CN112876096A

CN112876096A - Multi-silver-layer low-emissivity coated glass containing crystalline dielectric layer and preparation method and application thereof

Info

Publication number: CN112876096A
Application number: CN202110410111.XA
Authority: CN
Inventors: 吴斌; 陈波; 黄辉
Original assignee: Shanghai Yaohua Pilkington Glass Group Co ltd
Current assignee: Shanghai Yaohua Pilkington Glass Group Co ltd
Priority date: 2021-04-16
Filing date: 2021-04-16
Publication date: 2021-06-01

Abstract

The invention provides a multi-silver-layer low-emissivity coated glass containing a crystalline dielectric layer, and a preparation method and application thereof. The film structure of the coated glass comprises from the glass substrate to the outside: the glass substrate, at least 3 layers of composite low-radiation functional layers and protective layers which are continuously arranged; a dielectric layer is respectively arranged on the inner side and the outer side of the composite low-radiation functional layer; the composite low-radiation functional layer sequentially comprises a first crystalline state dielectric layer, a silver layer and a second crystalline state dielectric layer which are arranged in a stacked mode along the outward direction of the glass substrate. The invention adopts a vacuum magnetron sputtering coating method to prepare coated glass, and the coated glass is used as automobile front bumper laminated glass or building energy-saving glass. Through tests, the obtained coated glass has high transmittance and low sun-shading coefficient, can be bent and toughened, can meet the requirements of the automobile field and the building industry on the coated glass, and is more suitable for market demands.

Description

Multi-silver-layer low-emissivity coated glass containing crystalline dielectric layer and preparation method and application thereof

Technical Field

The invention relates to the field of coated glass for buildings and automobiles, in particular to multi-silver-layer low-emissivity coated glass, a preparation method and application thereof, and especially relates to multi-silver-layer low-emissivity coated glass containing a crystalline medium layer, and a preparation method and application thereof.

Background

The low-emissivity coated glass is a new generation of coated glass which can not only allow outdoor solar energy and visible light to transmit like common glass, but also reflect the secondary radiation heat of an object back like an infrared reflector, and can achieve the effects of controlling light, saving energy and heat, controlling and regulating and improving the environment when being used in any climate environment. Traditional low-emissivity glass includes single silver, two silver coated glass, in order to obtain lower shading coefficient and good light-heat ratio, only through the thickness of constantly increasing the silver layer, but the increase of silver layer thickness just means that the reduction of visible light transmission, colour selection are restricted, can't satisfy different customer's demand, then more complicated three silver or even four silver low-emissivity coated glass has just appeared.

CN 110092594a discloses a three-silver coated glass and a preparation method thereof, the three-silver coated glass sequentially comprises a glass substrate layer, a first dielectric layer, a first silver layer, a second dielectric layer, a second silver layer, a third dielectric layer, a third silver layer and a fourth dielectric layer from one side to the other side; the first dielectric layer, the second dielectric layer, the third dielectric layer and the fourth dielectric layer are all multilayer dielectric layers and are respectively selected from Si₃N₄Layer, TiO_xLayer, SnO_yLayer, ZnO_zLayer, ZnSnO_a+bAt least two of the layer and the AZO layer; wherein 0<x≤2，0<y≤2，0<z≤1，0<b≤2，0<a≤1。

CN 102514279a discloses a four-silver low-emissivity coated glass and a manufacturing process thereof, wherein the four-silver low-emissivity coated glass is provided with a coating on a glass substrate, and the coating film layer sequentially comprises from the glass substrate to the outside: the first interlayer dielectric combination layer is arranged on the first surface of the first substrate, and the second interlayer dielectric combination layer is arranged on the second surface of the second substrate.

CN 102092959A discloses a high-shading three-silver low-radiation coated glass containing three composite reflection reducing layers and a process, wherein the structure layers of the product from a glass substrate to the outside are sequentially a glass/composite reflection reducing layer (1), a silver layer (1), a protective layer (1), a composite reflection reducing layer (2), a silver layer (2), a protective layer (2), a composite reflection reducing layer (3), a silver layer (3), a protective layer (3) and a dielectric layer (1); the product adopts a vacuum magnetron sputtering coating process.

The above patent provides coated glass with different film layer structures, but the number of silver layers is limited, and with the increase of the number of silver layers, the advantages of high transmittance and low shading coefficient of the coated glass cannot be ensured, so that further improvement on the coated glass in performance is needed, and how to provide coated glass with multiple silver layers and the advantages of high transmittance and low shading coefficient becomes a problem which needs to be solved urgently.

Disclosure of Invention

Aiming at the defects in the prior art, the invention aims to provide multi-silver-layer low-emissivity coated glass containing a crystalline medium, and a preparation method and application thereof. The multi-silver-layer low-radiation coated glass containing the crystalline medium has high transmittance and low shading coefficient, can be bent and tempered, can meet the requirements of the building and automobile fields on the coated glass, and is more suitable for market demands.

In order to achieve the purpose, the invention adopts the following technical scheme:

in a first aspect, the present invention provides a multi-silver-layer low-emissivity coated glass containing a crystalline medium, wherein a film structure of the multi-silver-layer low-emissivity coated glass containing a crystalline medium comprises, from a glass substrate to the outside: the glass substrate, at least 3 layers of composite low-radiation functional layers and protective layers which are continuously arranged;

a dielectric layer is respectively arranged on the inner side and the outer side of the composite low-radiation functional layer;

the composite low-radiation functional layer sequentially comprises a first crystalline state dielectric layer, a silver layer and a second crystalline state dielectric layer which are arranged in a stacked mode from the glass substrate to the outside.

The film structure of the multi-silver-layer low-radiation coated glass comprises at least 3 composite low-radiation functional layers and dielectric layers which are arranged in succession, for example, 3 layers, 4 layers, 6 layers, 8 layers or 12 layers, but the structure is not limited to the values listed, and other values not listed in the numerical range are also applicable.

The invention discloses that the inner side and the outer side of the composite low-radiation functional layer are respectively provided with a dielectric layer, which means that the inner side and the outer side of each composite low-radiation functional layer are respectively provided with a dielectric layer along the outward direction of the glass substrate. Taking 3 layers of continuously arranged composite low-radiation functional layers as an example, the film layer structure is as follows: the glass substrate, a dielectric layer, a composite low-radiation functional layer, a dielectric layer and a protective layer.

The film structure of the coated glass comprises at least 3 continuously arranged composite low-radiation functional layers, and each composite low-radiation functional layer comprises a first crystalline state dielectric layer, a silver layer and a second crystalline state dielectric layer, so that the coated glass with multiple silver layers is formed; the emissivity of the multi-silver-layer low-emissivity coated glass containing the crystalline dielectric layer is less than or equal to 0.018.

The first crystalline state dielectric layer and the second crystalline state dielectric layer have the advantages of high thermal stability, chemical corrosion resistance and salt mist resistance, have excellent protection effect on the silver layer, and can be used as a good crystal bed of the metal silver layer, so that the silver layer can well grow. The first crystalline state medium layer and the second crystalline state medium layer have higher refractive index (n >2), so that the visible light transmittance is greatly improved, and the service life of the coated glass is prolonged.

Preferably, the material of the dielectric layer comprises Si₃N₄、TiO₂、ZnSnO_x、ZrO₂、NbO_yOr TaO, or a combination of at least two of them, a typical but non-limiting combination including Si₃N₄With TiO₂Combination of (A) and (B), Si₃N₄And ZnSnO_xCombination of (A) and (B), Si₃N₄And ZrO₂Combination of (5), ZnSnO_xAnd NbO_yCombination of (5), ZnSnO_xIn combination with TaO, or Si₃N₄、TiO₂、ZnSnO_x、ZrO₂In combination with TaO.

Where 0< x.ltoreq.2, it may be, for example, 0.1, 0.2, 0.5, 1, 1.5 or 2, but is not limited to the values listed, and other values not listed in the numerical range are likewise suitable.

0< y.ltoreq.2, for example 0.1, 0.2, 0.5, 1, 1.5 or 2, but is not limited to the values listed, and other values not listed in the numerical range are likewise suitable.

Preferably, the thickness of the dielectric layer is 20nm to 50nm, and may be, for example, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm or 50nm, but is not limited to the values recited, and other values not recited within the range of values are equally applicable.

Preferably, the material of the first crystalline medium layer is Zn₂SnO₄And/or Nb₂O₅。

Preferably, the material of the second crystalline dielectric layer is Zn₂SnO₄And/or Nb₂O₅。

Preferably, the thickness of the first crystalline medium layer is 8nm to 20nm, and may be, for example, 8nm, 10nm, 12nm, 14nm, 16nm, 18nm or 20nm, but is not limited to the values recited, and other values not recited within the range of values are also applicable.

Preferably, the silver layer has a thickness of 5nm to 20nm, which may be, for example, 5nm, 8nm, 10nm, 12nm, 14nm, 16nm, 18nm or 20nm, but is not limited to the values recited, and other values not recited within the range of values are equally applicable.

Preferably, the thickness of the second crystalline dielectric layer is 8nm to 20nm, and may be, for example, 8nm, 10nm, 12nm, 14nm, 16nm, 18nm or 20nm, but is not limited to the values recited, and other values not recited in the range of values are also applicable.

Preferably, the material of the protective layer is ZrO₂、NbO_a、SiC_b、Si₃N₄、SiNC_cOr TiN_dAny one or a combination of at least two of the above, typical but not limiting combinations include ZrO₂And NbO_aCombinations of (3), SiC_bWith Si₃N₄Combination of (A) and (B), Si₃N₄And SiNC_cCombination of (1), SiNC_cAnd TiN_dCombination of (2), NbO_aWith SiC_bOr ZrO₂、NbO_a、SiC_b、Si₃N₄And TiN_dCombinations of (a) and (b).

Where 0< a.ltoreq.2, for example, may be 0.1, 0.2, 0.5, 1, 1.5 or 2, but is not limited to the values listed, and other values not listed in the numerical ranges are likewise suitable.

0< b.ltoreq.4, for example 0.1, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5 or 4, but is not limited to the values listed, and other values not listed in the numerical range are likewise suitable.

0< c.ltoreq.4, for example 0.1, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5 or 4, but is not limited to the values listed, and other values not listed in the numerical range are likewise suitable.

0< d.ltoreq.4, for example 0.1, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5 or 4, but is not limited to the values listed, and other values not listed in the numerical range are likewise suitable.

Preferably, the protective layer has a thickness of 5nm to 15nm, which may be, for example, 5nm, 8nm, 10nm, 12nm, 14nm or 15nm, but is not limited to the values listed, and other values not listed within the range of values are equally applicable.

The protective layer of the invention has the function of ensuring the film surface quality of the coated glass in the processes of later processing hot bending, steel bending, interlayer and the like.

In a second aspect, the present invention provides a method for preparing a multi-silver-layer low-emissivity coated glass containing a crystalline medium layer as described in the first aspect, wherein the preparation method comprises the following steps:

a vacuum magnetron sputtering coating method is adopted to coat a dielectric layer, at least 3 layers of continuously arranged composite low-radiation functional layers, the dielectric layer and a protective layer on a glass substrate.

Preferably, the preparation method further comprises a heat treatment process of the coated glass.

The heat treatment method comprises the steps of heat treating the coated glass or respectively and independently heat treating the first crystalline state dielectric layer and the second crystalline state dielectric layer. The method for heat-treating the coated glass comprises substrate heating or toughening heat treatment; the method for separately thermally treating the first crystalline dielectric layer and the second crystalline dielectric layer comprises laser treatment and/or irradiation treatment. The substrate heating is carried out before plating of the coated glass, and the laser treatment, the radiation treatment and the tempering heat treatment are carried out after plating.

The temperature of the heat-treated coated glass is 500-720 ℃, for example, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃ or 720 ℃, but not limited to the values listed, and other values not listed in the numerical range are also applicable.

The temperature of the first crystalline dielectric layer is 500-720 ℃, for example 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃ or 720 ℃, but not limited to the values listed, and other values not listed in the numerical range are also applicable.

The temperature of the second crystalline dielectric layer is 500-720 ℃, such as 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃ or 720 ℃, but not limited to the values listed, and other values not listed in the numerical range are also applicable.

The heat treatment of the invention is carried out for the purposes of: so that the amorphous material generated by sputtering is transformed into a crystalline stable structure.

Preferably, the dielectric layer is sputtered in argon nitrogen atmosphere or argon oxygen atmosphere through a target of an alternating current cathode.

Preferably, the plating of the composite low-radiation functional layer is to sequentially plate a first crystalline state dielectric layer, a silver layer and a second crystalline state dielectric layer.

Preferably, the first crystalline dielectric layer is sputtered in an argon atmosphere by an oxidized ceramic target of an alternating current cathode.

Preferably, the silver layer is sputtered by a direct current flat target silver target in an argon atmosphere.

Preferably, the second crystalline dielectric layer is sputtered in an argon atmosphere by an oxidized ceramic target of an alternating current cathode.

Preferably, the protective layer is sputtered in an argon atmosphere or an argon-nitrogen atmosphere by means of an alternating current round target.

In a third aspect, the invention provides the use of the multi-silver-layer low-emissivity coated glass containing the crystalline dielectric layer in the first aspect, and the multi-silver-layer low-emissivity coated glass containing the crystalline dielectric layer can be used as energy-saving building glass and can also be used on automotive front bumper laminated glass to achieve the effects of energy conservation and environmental protection.

The recitation of numerical ranges herein includes not only the above-recited numerical values, but also any numerical values between non-recited numerical ranges, and is not intended to be exhaustive or to limit the invention to the precise numerical values encompassed within the range for brevity and clarity.

Compared with the prior art, the invention has the beneficial effects that:

the multi-silver-layer low-emissivity coated glass containing the crystalline state dielectric layer has a unique film layer structure, improves the traditional low-emissivity coated glass, solves the problem that the visible light transmittance of the traditional low-emissivity coated glass is reduced after the number of silver layers is increased, and particularly improves the service life of the coated glass by using the crystalline state dielectric layer to replace the blocking protection effect of the dielectric layer. The multi-silver-layer low-emissivity coated glass provided by the invention has the advantages of higher visible light transmittance, lower emissivity, good photo-thermal ratio and good corrosion resistance, can be bent and tempered, can meet the requirements of the automobile field on coated glass, and is more suitable for the market demands.

Detailed Description

The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.

Example 1

The embodiment provides a multi-silver-layer low-emissivity coated glass containing crystalline medium, and the film structure of the multi-silver-layer low-emissivity coated glass comprises, from a glass substrate to the outside: the glass substrate, 3 layers of composite low-radiation functional layers and protective layers which are continuously arranged;

the 3 layers of continuously arranged composite low-radiation functional layers comprise a first composite low-radiation functional layer, a second composite low-radiation functional layer and a third composite low-radiation functional layer;

the first composite low-radiation functional layer, the second composite low-radiation functional layer and the third composite low-radiation functional layer respectively and independently comprise a first crystalline state dielectric layer, a silver layer and a second crystalline state dielectric layer;

the material composition and the film thickness of each film layer of the coated glass from the glass substrate to the outside are shown in table 1.

The magnetron sputtering coating machine specifically implemented in this embodiment includes 23 ac cathodes and 8 dc planar cathodes, and adopts the process parameters listed in table 1, and uses 11 ac round targets, 3 dc single targets, and 14 target positions for production, and the low-emissivity coated glass with a multi-silver layer containing a crystalline medium in this embodiment is prepared by sequentially coating the films in the order of the films. The glass substrate is cleaned and dried before coating, then is subjected to pre-vacuum transition in a vacuum magnetron sputtering coating machine, and then a coating process is started, wherein the process parameters and the target position are shown in table 1.

The preparation method also comprises the step of heating the coated glass to 550 ℃ by adopting a substrate heating method before plating all crystalline state dielectric layers, so that the plated material is changed from an amorphous state to a crystalline state.

TABLE 1

According to the film system structure and the production method, a three-silver-layer low-emissivity coating film containing a crystalline medium layer is prepared on a 6mm glass substrate, and the emissivity epsilon, SHGC and Tv (visible light transmittance) of the coated glass obtained in the embodiment are detected to be 0.015, 0.36 and 76 respectively.

Referring to GB/T18951.1, the acid resistance and alkali resistance experiments of the low-emissivity coated glass with a three-silver layer and a crystalline dielectric layer prepared in the embodiment are carried out, the coated glass is respectively soaked in 1mol/L hydrochloric acid and 1mol/L sodium hydroxide solution, the film layer begins to obviously fall off after 4 hours of the glass in the hydrochloric acid solution, and the film layer does not obviously fall off after 24 hours of the glass in the sodium hydroxide solution.

Example 2

The embodiment provides a multi-silver-layer low-emissivity coated glass containing crystalline medium, and the film structure of the multi-silver-layer low-emissivity coated glass comprises, from a glass substrate to the outside: 4 layers of composite low-radiation functional layers and protective layers are continuously arranged on the glass substrate;

the 4 continuously arranged composite low-radiation functional layers comprise a first composite low-radiation functional layer, a second composite low-radiation functional layer, a third composite low-radiation functional layer and a fourth composite low-radiation functional layer;

the first composite low-radiation functional layer, the second composite low-radiation functional layer, the third composite low-radiation functional layer and the fourth composite low-radiation functional layer respectively and independently comprise a first crystalline dielectric layer, a silver layer and a second crystalline dielectric layer;

the material composition and the film thickness of each film layer of the coated glass from the glass substrate to the outside are shown in table 2.

The magnetron sputtering coating machine used in the specific implementation of this embodiment includes 23 ac cathodes and 8 dc planar cathodes, and adopts the process parameters listed in table 2, and uses 14 ac round targets and 4 dc single targets, and altogether 18 target positions to produce, and the low-emissivity coated glass with a multi-silver layer containing crystalline medium described in this embodiment is prepared by sequentially coating the films in the order of the films. The glass substrate is cleaned and dried before coating, then is subjected to pre-vacuum transition in a vacuum magnetron sputtering coating machine, and then a coating process is started, wherein the process parameters and the target position are shown in table 2.

The preparation method further comprises the step of heating the first crystalline state medium layer and the second crystalline state medium layer to 680 ℃ by adopting a toughening heat treatment method after plating, and preserving heat for 2-3 minutes to enable the materials of all the crystalline state medium layers to be changed into crystalline states from amorphous states.

TABLE 2

According to the film system structure and the production method, a four-silver-layer low-emissivity coating film containing a crystalline medium layer is prepared on a 6mm glass substrate, and through detection, the emissivity epsilon of the coated glass obtained in the embodiment is 0.010, the SHGC is 0.33, and the Tv (visible light transmittance) is 68%.

Referring to GB/T18951.1, the acid resistance and alkali resistance experiments of the four-silver-layer low-emissivity coated glass containing the crystalline dielectric layer prepared in the embodiment are carried out, the coated glass is respectively soaked in 1mol/L hydrochloric acid and 1mol/L sodium hydroxide solution, the film layer begins to obviously fall off after 3 hours of the glass in the hydrochloric acid solution, and the film layer does not obviously fall off after 24 hours of the glass in the sodium hydroxide solution.

Example 3

In this embodiment, a coated glass with multiple silver layers and low radiation is provided, except that the material of the first crystalline state dielectric layer and the material of the second crystalline state dielectric layer in the composite low radiation functional layer are replaced with Nb₂O₅The heat treatment process was changed to laser heating the first crystalline dielectric layer and the second crystalline dielectric layer to 500 c, and the rest was the same as in example 1.

According to the film system structure and the production method, the three-silver-layer low-radiation coating film containing the crystalline dielectric layer is prepared on the glass substrate. The coated glass obtained in this example was examined to have an emissivity of ∈ 0.016, an SHGC of 0.36, and a Tv (visible light transmittance) of 74%.

Referring to GB/T18951.1, the acid resistance and alkali resistance experiments of the low-emissivity coated glass with a three-silver layer and a crystalline dielectric layer prepared in the embodiment are carried out, the coated glass is respectively soaked in 1mol/L hydrochloric acid and 1mol/L sodium hydroxide solution, the film layer begins to obviously fall off after 3 hours of glass in the hydrochloric acid solution, and the film layer does not obviously fall off after 24 hours of glass in the sodium hydroxide solution.

Comparative example 1

The comparative example provides a coated glass with multiple silver layers and low radiation, and the rest is the same as that in the example 1 except that the first crystalline state dielectric layer and the second crystalline state dielectric layer in the composite low radiation functional layer are replaced by dielectric layers.

Taking the first composite low-radiation functional layer as an example, replacing the first crystalline dielectric layer with a dielectric layer with the thickness of 10nm and the material of AZO; and replacing the second crystalline dielectric layer with a dielectric layer with the thickness of 10nm and the material of AZO.

According to the film system structure and the production method, the three-silver-layer low-emissivity coating film containing the crystalline dielectric layer is prepared on the 6mm glass substrate. The coated glass obtained in this comparative example was found to have an emissivity e of 0.014, an SHGC of 0.36 and a Tv (visible light transmittance) of 75%.

Referring to GB/T18951.1, the acid resistance and alkali resistance experiments of the low-emissivity coated glass with three silver layers prepared in the comparative example are carried out, the coated glass is respectively soaked in 1mol/L hydrochloric acid and 1mol/L sodium hydroxide solution, the film layer completely falls off after 5 minutes of the glass in the hydrochloric acid solution, and the obvious film layer falls off after 8 hours of the glass in the sodium hydroxide solution.

Compared with example 1, the visible light transmittance and the emissivity of the coated glass obtained in the comparative example are similar to those of the coated glass obtained in example 1, but the corrosion resistance is far worse than that of example 1.

Comparative example 2

The comparative example provides a coated glass with multiple silver layers and low radiation, and the rest is the same as the example 2 except that the first crystalline state dielectric layer and the second crystalline state dielectric layer in the composite low radiation functional layer are both replaced by common dielectric layers AZO.

Taking the first composite low-radiation functional layer as an example, replacing the first crystalline dielectric layer with a dielectric layer with the thickness of 12nm and the material of AZO; and replacing the second crystalline dielectric layer with a dielectric layer with the thickness of 12nm and the material of AZO.

According to the film system structure and the production method, a four-silver-layer low-emissivity coating film containing a crystalline medium layer is prepared on a 6mm glass substrate, and the emissivity epsilon of the coated glass obtained by the comparative example is 0.009, SHGC is 0.33 and Tv (visible light transmittance) is 65 percent through detection.

Referring to GB/T18951.1, the acid resistance and alkali resistance experiments of the four-silver-layer low-emissivity coated glass prepared in the comparative example are carried out, the coated glass is respectively soaked in 1mol/L hydrochloric acid and 1mol/L sodium hydroxide solution, the film layer completely falls off after 5 minutes of the glass in the hydrochloric acid solution, and the obvious film layer falls off after 5 hours of the glass in the sodium hydroxide solution.

Compared with example 2, the visible light transmittance and the emissivity of the coated glass obtained in the comparative example are similar to those of the coated glass obtained in example 2, but the corrosion resistance is far worse than that of example 2.

Comparative example 3

The comparative example provides a coated glass with multiple silver layers and low radiation, and the rest is the same as the example 1 except that the second crystalline state dielectric layer of the composite low radiation functional layer is replaced by a metal barrier layer NiCr.

Taking the first composite low-radiation functional layer as an example, the second crystalline dielectric layer is replaced by a metal barrier layer with the thickness of 3nm and the material of NiCr.

According to the film system structure and the production method, the three-silver-layer low-emissivity coating film containing the crystalline medium layer is prepared on the glass substrate, and the emissivity epsilon, SHGC and Tv (visible light transmittance) of the coated glass obtained by the comparative example are detected to be 0.015, 0.34 and 69 percent.

The coated glass prepared in the comparative example is subjected to acid resistance and alkali resistance experiments by referring to GB/T18951.1, and is respectively soaked in 1mol/L hydrochloric acid and 1mol/L sodium hydroxide solution, so that the film layer begins to obviously fall off after 4 hours of glass in the hydrochloric acid solution, and the film layer does not obviously fall off after 24 hours of glass in the sodium hydroxide solution.

Compared with the example 1, the emissivity of the coated glass obtained in the comparative example is the same as that of the example 1, the acid and alkali resistance of the film layer is similar to that of the example 1, but the visible light transmittance is far lower than that of the example 1.

Comparative example 4

The comparative example provides a coated glass with multiple silver layers and low radiation, and the other parts are the same as those in example 1 except that the first crystalline state dielectric layer and the second crystalline state dielectric layer of the composite low radiation layer are replaced by metal barrier layers.

Taking the first composite low-radiation functional layer as an example, replacing the first crystalline state dielectric layer with a metal barrier layer with the thickness of 3nm and the material of NiCr; and replacing the second crystalline dielectric layer with a metal barrier layer with the thickness of 3nm and the material of NiCr.

According to the film system structure and the production method, the three-silver-layer low-emissivity coating film containing the crystalline medium layer is prepared on the glass substrate, and the emissivity epsilon of the coated glass obtained by the comparative example is 0.018, the SHGC is 0.31, and the Tv (visible light transmittance) is 63% through detection.

Referring to GB/T18951.1, the acid resistance and alkali resistance tests of the low-emissivity coated glass with three silver layers prepared in the comparative example are carried out, the coated glass is respectively soaked in 1mol/L hydrochloric acid and 1mol/L sodium hydroxide solution, the film layer begins to fall off after the glass in the hydrochloric acid solution is 12 hours, and the film layer does not obviously fall off after the glass in the sodium hydroxide solution is 24 hours.

Compared with the example 1, the acid and alkali resistance of the coated glass obtained by the comparative example is far better than that of the example 1, but the visible light transmittance, the radiance and the sun-shading performance are far worse than those of the example 1.

The visible light transmittance Tv%, emissivity e, total solar transmittance SHGC, acid-proof time and alkali-proof time of the coated glass prepared by the methods of examples 1 to 3 and comparative examples 1 to 4 are shown in table 3.

TABLE 3

As can be seen from table 3, the low-emissivity coated glass with multiple silver layers and containing crystalline dielectric layers of the present invention has excellent visible light transmittance Tv%, emissivity epsilon, total solar transmittance SHGC, acid resistance and alkali resistance. Example 1 has more excellent acid resistance and alkali resistance than the comparative example; example 1 has more excellent visible light transmittance Tv% than comparative examples 3 to 4; example 2 has more excellent total solar transmittance SHGC, acid resistance and alkali resistance than comparative example 2.

In conclusion, the multi-silver-layer low-emissivity coated glass containing the crystalline dielectric layer provided by the invention has the advantages of higher visible light transmittance, lower emissivity, good photo-thermal ratio and good corrosion resistance, can be subjected to bending tempering, can meet the requirements of the automobile field and the building industry on coated glass, and is more suitable for the market demand.

The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. The multi-silver-layer low-emissivity coated glass containing the crystalline medium layer is characterized in that a film structure of the multi-silver-layer low-emissivity coated glass containing the crystalline medium layer outwards comprises from a glass substrate: the glass substrate, at least 3 layers of composite low-radiation functional layers and protective layers which are continuously arranged;

the composite low-radiation functional layer sequentially comprises a first crystalline state dielectric layer, a silver layer and a second crystalline state dielectric layer which are arranged in a stacked mode along the outward direction of the glass substrate.

2. The multi-silver-layer low-emissivity coated glass comprising crystalline medium layers of claim 1, wherein the material of the first crystalline medium layer comprises Zn₂SnO₄And/or Nb₂O₅；

Preferably, the material of the second crystalline dielectric layer comprises Zn₂SnO₄And/or Nb₂O₅。

3. The multi-silver-layer low-emissivity coated glass containing crystalline medium layers according to claim 1 or 2, wherein the thickness of the first crystalline medium layer is 8nm-20 nm;

preferably, the thickness of the silver layer is 5nm-20 nm;

preferably, the thickness of the second crystalline dielectric layer is 8nm-20 nm.

4. The low-emissivity coated glass with multiple silver layers and comprising crystalline dielectric layers according to any one of claims 1-3, wherein the material of the protective layer comprises ZrO₂、NbO_a、SiC_b、Si₃N₄、SiNC_cOr TiN_dAny one or a combination of at least two of them, wherein 0<a≤2，0<b≤4，0<c≤4，0<d≤4；

Preferably, the thickness of the protective layer is 5nm to 15 nm.

5. The multi-silver-layer low-emissivity coated glass comprising crystalline dielectric layers according to any one of claims 1-4, wherein the material of the dielectric layers comprises Si₃N₄、TiO₂、ZnSnO_x、ZrO₂、NbO_yOr TaO, wherein 0 is 0<x≤2，0<y≤2；

Preferably, the thickness of the dielectric layer is 20nm-50 nm.

6. The method for preparing the multi-silver-layer low-emissivity coated glass containing crystalline medium layers according to claims 1-5, wherein the method comprises the following steps:

7. The method according to claim 6, further comprising a heat treatment process for the coated glass.

8. The preparation method according to claim 6 or 7, wherein the method used in the heat treatment process of the coated glass comprises substrate heating, toughening heat treatment laser treatment or irradiation treatment.

9. The preparation method according to claim 6, wherein the plating of the composite low-emissivity functional layer is sequentially plating a first crystalline dielectric layer, a silver layer and a second crystalline dielectric layer;

preferably, the first crystalline medium layer is sputtered in an argon atmosphere by an oxidized ceramic target of an alternating current cathode;

preferably, the silver layer is sputtered in an argon atmosphere by a direct current flat target silver target;

10. The use of the multi-silver-layer low-emissivity coated glass containing the crystalline medium layer as claimed in any one of claims 1 to 5, wherein the multi-silver-layer low-emissivity coated glass containing the crystalline medium layer is used as automotive front windshield laminated glass or building energy-saving glass.