CN106564242B - Low radiation coated glass and its laminated glass articles containing two layers of infrared reflecting layer - Google Patents
Low radiation coated glass and its laminated glass articles containing two layers of infrared reflecting layer Download PDFInfo
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- CN106564242B CN106564242B CN201610974134.2A CN201610974134A CN106564242B CN 106564242 B CN106564242 B CN 106564242B CN 201610974134 A CN201610974134 A CN 201610974134A CN 106564242 B CN106564242 B CN 106564242B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
- B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/061—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10165—Functional features of the laminated safety glass or glazing
- B32B17/10174—Coatings of a metallic or dielectric material on a constituent layer of glass or polymer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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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
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3613—Coatings of type glass/inorganic compound/metal/inorganic compound/metal/other
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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
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3626—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer one layer at least containing a nitride, oxynitride, boronitride or carbonitride
-
- 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
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3644—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the metal being silver
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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
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3657—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having optical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/416—Reflective
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Surface Treatment Of Glass (AREA)
- Laminated Bodies (AREA)
Abstract
The present invention relates to the low radiation coated glass used on coating film on glass field, the especially vehicles, more specifically low radiation coated glass and its laminated glass articles containing two layers of infrared reflecting layer.The low radiation coated glass containing two layers of infrared reflecting layer includes glass substrate, is set gradually outward on the glass baseplate surface：Inner medium layer, the first infrared reflecting layer, middle dielectric layer, the second infrared reflecting layer, outermost dielectric layer.The present invention is especially the geometric thickness and optical thickness of outermost dielectric layer by rationally designing the thickness of each film layer, on the one hand improves mechanical stability, can substantially reduce scuffing during following process, scratch trace；On the other hand the ability to bear to chemical corrosivity substance is enhanced；Simultaneously, additionally it is possible to promote the albedo to infra-red radiation, improve the spectrum property of its laminated glass articles；In addition, also having the advantages that observing reflection colour in wide range keeps neutral.
Description
Technical field：
The present invention relates to Low emissivity (low-e) coated glasss used on coating film on glass field, the especially vehicles, more
Low radiation coated glass and its laminated glass articles specifically containing two layers of infrared reflecting layer.
Background technology：
As the promotion of the energy conservation and environmental awareness of people and the requirement to the comfort of vehicles seating are higher and higher,
Low emissivity (low-e) coated glass, which is applied to more and more widely on the vehicles, is used as transparent glass window, this is because low
Radiation film coating glass has the advantages that through visible light and reflects infrared ray, so as to significantly reduce air conditioning energy consumption and carry
The comfort level of high driver and passenger.Currently, the transparent glass window used on the vehicles is mostly Silver-based low emissivity coated glass,
The core material of Silver-based low emissivity coated glass is silver (Ag) layer of one layer or multilayer, due to silver (Ag) layer be easy to be corroded and
Oxidation, so the transparent dielectric layer for having and capable of penetrating visible light must all be deposited in the upper and lower of silver-colored (Ag) layer.In general, having
The low radiation coated glass of one silver layer is referred to as single silver low-radiation coated glass, and there are two the low radiation coated glass of silver layer for tool
It is referred to as double-silver low-emissivity coated glass, there are three the low radiation coated glass of silver layer to be referred to as three-silver low radiation plated film glass for tool
Glass.
In practice, more and more double-silver low-emissivity coated glass are widely used, general double-silver low-emissivity coated glass
Film structure be the silver layer of glass substrate/inner medium layer/first silver layer/middle dielectric layer/second/outermost dielectric layer.For answering
For double-silver low-emissivity coated glass on the vehicles, film layer will also allow for withstanding up to 600~700 DEG C
High-temperature heat treatment, and certain chemistry and mechanical damage can be born, therefore farthest away from the outermost dielectric layer pair of glass substrate
The protective effect of silver layer is even more important.Now in the art, the metal oxygen that outermost dielectric layer generally use refractive index is 1.8~2.6
Compound or metal nitride, and its geometric thickness is not higher than 100nm, in practice normally no higher than 70nm, this is because traditional
Ground generally believes if selecting bigger thickness that cannot obtain more neutral appearance color and sufficiently high production efficiency.Such as
Chinese patent CN1134921A discloses a kind of double-silver low-emissivity coated glass, film structure from glass substrate outward successively
It is：Si3N4Layer/nickel or nickel-chrome alloy layer/silver layer/nickel or nickel-chrome alloy layer/Si3N4Layer/nickel or nickel-chrome alloy layer/silver layer/nickel or
Nickel-chrome alloy layer/Si3N4Layer, outermost dielectric layer are Si3N4Layer, geometric thickness are 35~70nm.Similarly, Chinese patent
CN1078219A discloses a kind of high-performance and durable low-E glass, double silverskin architectures from glass substrate outward according to
It is secondary to be：Si3N4Layer/nickel-chrome alloy layer/silver layer/nickel-chrome alloy layer/silver layer/nickel-chrome alloy layer/Si3N4Layer, outermost dielectric layer are
Si3N4Layer, geometric thickness are 54~57.5nm.For these double silver-layer low-radiation glass, in use, manufactures and studied
It is found to still have following disadvantage in journey：1, mechanical stability is insufficient, and scuffing, scratch are easy tod produce during following process
The defects of；2, chemical stability is insufficient, and aqueous vapor, corrosive gas in air, not clean enough water, fingerprint etc. are easy to cause
Film layer is corroded；3, the geometric thickness of outermost dielectric layer is normally no higher than 70nm, and even multi-purpose 30~40nm is very easy to
Local defect caused by appearance mechanical friction, chemical erosion or high temperature.
Invention content：
The technical problem to be solved by the present invention is to the double-silver low-emissivity coated glass in for the above-mentioned prior art to exist
Mechanical stability is insufficient, chemical stability is insufficient and the geometric thickness of outermost dielectric layer is relatively thin and leads to local defect etc. and lacks
Point provides a kind of low radiation coated glass containing two layers of infrared reflecting layer, while also providing a kind of low-emission coated containing this
The laminated glass articles of glass.
The technical scheme adopted by the invention to solve the technical problem is that：It is low-emission coated containing two layers infrared reflecting layer
Glass, including glass substrate, it is characterised in that：It is set gradually outward on the glass baseplate surface：
Inner medium layer, geometric thickness are 15~40nm；
First infrared reflecting layer, geometric thickness are 7~16nm；
Middle dielectric layer, geometric thickness are 70~110nm；
Second infrared reflecting layer, geometric thickness are 7~16nm；
Outermost dielectric layer, geometric thickness be 125~180nm, optical thickness be 300~350nm, refractive index be 1.7~
2.6, the material of the outermost dielectric layer be selected from Zn, Sn, Ti, Nb, Zr, Hf, Mg, Ni, In, Al, Ga, W, Bi metal oxide and
At least one of its mixture, or selected from Si, Al, Zr, Ti, Y, Hf, Nb, Ta metal nitride or nitrogen oxides and its mix
Close at least one of object.
Further, first infrared reflecting layer or the second infrared reflecting layer are in silver, gold, copper, aluminium and its alloy
At least one.
Further, the geometric thickness of the outermost dielectric layer is 140~170nm, and optical thickness is 310~340nm.
Further, the outermost dielectric layer includes Si3N4Sublayer, AlN sublayers, ZnSnOx sublayers, ZnO sublayers, TiO2Son
Layer, SnO2Sublayer, WO3Sublayer, Bi2O3Sublayer, HfO2Sublayer and Nb2O5At least one of sublayer.
Further, when outermost dielectric layer includes Si3N4When sublayer, the Si3N4In sublayer doped with Al, Ni, Zr or
Hf。
Further, when outermost dielectric layer includes ZnO sublayers, in the ZnO sublayers doped with Al, Ga, Mo, Mg,
In, F or B.
Further, when outermost dielectric layer includes ZnSnOx sublayers, in the ZnSnOx sublayers doped with Al, Sb,
Mg, Ni or Y.
Further, the inner medium layer or middle dielectric layer be selected from Zn, Si, Sn, Ti, Nb, Zr, Hf, Mg, Ni, In,
At least one of Al, Ga, W, Bi metal oxide and its mixture, or it is selected from Si, Al, Zr, Ti, Y, Hf, Nb, Ta metal
Nitride or at least one of nitrogen oxides and its mixture.
Further, the inner medium layer further includes the first ZnO sublayers, the first ZnO sublayers be located at inner medium layer and
Between first infrared reflecting layer.
Further, the middle dielectric layer further includes the 2nd ZnO sublayers, and the 2nd ZnO sublayers are located at intermediate medium
Between layer and the second infrared reflecting layer.
Further, infrared with first between outermost dielectric layer and the second infrared reflecting layer, and/or in middle dielectric layer
Barrier layer is set between reflecting layer, the geometric thickness of the barrier layer is 0.3~5nm, the barrier layer be selected from Ni, Cr, Ti,
The metal of Zn, Sn, Hf, Zr, Al metal and its alloy, non-fully oxide, non-fully at least one of nitride.
Meanwhile the present invention also provides a kind of laminated glass articles, including two blocks of glass and it is clipped between two blocks of glass
Interbed, it is characterised in that：It is selected from above-mentioned low radiation coated glass, the low radiation coated glass at least one piece in two blocks of glass
Plated film be located at close to middle layer one side.
The present invention has the advantages that due to taking above-mentioned technical proposal：
Low radiation coated glass and its laminated glass articles of the present invention containing two layers of infrared reflecting layer, pass through conjunction
The thickness of each film layer of reason design is especially the geometric thickness and optical thickness of outermost dielectric layer, on the one hand improves mechanically stable
Property can substantially reduce scuffing during following process, scratch trace；On the other hand it enhances to chemical corrosivity substance
Ability to bear；Simultaneously, additionally it is possible to promote the albedo to infra-red radiation, improve the spectrum property of its laminated glass articles；
In addition, also having the advantages that observing reflection colour in wide range keeps neutral.
Description of the drawings：
Fig. 1 is the film layer structure schematic diagram of the low radiation coated glass of the present invention containing two layers of infrared reflecting layer；
Fig. 2 is that outermost dielectric layer is ZnO:Its ZnSnOx thicknesses of layers and normal incidence reflection colour when Al 8nm/ZnSnOx
Coordinate relational graph；
Fig. 3 is that outermost dielectric layer is ZnO:Its ZnSnOx thicknesses of layers and 60 ° of incident reflection colours when Al 8nm/ZnSnOx
Coordinate relational graph；
Fig. 4 is one embodiment structural schematic diagram of laminated glass articles of the present invention；
Fig. 5 is another example structure schematic diagram of laminated glass articles of the present invention；
Fig. 6 is the transmitted light spectrogram of embodiment 1 and comparative example 1 of the present invention；
Fig. 7 is the reflectance spectrum figure of embodiment 1 and comparative example 1 of the present invention；
In figure：1, inner medium layer；2, the first infrared reflecting layer；3, middle dielectric layer；4, the second infrared reflecting layer；5, it is outermost
Dielectric layer；6, the first barrier layer；7, the second barrier layer；8, inner layer glass substrate；9, middle layer；10, glass outer substrate；11,
First ZnO sublayers；31, the 2nd ZnO sublayers；100, glass substrate；101, it is low-emission coated；A+, it is red；A-, green；B+, it is yellow
Color；B-, blue.
Specific implementation mode：
Present disclosure is described further below in conjunction with attached drawing, is not filling the bright thicknesses of layers
It is geometric thickness；Wherein, the refractive index value of film layer is the refractive index value at 550nm wavelength, and the optical thickness of film layer is
The product of the geometric thickness of refractive index and film layer at 550nm wavelength.
As shown in Figure 1, the low radiation coated glass of the present invention containing two layers of infrared reflecting layer, including glass substrate
100, it is characterised in that：It is set gradually outward on 100 surface of the glass substrate：
Inner medium layer 1, geometric thickness are 15~40nm；
First infrared reflecting layer 2, geometric thickness are 7~16nm；
Middle dielectric layer 3, geometric thickness are 70~110nm；
Second infrared reflecting layer 4, geometric thickness are 7~16nm；
Outermost dielectric layer 5, geometric thickness be 125~180nm, optical thickness be 300~350nm, refractive index be 1.7~
2.6, the material of the outermost dielectric layer is selected from the metal oxides such as Zn, Sn, Ti, Nb, Zr, Hf, Mg, Ni, In, Al, Ga, W, Bi
And its at least one of mixture, or selected from metal nitrides or the nitrogen oxides such as Si, Al, Zr, Ti, Y, Hf, Nb, Ta and
At least one of its mixture.
Wherein, outermost dielectric layer 5 is each by rationally designing for protecting its other film layer between glass substrate 100
The thickness of film layer is especially the geometric thickness and optical thickness of outermost dielectric layer 5, and thermal stability, the chemistry that can improve membrane system are steady
Qualitative and mechanical stability to realize high-durability, and can make final laminated glass articles have neutral color
Reflection appearance.Preferably, the outermost dielectric layer 5 includes Si3N4Sublayer, AlN sublayers, ZnSnOx sublayers, ZnO sublayers, TiO2Son
Layer, SnO2Sublayer, WO3Sublayer, Bi2O3Sublayer, HfO2Sublayer and Nb2O5At least one of sublayer namely the outermost medium
Layer 5 can be Si3N4Sublayer, AlN sublayers, ZnSnOx sublayers, ZnO sublayers, TiO2Sublayer, SnO2Sublayer, WO3Sublayer, Bi2O3Son
Layer, HfO2Sublayer or Nb2O5Sublayer can also be made of arbitrary two layers or two layers or more of sublayer in above-mentioned sublayer.
Meanwhile being herein ZnO with outermost dielectric layer 5:Al/ZnSnOx citings illustrate of the present invention containing two
The laminated glass articles that the low radiation coated glass of layer infrared reflecting layer is constituted have the reflection appearance of neutral color, wherein ZnO:
Al indicates the ZnO sublayers for being doped with Al, ZnO:The thickness of Al is 8nm, by changing the thickness of ZnSnOx i.e. from traditional 20nm
400nm is increased to, measures the normal incidence reflection colour and 60 ° of incident reflection colours of final laminated glass articles respectively, to
Influence of the change of assessment ZnSnOx thicknesses of layers to the low angle and high angle reflection colour of its laminated glass articles.A+ in figure
Red is represented, a- represents green, and b+ represents yellow, and b- represents blue；In coordinate system, more to the close expression color of coordinate origin
It is more shallow, it is on the contrary then indicate that color is deeper.
From in Fig. 2 and Fig. 3 as can be seen that when the thickness of ZnSnOx is 20nm (in traditional double-silver low-emissivity coated glass
The typical thickness of ZnSnOx) when, the low angle of laminated glass articles and 60 degree of reflection colour are the indigo plant of pleasant respectively
It is green and light blue；When being even up to hundreds of nanometers with the increase of the thickness of ZnSnOx, in most thickness ranges,
Inaesthetic color is presented in the reflection colour of laminated glass articles, such as can be seen from Figure 2 the thickness of ZnSnOx is
The normal incidence reflection colour of its laminated glass articles is dark purple when 40nm, and the normal incidence of its laminated glass articles is anti-when 100nm
It is in navy blue to penetrate color, and the normal incidence reflection colour of its laminated glass articles is dark green when 120nm；Or high angle observation and
Significant color distortion is presented when observing in low angle, such as its laminated glass articles when the thickness of ZnSnOx is 120nm in Fig. 2
Normal incidence reflection colour is dark green, and in Fig. 3 ZnSnOx thickness be 120nm when its laminated glass articles 60 ° of incidences it is anti-
It penetrates color and significant purple is but presented.Based on this, before as the transparent glass window on the vehicles, especially automobile
Gear, skylight, rear shelves or side window, which are often required that in low angle and high angle observation, neutral or certain pleasant coloring
The thickness of appearance, such as blue-green, light blue or bluish violet, traditional ZnSnOx has practical value, but simply increases
The thickness of ZnSnOx is difficult then to obtain the laminated glass articles with practical value.On the contrary, in the present invention, passing through rational design
The thickness of each film layer is especially the geometric thickness and optical thickness of outermost dielectric layer 5, such as ZnSnOx shown in Fig. 2 and Fig. 3
Thickness its laminated glass articles when being 145nm normal incidence reflection colour in pale blue green, 60 ° of incident reflection colours are in neutrality
Color；The normal incidence reflection colour of its laminated glass articles is in light blue, 60 ° of incident reflection face when the thickness of ZnSnOx is 150nm
Color is in neutrality color.Herein, when the thickness of ZnSnOx is 145nm or 150nm, the geometric thickness of corresponding outermost dielectric layer 5
It is 311nm or 321nm for 153nm or 158nm, optical thickness；In conjunction with Fig. 2 and Fig. 3 as it can be seen that the thickness in ZnSnOx is 145nm
Or near 150nm, there are a thickness ranges, its laminated glass articles can be made to reflect face when low angle and high angle are observed
Color is almost the same and appearance color with pleasant, i.e. the thickness in two dotted ellipse regions in Fig. 2 and Fig. 3, preferably most
The geometric thickness of outer dielectric layer 5 is 140~170nm, and optical thickness is 310~340nm, and the thickness setting of outermost dielectric layer 5 exists
The laminated glass product of membrane system structure within the scope of this has great practical value.Although in addition, empty in figure 2 and figure 3
There is also the selections of other thickness for line elliptic region, such as ZnSnOx thickness is 368nm, although its appearance color same good one
It causes, but considers the blocked up some problem brought of film layer, such as stress in thin film increases, production cost is excessively high, technique controlling difficulty
Increase, does not have practical value also.
Preferably, in order to advanced optimize film performance, it includes Si that can work as outermost dielectric layer 53N4It is described when sublayer
Si3N4Doped with Al, Ni, Zr or Hf in sublayer.Equally, it when outermost dielectric layer 5 includes ZnO sublayers, is mixed in the ZnO sublayers
It is miscellaneous to have Al, Ga, Mo, Mg, In, F or B；When outermost dielectric layer includes ZnSnOx sublayers, in the ZnSnOx sublayers doped with
Al, Sb, Mg, Ni or Y.
Wherein, 2 and second infrared reflecting layer of the first infrared reflecting layer, 4 major function is for reflecting infrared ray, subtracting
Few infrared ray is transmitted from low radiation coated glass, so the film material of the first infrared reflecting layer 2 and the second infrared reflecting layer 4
Any material for capableing of reflecting infrared energy can be selected, such as (but being not limited to) in silver, gold, copper, aluminium and its alloy
At least one, in the present invention preferably silver or argentiferous alloy, wherein the alloy of argentiferous in the present invention preferably silver with
The alloy of at least one of gold, aluminium, copper.Silver has been selected in an embodiment of the present invention, can effectively reduce radiance, has been improved
Heat-proof quality.
Wherein, the inner medium layer 1 and middle dielectric layer 3 can reduce the reflection of visible light region, be infrared reflecting layer
Suitable growth basis is provided and keeps the high-temperature stability of infrared reflecting layer.Also, inner medium layer 1 due to and glass substrate
100 are in direct contact, additionally it is possible to obstruct Na atoms, oxygen atom and other foreign atoms in glass substrate 100 to infrared reflecting layer
Intrusion destroy, and enough adhesion strengths are provided between low radiation film and glass substrate 100.Preferably, interior Jie
Matter layer 1 or middle dielectric layer 3 be selected from the metal oxides such as Zn, Si, Sn, Ti, Nb, Zr, Hf, Mg, Ni, In, Al, Ga, W, Bi and
At least one of its mixture, or selected from metal nitrides or the nitrogen oxides such as Si, Al, Zr, Ti, Y, Hf, Nb, Ta and its
At least one of mixture.
Further, the inner medium layer 1 further includes the first ZnO sublayers 11, and the first ZnO sublayers 11 are located at interior medium
Between layer 1 and the first infrared reflecting layer 2.Similarly, the middle dielectric layer 3 further includes the 2nd ZnO sublayers 31, and described second
ZnO sublayers 31 are located between middle dielectric layer 3 and the second infrared reflecting layer 4.
Optionally, the first barrier layer 6 is set between outermost dielectric layer 5 and the second infrared reflecting layer 4, and/or in centre
Second barrier layer 7 is set between dielectric layer 3 and the first infrared reflecting layer 2, it is red in subsequent medium layer deposition process for preventing
Outer reflective layer metal is by Oxidative demage, and for improving infrared reflecting layer-dielectric layer interfacial adhesion, first barrier layer
6 and second barrier layer 7 geometric thickness be 0.3~5nm, first barrier layer, 6 and second barrier layer 7 be selected from Ni, Cr, Ti,
The metal of the metals such as Zn, Sn, Hf, Zr, Al and its alloy, non-fully oxide, non-fully at least one of nitride.
Laminated glass articles of the present invention as shown in Figure 4 and Figure 5, including two blocks of glass and be clipped in two blocks of glass it
Between middle layer 9, two blocks of glass are respectively inner layer glass substrate 8 and glass outer substrate 10；In Fig. 4, glass outer substrate
Close to the one side setting low-emission coated 101 of middle layer 9 on 10, i.e. the glass outer of this laminated glass articles is of the present invention
Low radiation coated glass；In Figure 5, the one side on inner layer glass substrate 8 close to middle layer 9 is arranged low-emission coated 101,
I.e. the inner layer glass of this laminated glass articles is low radiation coated glass of the present invention.The interlayer that the present invention protects as a result,
Glassware, including two blocks of glass and the middle layer 9 that is clipped between two blocks of glass, wherein be selected from least one piece in two blocks of glass
The plated film of above-described low radiation coated glass, the low radiation coated glass is located at the one side close to middle layer 9.
In order to be described in more detail and more support to convincingness the inventive point of the present invention, it is detailed now to enumerate some embodiments
It illustrates.
Embodiment 1-4
Low radiation coated glass of the present invention containing two layers of infrared reflecting layer, it is set forth below for embodiment in
Two infrared reflecting layers are silver layer namely double-silver low-emissivity coated glass, now enumerate Examples 1 to 4 and corresponding comparative example 1
~3 are compared and illustrate technical solution of the present invention in spectrum, machinery, chemically and thermally the improvement effect in stability.
The white glass of sodium-calcium-silicate float glass process for being 2.1 millimeters using thickness is glass substrate, by cutting, edging, washing and baking
After the processes such as dry, coated film deposition is carried out into magnetron sputtering plating line, background vacuum is higher than 6 × 10-4Pa, on the glass substrate
It is sequentially depositing film layer as shown in Table 1 and Table 2.Wherein, film layer shown in Tables 1 and 2 is splashed using pulse direct current except Ag, NiCrOx
It is outer to penetrate flat target deposition, remaining film layer uses medium frequency reactive sputtering rotary target heavy in oxidizing atmosphere or nitriding atmosphere
Product controls to obtain the film layer of suitable thickness by controlling power, gas ratio and movement velocity on each target.
Table 1：Comparative example 1-2 and embodiment 1-2 film layer structures
Table 2：Comparative example 3-4 and embodiment 3-4 film layer structures
The low radiation coated glass that plated film in Tables 1 and 2 is completed produces work according to the automobile laminated safety glass of standard
Skill, such as including big or small slice pairing, high-temperature molding and the techniques such as piece are closed, it is finally made laminated glass articles of the present invention.
Meanwhile with reference to ISO9050：2003 and D65 (10 degree) canonical measures and its dominant spectral index of calculating, as a result such as 4 institute of table 3 and table
Show.
Table 3：The dominant spectral index for the laminated glass articles that comparative example 1-2 and embodiment 1-2 are obtained
Table 4：The dominant spectral index for the laminated glass articles that comparative example 3-4 and embodiment 3-4 are obtained
Wherein：TL is visible transmission ratio；Tds is the direct transmittance of sunlight；Tts is total solar energy transmittance；RL is
Visible light reflectance；Rds is the direct reflectivity of sunlight；L*a*b* is color space coordinate.
It is compared by table 1 it is found that the main distinction of embodiment 1 and comparative example 1 is total film of the outermost dielectric layer of embodiment 1
Thickness reaches 158nm, and optical thickness is about 321nm, and comparative example 1 is according to traditional thicknesses of layers design theory, outermost Jie
The total film thickness of matter layer is only 35nm, and optical thickness is about 71nm.It can be obtained in conjunction with Fig. 6 and Fig. 7 analyses, embodiment 1 is relative to right
The spectrum of ratio 1 is significantly improved near infrared band (780-1200nm), is embodied as lower near-infrared and is penetrated
With higher near-infrared reflection.Meanwhile in conjunction with the measurement result of table 3, embodiment 1 can obtain lower relative to comparative example 1
Tds values, Tts values and higher Rds values.Therefore, in conclusion the infrared function of heat reflection of embodiment 1 more preferably.
Meanwhile the embodiment of table 1 and table 32 and comparison 2 are analyzed and can be obtained：Traditional design method has low in design
Tds values (<38%) and high Rds values (>35%) when double silver low-emissivity coated laminated glass, it is red to enhance that Ag tunics thickness need to be increased
External reflectance ability, the total film thickness of its infrared reflecting layer as shown in comparative example 2 in table 1 have reached 22.8nm.And correspondingly, embodiment
Use technical solution of the present invention, the total film thickness of infrared reflecting layer relatively thin can reach same infrared external reflection ability in 2,
And spectrum appearance is more preferable, is presented as lower RL and more neutral color coordinates.
Table 2 and table 4 are analyzed and can be obtained, when in low-emission coated laminated glass comprising there is relatively strong inhale to infra-red radiation
When glass substrate (the green glass of such as Solar) of receipts ability, Tds values and Tts values can be further decreased.The folder of traditional design thinking design
Layer glass, comparative example 3 as shown in Table 2, it is necessary to which controlling Ag layers of overall thickness can not be excessively high to ensure that TL is higher than 70%.And use this
The embodiment 3 of inventive technique scheme improves visible light anti-reflection, infrared increasing reflecting effect, further reduces Tds, Tts
Value, improves Rds values.In example 4, infrared external reflection layer thickness can be further increased, to realize that stronger infrared light is anti-
It penetrates.
In the following, the mechanical performance of embodiment 1-4 and comparative example 1-3, thermal stability and chemical stability are assessed, and
In table 5 by acquired results record.
Mechanical properties, the ability that main investigation film layer bears frictional dissipation include friction assessment by hand and Taper mills
Consumption assessment.Wherein friction assessment is rubbed using the clean cotton for dipping in alcohol, finger pressing on film surface repeatedly by hand, and one back and forth
Friction is denoted as 1 time, and continuous friction 40 times is scored as follows according to the destruction situation of film surface：
1 point dabs i.e. demoulding
2 points firmly wipe demoulding
3 points of slight demouldings
4 points, without demoulding, only slightly scratch
5 points of film surface appearances are good, and no macroscopic destroys
Load 1N/cm is arranged using on straight line abrasion instrument for heat-treatment sample2, dip in mud with non-dust cloth and carry out
Abrasion, reciprocal 200 back and forth, measures the mist degree after its abrasion, calculates its increment value.
In terms of thermal stability, due to the low radiation coated glass in Tables 1 and 2 under same heat treatment process appearance, side
Resistance assesses its thermal stability difference without significant difference, therefore by measuring mist degree.
In terms of chemical stability, the low radiation coated glass in Tables 1 and 2 is exposed to corrosive neutral salt spray atmosphere
Lower 170 hours, assess its cosmetic variation.
Table 5：Comparative example 1-4 and embodiment 1-4 heat treatments, mechanically and chemically stability assessment
By table 5 as it can be seen that the embodiment 1 of technical solution of the present invention, embodiment 2, embodiment 3 and embodiment 4 present compared with
Good thermal stability, film surface does not occur presentation quality deterioration after high-temperature heat treatment, and level of haze is relatively low, on the whole with comparative example 1-
3 quite, it can be seen that, film structure provided by the invention and traditional film structure are suitable on thermal stability.
By table 5 as it can be seen that excellent abrasion performance property is presented in the film layer after heat treatment, skill of the present invention in the case of same abrasion
The embodiment 1-4 of art scheme shows the lower degree of wear.
Similar low, the film layer after being heat-treated shows excellent resisting salt fog corrosion property, in the case of same salt air corrosion
Embodiment 1, embodiment 2 and the embodiment 3 of technical solution of the present invention show good corrosion ability to bear, especially through excessively high
Warm the glass of processing.Occur significantly corroding in the comparative example 1 of traditional design, comparative example 2 and 3 coated glass of comparative example
When, only there is extremely slight corrosion failure dot in the embodiment 1-4 with thicker outermost dielectric layer 5.
In short, based on above-mentioned comparative example 1, comparative example 2, comparative example 3 and embodiment 1, embodiment 2, embodiment 3 and embodiment
4 measurement is analyzed, compares, it is seen that the low radiation coated glass provided in technical solution of the present invention, with high-temperature stability phase
While working as, there is better spectrum property index and machinery, chemical durability.
Present invention embodiment enumerated above is describing film layer structure and corresponding film material, while embodiment
It only lists a part, and such as specific depositing operation, parameter, more embodiments and is fabricated to low radiation coated glass
The concrete technology and parameter of laminated glass articles do not describe, it is to be appreciated that these parts not described are all that this field is general
Known to logical technical staff, therefore the part not described does not influence invention which is intended to be protected.
The above content is to low radiation coated glass and its laminated glass of the present invention containing two layers of infrared reflecting layer
Product has been described in detail, but the present invention is not limited to by specific embodiments described above content, so all foundations
Any improvement, equivalent modifications and the replacement etc. that technical key point of the present invention carries out, belong to the scope of protection of the invention.
Claims (8)
1. the low radiation coated glass containing two layers of infrared reflecting layer, including glass substrate, it is characterised in that：In the glass base
It is set gradually outward in plate surface：
Inner medium layer, geometric thickness are 15~40nm；
First infrared reflecting layer, geometric thickness are 7~16nm；
Middle dielectric layer, geometric thickness are 70~110nm；
Second infrared reflecting layer, geometric thickness are 7~16nm；
Outermost dielectric layer, geometric thickness are 125~180nm, and optical thickness is 300~350nm, and refractive index is 1.7~2.6,
The outermost dielectric layer includes Si3N4Sublayer, AlN sublayers, ZnSnOx sublayers, ZnO sublayers, TiO2Sublayer, SnO2Sublayer, WO3Son
Layer, Bi2O3Sublayer, HfO2Sublayer and Nb2O5At least one of sublayer；
When outermost dielectric layer includes Si3N4When sublayer, the Si3N4Doped with Al, Ni, Zr or Hf in sublayer；
When outermost dielectric layer includes ZnO sublayers, doped with Al, Ga, Mo, Mg, In, F or B in the ZnO sublayers；
When outermost dielectric layer includes ZnSnOx sublayers, doped with Al, Sb, Mg, Ni or Y in the ZnSnOx sublayers.
2. the low radiation coated glass according to claim 1 containing two layers of infrared reflecting layer, it is characterised in that：Described
One infrared reflecting layer or the second infrared reflecting layer are selected from least one of silver, gold, copper, aluminium and its alloy.
3. the low radiation coated glass according to claim 1 containing two layers of infrared reflecting layer, it is characterised in that：It is described most
The geometric thickness of outer dielectric layer is 140~170nm, and optical thickness is 310~340nm.
4. the low radiation coated glass according to claim 1 containing two layers of infrared reflecting layer, it is characterised in that：In described
Dielectric layer or middle dielectric layer be selected from Zn, Si, Sn, Ti, Nb, Zr, Hf, Mg, Ni, In, Al, Ga, W, Bi metal oxide and its
At least one of mixture, or selected from Si, Al, Zr, Ti, Y, Hf, Nb, Ta metal nitride or nitrogen oxides and its mixing
At least one of object.
5. the low radiation coated glass according to claim 1 containing two layers of infrared reflecting layer, it is characterised in that：In described
Dielectric layer further includes the first ZnO sublayers, and the first ZnO sublayers are between inner medium layer and the first infrared reflecting layer.
6. the low radiation coated glass according to claim 1 containing two layers of infrared reflecting layer, it is characterised in that：In described
Between dielectric layer further include the 2nd ZnO sublayers, the 2nd ZnO sublayers are between middle dielectric layer and the second infrared reflecting layer.
7. the low radiation coated glass according to claim 1 containing two layers of infrared reflecting layer, it is characterised in that：Outermost
Barrier layer, institute are set between dielectric layer and the second infrared reflecting layer, and/or between middle dielectric layer and the first infrared reflecting layer
The geometric thickness for stating barrier layer is 0.3~5nm, and the barrier layer is selected from Ni, Cr, Ti, Zn, Sn, Hf, Zr, Al metal and its conjunction
The metal of gold, non-fully oxide, non-fully at least one of nitride.
8. a kind of laminated glass articles, including two blocks of glass and the middle layer that is clipped between two blocks of glass, it is characterised in that：Two pieces
It is selected from the low radiation coated glass described in claim 1-7 any one, the low radiation coated glass at least one piece in glass
Plated film be located at close to middle layer one side.
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Cited By (2)
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| WO2021105884A1 (en) * | 2019-11-26 | 2021-06-03 | Guardian Europe S.A.R.L. | Coated article with low-e coating having protective contact layer including ag, ni, and cr for protecting silver based ir reflecting layer(s), and method of making same |
| US11899227B2 (en) | 2019-07-31 | 2024-02-13 | Ningbo Radi-Cool Advanced Energy Technologies Co., Ltd. | Solar reflecting film and preparation method thereof |
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| CN108973265A (en) * | 2018-09-26 | 2018-12-11 | 光驰科技(上海)有限公司 | A kind of glass shell for electronic device |
| CN111253085A (en) * | 2020-03-25 | 2020-06-09 | 四川猛犸半导体科技有限公司 | Thin film device |
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| CN214571567U (en) * | 2020-12-31 | 2021-11-02 | 江苏数字鹰科技股份有限公司 | Low-emissivity coated glass for unmanned aerial vehicle body |
| CN114907020A (en) * | 2021-02-08 | 2022-08-16 | 深圳南玻应用技术有限公司 | Laminated coated glass |
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