of routine, wherein molten glass deposit on the bath of molten metal and controlled cooling to form float glass belt.Though do not limit the present invention, the glass examples that is fit 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.The limiting examples that can be used to implement glass of the present invention comprises
GL-35
TM,
Solarphire
And
Glass all is purchased the Inc. from PPG Industries, Pittsburgh, Pennsylvania.This glass has smooth surface, perhaps 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 have planar and 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 that transmission of visible light is greater than or equal to 85% under 550 nanometers, 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%.
First coating (undercoat) 14 provides various performance advantages for the goods 10 of this coating, as described in detail further below.In a kind of unrestricted embodiment of the present invention, first coating 14 can be a uniform coating." uniform coating " refers to a kind of coating, and wherein this material is to be distributed in this coating randomly everywhere.Interchangeablely be, first coating 14 can comprise a plurality of coatings or film, (such as two or more coated membrane independently).Also interchangeable is that first coating 14 can be a gradient layer." gradient layer " meaning layer has two or more a plurality of component and this concentration of component is changed with apart from the variable in distance of this base material and continuously (perhaps segmentation).
In a kind of unrestricted embodiment, 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, first coating 14 comprises the mixture of silicon-dioxide and titanium dioxide, and this dioxide-containing silica scope be 0.1 weight % (wt.%) to 99.9wt.% and this content of titanium dioxide scope be 99.9wt.%-0.1wt.%.First coating 14 can be a uniform coating.Interchangeable is that first coating 14 is gradient claddings, wherein runs through the ratio variation of the relative titanium dioxide of silicon-dioxide of this coating.For example, first coating 14 can be rich in silicon-dioxide in this base material adjacent zone and be rich in titanium dioxide in these first coating, 14 exterior lateral area.
As discussed above, 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, is 0.1wt.%-99.9wt.% and another material is 99.9wt.%-0.1wt.% such as a kind of material.
In addition, 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, and comprises the mixture of 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, first coating 14 comprises silicon-dioxide and titanium dioxide and at least a other hopcalite that is selected from aluminum oxide, zirconium white and phosphorous oxides.This oxide compound relative proportion can be the quantity that exists of any requirement, be that 0.1wt.%-99.9wt.%, second material are 99.9wt.%-0.1wt.% such as a kind of material, and the 3rd material is 0.1wt.%-99.9wt.%.
A kind of first specific coating 14 of the present invention comprises the mixture of 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.%.
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, conductive coating, sunshine control coating, low emissivity coatings and photolytic activity coating.
In a kind of unrestricted embodiment, second coating 16 comprises at least a conductive oxide layer, such as doped oxide layer.For example, 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 among Si or the In.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, second coating 16 is the adulterated doped tin oxide coatings of fluorine, and fluorine content is less than 20wt.% in this coating precursor material, based on this precursor material gross weight, such as less than 15 weight %, such as less than 13wt.%, such as less than 10wt.%, such as less than 5wt.%.Second coating 16 can be amorphous, crystalline or partial crystallization at least.
In a kind of unrestricted embodiment, second coating 16 comprises the adulterated stannic oxide of fluorine, and its thickness is greater than 200nm, such as greater than 250nm, such as greater than 350nm, such as greater than 380nm, such as greater than 400nm, such as greater than 420nm.In a kind of unrestricted embodiment, this thickness range is 350nm-420nm.
The surface resistivity that undercoat 14 of the present invention provides for external coating (EC) 16 (for example adulterated stannic oxide of fluorine) less than 15 ohm-sq (Ω/), such as less than 14 Ω/, such as less than 13.5 Ω/, such as less than 13 Ω/, such as less than 12 Ω/, such as less than 11 Ω/, such as less than 10 Ω/.
In another non-limiting embodiments, second coating 16 can be the photolytic activity coating.This term " photolytic activity " or " photolytic activity ground " refer to when producing hole-electron pair through the CF radiation irradiation time such as ultraviolet (" UV ") light.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 that is exposed to such as UV, just interact with degraded or decompose this organic pollutant with organic pollutant on this coatingsurface." 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, the water droplet contact angle reduces in time on this coating.For example, be at coatingsurface and be exposed to that intensity is 24W/m within this material optical absorption band
2Radiation after 60 minutes, this contact angle can reduce to numerical value less than 15 °, such as less than 10 °, and the super hydrophilic that can become for example, is reduced to less than 5 °.Though be photoactive, it is light-catalysed to the automatically cleaning degree that this coating can need not to be, and promptly can need not to be enough light-catalysed with in that rationally or economically the available period makes the organic materials decomposition of similar dust and dirt on this coatingsurface.For example, this photocatalytic activity can be less than 4x10
-3Every centimetre minute (cm
-1Min
-1), such as less than 3x10
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-1Min
-1
This photolytic activity coating can comprise at least a Photoactive coating layer material and optional at least a additive or doping agent, its configuration so that the coating of this coating and this dopant material of nothing compared with the photolytic activity effect.This Photoactive coating layer material can comprise at least a 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 partial crystallization at least.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, just 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 phase 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 includes but are not limited to, and is 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 in any mixture or its combination one or more.
In a kind of unrestricted embodiment, the titanium dioxide thickness that second coating 16 comprises is greater than 10nm, such as greater than 20nm, such as greater than 30nm, such as greater than 40nm, such as greater than 50nm, such as greater than 60nm, such as greater than 70nm, such as greater than 80nm, such as greater than 90nm, such as greater than 100nm, such as in the 10nm-150nm scope.
In a kind of unrestricted embodiment, the reflectivity in the visible region that first coating 14 of the present invention can provide for these goods 10 with titanium dioxide second coating 16 is less than 23%, such as less than 20%, such as less than 19%, such as less than 18%, such as less than 17%, such as less than 16%, such as less than 15%, such as less than 14%, such as less than 12%, such as less than 11%, such as less than 10%.
In a kind of unrestricted practice of the present invention, one or more CVD coating units can use the one or more positions in the float glass belt manufacturing process of routine.For example, the CVD coating unit can work as this float glass belt when passing this tin bath, pass this annealing furnace or break away from this annealing furnace at it after it breaks away from this tin bath, before it enters this annealing furnace, when it and use later on.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 passed 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 first coating 14 and/or 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 the position, and the temperature of this position band is less than 1300 °F (704 ℃), such as less than 1250 °F (677 ℃), such as less than 1200 °F (649 ℃), such as less than 1190 °F (643 ℃), such as less than 1150 °F (621 ℃), such as less than 1130 °F (610 ℃), such as in 1190-1200 (643 ℃-649 ℃) scopes.It is useful that this has second coating 16 (for example adulterated stannic oxide of fluorine) that reduces surface resistivity to deposition especially, because this depositing temperature surface resistivity low more, that produced is low more.
For example, for formation comprises first coating 14 of 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, for example, titanium isopropoxide, purity titanium tetraethoxide etc.The exemplary precursor material that is fit to the present invention's practice includes but are not limited to tetra isopropyl titanate (TPT).Interchangeable is that this titanium dioxide precursor material can be a titanium tetrachloride.The example of alumina precursor includes but are not limited to, the three second month in a season-butanolate (ATSB) of dimethyl aluminium isopropoxide (DMAP) and aluminium.In a kind of unrestricted embodiment, by in inert atmosphere at room temperature in molar ratio rate 2: 1 isopropoxide that mixes trimethyl aluminium and aluminium 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.
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 about 50 weight %, and it limits the refractive index lower limit of institute's synthetic earth silicon/titanic oxide coating successively.Therefore, dopant material can add this silicon-dioxide and titanium dioxide precursor composition so that silica deposit speed is quickened.This doping agent forms the part of institute's synthetic oxide mixture and therefore, can selectedly think that institute's synthetic coating provides the performance of improvement.Can be used for functional coat example of the present invention and include but are not limited to, the material that comprises in phosphorus, aluminium and the zirconium one or more is to form the oxide compound of these materials in institute's synthetic coating.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 and is used for the titanium dioxide external coating (EC) by utilizing undercoat of the present invention to suppress layer 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.Coating of titanium dioxide is deposited on this undercoat then.Table 1 shows the coating structure (forming and thickness) that is used for sample 1-4.This primer depo-sition is a plurality of retes with three kinds of primary coat tunics; 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 | |
|
| First primer thickness [nm] | 13 | 11 | 29 | 13 |
| The volume % of phosphorous oxides in first undercoat | 5 | 10 | 5 | 5 |
| The volume % of silicon-dioxide in first undercoat | 75 | 80 | 70 | 75 |
| The volume % of titanium dioxide in |
20 | 10 | 25 | 20 |
| Second primer thickness [nm] | 23 | 33 | 21 | 27 |
| The volume % of phosphorous oxides in |
2 | 2 | 2 | 2 |
| The volume % of silicon-dioxide in second undercoat | 49 | 58 | 48 | 62 |
| The volume % of titanium dioxide in 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 does not have this undercoat).Use conventional at the coated side of this base material
Software is at D65, and 10 ° of viewers locate to simulate this color data.
Table 2
With regard to this sample, to compare with the goods that do not have this undercoat, 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 provide the enhanced photolytic activity 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 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 |
| |
92 |
| Sample 9 | 61 |
Embodiment 3
Present embodiment has illustrated by utilizing undercoat of the present invention to reduce the surface resistivity of the adulterated stannic oxide external coating (EC) of fluorine.
This undercoat is silicon-dioxide, titanium dioxide, the phosphorous oxides undercoat that CVD deposits.The precursor that uses is TEOS (silicon-dioxide), TPT (titanium dioxide), and TEP (phosphorous oxides).On this undercoat and uncoated (sample as a comparison) on glass the deposition all thickness the adulterated stannic oxide external coating (EC) of fluorine.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 adulterated doped tin oxide coatings of fluorine.Fig. 2 is presented at the surface resistivity average specific of the adulterated doped tin oxide coatings of fluorine on the undercoat of the present invention in the low 1-3 ohm-sq of the adulterated stannic oxide layer of the fluorine of same thickness on glass.In Fig. 2, empty square and dotted line are illustrated in the adulterated stannic oxide of fluorine on glass.Closed circular and solid line are illustrated in the adulterated doped tin oxide coatings of fluorine on the undercoat of the present invention.This undercoat (forming and thickness) is identical to each sample.
Precursor applies (12 inches * 24 inches of a slice transparent glasses to use the CVD method to use as mentioned above; 30cm * 61cm).Half glass surface is directly at adulterated doped tin oxide coatings of coating fluorine on glass and the adulterated stannic oxide external coating (EC) of second half coating silicon dioxide of this glass, titanium dioxide, phosphorus undercoat and fluorine.Cut sample and as described below the analysis from the glass sheet various piece.
(1) x-ray fluorescence (XRF) data
The amount (higher slightly under the stacked situation of FTO/UL coating) 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 among Fig. 4.With directly comparing at the adulterated doped tin oxide coatings of fluorine on glass (FTO), the stacked mist degree of the adulterated stannic oxide of this fluorine (FTO)/undercoat (UL) coating is higher and transparence is also higher.Therefore, undercoat of the present invention also provides the goods mist degree of raising coating and the method for transparence.This can be used for area of solar cell, and wherein the mist degree that is 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
Measure by this etching method, compare with this FTO (FTO external coating (EC) 334nm) on UL, under the situation of (356nm) on glass, this FTO coat-thickness is bigger in the FTO coating.
(5) coating porosity
Use scanning electron microscopy (SEM) to watch this coating.Directly in this FTO coating on glass, see a lot of apertures.In this FTO/UL coating is stacked, do not observe the hole.
(6) surfaceness
For 10 microns (um) * 10um; 5um * 5um; And the area of 1um * 1um uses atomic force microscopy (AFM) analytical table surface roughness.The result is presented in the table 9.Be higher than directly at FTO on glass in the stacked situation lower surface roughness of FTO/UL coating.The surfaceness raising is risen the coating mist degree and therefore, has been 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
Present embodiment has illustrated the influence 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 the 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 be 5 nanometers at interval from 10 nanometers to 120 nanometers.
If Fig. 4 shows at this TiO on glass
2Functional coat thickness increases, then this reflectivity mobility scale wide any amount of 11.7%＜R＜38.8% (that is, from).Yet, if this TiO
2Functional coat is to be deposited on the undercoat, then 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 the situation of not having first coating sensitive.
In some zones, use the present invention's first coating, this reflectivity can significantly reduce.Table 10 shows that titanium dioxide coarseness is the reflectivity difference under 55nm and the 165nm.
Table 10
| The reflectivity of no undercoat | The reflectivity of band undercoat | |
| 55nm?TiO 2 | 38.8％ | 26.4％ |
| 165nm?TiO 2 | 35.6％ | 25.5％ |
Present embodiment has illustrated the influence of undercoat of the present invention for the color (for example a* and b*) of the goods that apply.
Fig. 5 shows for 10nm-120nm TiO on transparent glass
2(empty rhombus and dotted line) and at (13nm 75% SiO of the same coating on undercoat on the 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 nanometers at interval from 10 nanometers to 120 nanometers.
If Fig. 5 shows this TiO
2Functional coat thickness increases, the TiO of this no undercoat
2Coating color (a* and b*) intensity of variation very big (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 the 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 do not resemble no undercoat sensitivity.
Embodiment 7
This embodiment has illustrated the influence 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 does not have undercoat, and two undercoats of table 11 are for the photocatalytic activity influence 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 and do not deviate from that the present invention can improve under the disclosed ultimate principle of above-mentioned explanation.Therefore, the detailed disclosed specific embodiments of the application only is 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 (20)
1. the goods of a coating comprise:
Base material;
First coating that forms on this base material at least a portion, this first coating comprise among P, Si, Ti, Al and the Zr at least two kinds oxide compound; And
The functional coat that forms on this first coating at least a portion, wherein this functional coat is selected from conductive coating and photolytic activity coating.
2. the goods of claim 1, wherein this first coating comprises the oxide compound of Ti and Si at least.
3. the goods of claim 1, wherein this first coating comprises the oxide compound of Ti, Si and P at least.
4. the goods of claim 1, wherein this first coating comprises the oxide compound of Ti, Si and Al at least.
5. the goods of claim 1, wherein this first coating comprises 30-80 volume % silicon-dioxide, 1-15 volume % phosphorous oxides and 5-69 volume % titanium dioxide.
6. the goods of claim 1, wherein this first coat-thickness is 10nm-120nm, such as 30nm-70nm.
7. the goods of claim 1, wherein this first coating is a gradient cladding.
8. the goods of claim 1, wherein this first coating is a laminated coating, it comprises:
Comprising 5-10 volume % phosphorous oxides, 70-80 volume % silicon-dioxide and 10-25 volume % titanium dioxide and thickness is the first layer of 11nm-29nm;
The second layer that comprises 2 volume % phosphorous oxidess, 48-62 volume % silicon-dioxide and 36-50 volume % titanium dioxide and thickness 21nm-33nm; And
Comprise 5-11 volume % phosphorous oxides, 70-80 volume % silicon-dioxide and 9-25 volume % titanium dioxide and thickness and be the 3rd layer of 15nm-23nm.
9. the goods of claim 1, wherein this functional coat is a conductive coating, its comprise among Zn, Fe, Mn, Al, Ce, Sn, Sb, Hf, Zr, Ni, Zn, Bi, Ti, Co, Cr, Si and the In one or more oxide compound or these materials in two or more alloy.
10. the goods of claim 9, wherein this functional coat comprises at least a doping agent that is selected from F, In, Al and Sb.
11. the goods of claim 10, wherein this functional coat comprises the adulterated stannic oxide of fluorine.
12. the goods of claim 1, wherein this functional coat is the photolytic activity coating that comprises titanium dioxide.
13. the goods of claim 1, wherein the color gamut that has of these goods is-10≤a
*≤ 2 and-15≤b
*≤ 0.
14. 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.
15. the goods of claim 12, wherein the thickness of this titanium dioxide is for 10nm at least, such as 113nm-121nm.
16. the goods of claim 1, wherein first coating comprises Si, and the oxide compound of Ti and P and this functional coat are selected titanium dioxide and the adulterated stannic oxide of fluorine for use.
17. the goods of claim 1, wherein first coating mixture and this functional coat that comprise silicon-dioxide, titanium dioxide and aluminum oxide comprises titanium dioxide.
18. the method for the goods that preparation applies comprises:
Glass baseplate is provided;
By first coating composition is formed first coating towards the glass baseplate orientation through CVD on glass baseplate at least a portion, first coating ingredients comprises silica precursor, titanium dioxide precursor and comprises the silicon-dioxide promotor of at least a promoter material, and this promoter material has at least a among P, Al and the Zr; And
By second coating composition is formed functional coat through CVD towards the glass baseplate orientation on first coating at least a portion, this second coating composition comprises adulterated stannic oxide precursor composition of fluorine or titanium dioxide precursor composition.
19. the method for claim 18 wherein first is coated with and is deposited as gradient cladding.
20. the method for claim 18 wherein first is coated with and is deposited as laminated coating.
Applications Claiming Priority (7)
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|---|---|---|---|
| US12/273,617 | 2008-11-19 | ||
| US12/273,641 US8133599B2 (en) | 2008-11-19 | 2008-11-19 | Undercoating layers providing improved photoactive topcoat functionality |
| US12/273,617 US7998586B2 (en) | 2008-11-19 | 2008-11-19 | Undercoating layers providing improved topcoat functionality |
| US12/273,623 | 2008-11-19 | ||
| US12/273,623 US20100124642A1 (en) | 2008-11-19 | 2008-11-19 | Undercoating layers providing improved conductive topcoat functionality |
| 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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| JP (1) | JP5343133B2 (en) |
| CN (1) | CN102239221B (en) |
| CA (1) | CA2743845A1 (en) |
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- 2009-11-13 DE DE112009003493T patent/DE112009003493T5/en not_active Withdrawn
- 2009-11-13 JP JP2011537513A patent/JP5343133B2/en not_active Expired - Fee Related
- 2009-11-13 CN CN200980148470.XA patent/CN102239221B/en not_active Expired - Fee Related
- 2009-11-13 CA CA2743845A patent/CA2743845A1/en not_active Abandoned
- 2009-11-13 RU RU2011124950/05A patent/RU2481364C2/en not_active IP Right Cessation
- 2009-11-13 WO PCT/US2009/064292 patent/WO2010059507A1/en active Application Filing
Patent Citations (2)
| 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 |
| US20060029813A1 (en) * | 2004-08-09 | 2006-02-09 | Kutilek Luke A | Coated substrates that include an undercoating |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104039731A (en) * | 2012-01-10 | 2014-09-10 | Ppg工业俄亥俄公司 | Coated glasses having low sheet resistance, smooth surface, and/or low thermal emissivity |
| CN104039731B (en) * | 2012-01-10 | 2017-06-06 | Vitro可变资本股份有限公司 | The glass of the coating with low film resistor, smooth surface and/or low-heat emissivity |
| CN105074937A (en) * | 2013-03-12 | 2015-11-18 | Ppg工业俄亥俄公司 | Solar cell with selectively doped conductive oxide layer and method of making the same |
| CN108807566A (en) * | 2013-03-12 | 2018-11-13 | Vitro可变资本股份有限公司 | Solar cell and preparation method thereof with chosen property doped conductive oxide layer |
| US11031514B2 (en) | 2013-03-12 | 2021-06-08 | Vitro, S.A.B. De C.V. | Solar cell with selectively doped conductive oxide layer and method of making the same |
| CN106655995A (en) * | 2017-02-09 | 2017-05-10 | 河南弘大新材科技有限公司 | Self-cleaning type photoelectric conversion solar tile |
| CN106655995B (en) * | 2017-02-09 | 2019-03-12 | 河南弘大新材科技有限公司 | Self-cleaning photoelectric conversion solar tile |
| CN107458052A (en) * | 2017-07-18 | 2017-12-12 | 南京工业职业技术学院 | A kind of automatically cleaning polyethylene film and preparation method thereof |
| CN107458052B (en) * | 2017-07-18 | 2019-07-02 | 南京工业职业技术学院 | A kind of automatically cleaning polyethylene film and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| RU2011124950A (en) | 2012-12-27 |
| WO2010059507A1 (en) | 2010-05-27 |
| RU2481364C2 (en) | 2013-05-10 |
| CA2743845A1 (en) | 2010-05-27 |
| JP2012509214A (en) | 2012-04-19 |
| DE112009003493T5 (en) | 2012-09-06 |
| CN102239221B (en) | 2013-12-25 |
| JP5343133B2 (en) | 2013-11-13 |
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