CN111072290A

CN111072290A - Low-emissivity colorful film and preparation method thereof

Info

Publication number: CN111072290A
Application number: CN201911207260.5A
Authority: CN
Inventors: 尹铮杰; 翟怀伦; 赵锦玲; 颜毓雷; 王明辉; 其他发明人请求不公开姓名
Original assignee: Ningbo Ruiling New Energy Technology Co ltd
Current assignee: Ningbo Ruiling New Energy Technology Co ltd; Ningbo Radi Cool Advanced Energy Technologies Co Ltd
Priority date: 2019-11-29
Filing date: 2019-11-29
Publication date: 2020-04-28

Abstract

The invention relates to the field of a colorful film, in particular to a low-radiation colorful film which is characterized by comprising a base material capable of transmitting visible light, and a transparent oxide layer and a functional layer which are sequentially and alternately stacked and attached on the base material; the transparent oxide layer is at least three layers, and the thickness of each layer is independently selected from 10nm to 200 nm; the functional layer is at least two layers, and the thickness of each layer is independently selected from 0.1nm to 30 nm; the total thickness of each layer of the functional layer is at least 5 nm; the functional layer is made of Ag metal or alloy with Ag as a main component, and the mass fraction of Ag in the alloy is more than or equal to 80%. The product can be shifted along with the sight of an observer, can see different color changes, is gorgeous and attractive, has decorative performance, can be used in a plurality of fields, and is particularly suitable for being applied to the building field such as glass doors, glass windows, glass walls, glass roofs and the like due to the low radiation characteristic.

Description

Low-emissivity colorful film and preparation method thereof

Technical Field

The invention relates to the field of a colorful film, in particular to a low-emissivity colorful film and a preparation method thereof.

Background

With the rapid development of economy, the living standard of people is gradually improved, and new technologies are continuously appeared. The colorful film is a novel composite material, and can show different appearances along with the change of perspective conditions, reflection conditions and illumination conditions. The product characteristics of the color-glare film are many, for example: (1) color varies with viewing angle and illumination; (2) appear different colors in reflection and transmission; (3) corrosion-resistant, non-metallic techniques; (4) the radio frequency interference is avoided; (5) the colorful film glass has a three-dimensional colorful 3D reflection effect. The product has the colorful effect of reflecting various colorful lights in a three-dimensional way and has high reflectivity, so the product is uniformly favored by designers at home and in peripheral, has very wide application prospect, and is mainly applied to the walls of multimedia classrooms, movie and television rehearsal occasions and dance classrooms, or used as a film coating of glass products and the like. However, the existing color-glare film has various disadvantages, such as: 1. the function is single, and the high reflection effect of colorful light and near infrared wave bands is not achieved at the same time; 2. the existing colorful film is complex in process, low in efficiency and high in cost, and the colorful effect is achieved by coating hundreds of layers of materials with high and low refractive indexes; 3. the existing colorful film has low reflectivity in a near infrared band of 700nm-2500nm and poor heat insulation effect; 4. the existing colorful film has low emissivity of 7-14 mu m and does not have passive cooling effect.

Disclosure of Invention

The invention relates to a low-radiation colorful film which is characterized by comprising a base material capable of transmitting visible light, and a transparent oxide layer and a functional layer which are sequentially and alternately stacked and adhered on the base material;

the transparent oxide layer is at least three layers, and the thickness of each layer is independently selected from 10nm to 200 nm;

the functional layer is at least two layers, and the thickness of each layer is independently selected from 0.1nm to 30 nm; the total thickness of each layer of the functional layer is at least 5 nm; the functional layer is made of Ag metal or alloy with Ag as a main component, and the mass fraction of Ag in the alloy is more than or equal to 80%.

Optionally, the thickness of each layer of the transparent oxide layer is independently selected from 50nm to 150 nm.

Optionally, the thickness of each layer of the functional layer is independently selected from 5nm to 10 nm.

Optionally, the other metal In the alloy is selected from one or more of Al, Cu, Zn, Cu, In, Pt, Pd and Au.

Optionally, a portion of the metal in the functional layer is oxidized.

Optionally, the main component of the transparent oxide layer is a metal oxide and/or a metal dopant.

Optionally, the metal oxide is selected from TiO₂、SnO₂、ZnO、Nb₂O₅And Ta₂O₅One or more of (a).

Optionally, the doping material In the metal dopant is selected from at least one of Al, Ga, Zr, B, In, Y, Sb, and Mo, and the doped metal oxide is selected from tin oxide and/or zinc oxide.

Optionally, the substrate is selected from glass or a flexible plastic material.

Optionally, the substrate has a passive radiation cooling function.

Optionally, the substrate is doped with inorganic particles, and the emissivity of the substrate in a 7-14 μm waveband is over 75%.

According to another aspect of the invention, the invention also relates to a preparation method of the low-emissivity color-glare film, which comprises the following steps: and sputtering the transparent oxide layer and the functional layer on the substrate in sequence through a magnetron sputtering process.

According to a further aspect, the invention also relates to a glass window, a glass door, a glass wall or a glass roof with the low-emissivity color-glare film attached to the surface.

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

(1) the transmittance of the low-radiation colorful film in a visible light wave band of 400 nm-700 nm is 20% -80%, visible light can penetrate through the low-radiation colorful film, a plurality of absorption peaks are arranged in the visible light wave band of 400 nm-700 nm, the low-radiation colorful film has a good colorful effect, different reflection spectrums can be generated after the product is incident with light rays in different directions, an observer can see that the product presents different color changes along with the line of sight transfer, and the low-radiation colorful film is gorgeous and has decorative performance; the reflectivity of the sunlight in a near-infrared band of 700nm-2500nm is more than or equal to 60 percent, and the heat of the near-infrared band in the sunlight is prevented from entering a room; the high-emissivity glass has high emission at an atmospheric window waveband of 7-14 mu m, the emissivity is more than or equal to 75 percent, and the passive cooling effect is achieved; the event is applied to the glass door, glass window, glass wall or the glass top of building with the various membrane of dazzling of low radiation that this application provided, not only can let light see through glass and get into indoorly, can also effectively reflect the near infrared ray in the sunlight, and can effectively reduce the temperature in the building.

(2) The preparation method of the low-emissivity colorful film adopts a magnetron sputtering process, the process is simple, the cost is low, and the prepared product has good adhesive force.

(3) The glass has high reflection characteristic of near infrared light wave band, and is particularly suitable for being applied to the building field, such as glass doors, glass windows, glass walls, glass roofs and the like.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.

Fig. 1 shows Lambda950 test results of a low-emissivity color film prepared in example 1 of the present invention;

FIG. 2 is a Lambda950 test result of a prior art glare film;

fig. 3 is a Lambda950 test result of the low-emissivity color film prepared in example 2 of the present invention;

FIG. 4 shows the results of Lambda950 test of the film of comparative example 1 according to the invention.

Detailed Description

Reference will now be made in detail to embodiments of the invention, one or more examples of which are described below. Each example is provided by way of explanation, not limitation, of the invention. In fact, it will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope or spirit of the invention. For instance, features illustrated or described as part of one embodiment, can be used on another embodiment to yield a still further embodiment.

It is therefore intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents. Other objects, features and aspects of the present invention are disclosed in or are apparent from the following detailed description. It is to be understood by one of ordinary skill in the art that the present discussion is a description of exemplary embodiments only, and is not intended as limiting the broader aspects of the present invention.

Ag has low radiance, can effectively reduce the heat radiation passing through the product, but has low deviation value of the refractive index of the product and the refractive index of the transparent oxide, and is not easy to generate dazzling effect. The individual layer thickness of the functional layer cannot be too thick, otherwise the glare effect cannot be formed, and if the overall thickness of the functional layer is too thin, the low radiation will also be greatly reduced. The inventor verifies and finds that the high-low refractive index difference of different materials can be adjusted by reasonably controlling the number and the thickness of the transparent oxide layer and the functional layer, so that the manufactured product has low radiation and colorful characteristics when at least three layers of transparent oxides and two layers of functional layers are provided.

In some embodiments, the outermost layer of alternating portions of the transparent oxide layer and the functional layer is a transparent oxide layer.

In some embodiments, the transparent oxide layer may also be selected from 4, 5, 6, 7, 8 or more layers; the functional layer may also be selected from 3, 4, 5, 6, 7 or more layers.

In some embodiments, the thickness of each layer of the transparent oxide layer is independently selected from 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, 110nm, 120nm, 130nm, 140nm, 150nm, 160nm, 170nm, 180nm, 190nm, or 200nm, or a range of any two of the foregoing, preferably from 50nm to 150 nm.

In some embodiments, the total thickness of the layers of transparent oxide is at least 80nm, preferably at least 140 nm.

In some embodiments, the content of Ag in the alloy in mass percent may also be 82%, 84%, 86%, 88%, 90%, 92%, 94%, 95%, 96%, 97%, 98%, 99%, 99.9%, or 100%.

In some embodiments, the thickness of each layer of the functional layer may also be independently selected from 0.1nm, 0.2nm, 0.3nm, 0.4nm, 0.5nm, 0.6nm, 0.7nm, 0.8nm, 0.9nm, 1nm, 2nm, 3nm, 4nm, 5nm, 6nm, 7nm, 9nm, 10nm, 11nm, 12nm, 13nm, 14nm, 15nm, 16nm, 18nm, 20nm, 22nm, 24nm, 26nm, 28nm, or 30nm, or a range of any two of the foregoing, preferably from 5nm to 10 nm.

In some embodiments, the total thickness of the functional layer layers is at least 5nm, preferably at least 9nm, and optionally ≧ 15 nm.

In some embodiments, the other metal In the alloy is selected from one or more of Al, Cu, Zn, Cu, In, Pt, Pd, and Au.

In some embodiments, the metal in the functional layer is partially oxidized, e.g., silver is partially doped with silver oxide.

In some embodiments, the transparent oxide layer has an average light transmittance of 70% or more, and may be 80%, 90%, 95% or more at 400nm to 700 nm.

In some embodiments, the transparent oxide layer is primarily composed of a metal oxide and/or a metal dopant.

In some embodiments, the metal oxide is selected from TiO₂、SnO₂、ZnO、Nb₂O₅And Ta₂O₅One or more of (a).

In some embodiments, the doping material In the metal dopant is selected from at least one of Al, Ga, Zr, B, In, Y, Mo, and the doped metal oxide is selected from tin oxide and/or zinc oxide.

Further, the metal dopant is selected from indium-doped tin oxide (ITO), aluminum-doped zinc oxide (AZO), gallium-doped zinc oxide (GZO), indium-doped zinc oxide (IZO), antimony-doped tin oxide (ATO), molybdenum-doped zinc oxide (MZO), or a combination thereof.

In some embodiments, the substrate is selected from glass or a flexible plastic material.

In some embodiments, the substrate has passive radiation cooling capability.

In some embodiments, the substrate may further comprise inorganic particles.

In some embodiments, the inorganic particles are selected from SiO₂、CaCO₃、Si₃N₄、BaSO₄、ZnO、Al₂O₃Glass beads and ceramic beads.

In some embodiments, the substrate is pretreated to improve adhesion to the transparent oxide layer and the functional layer, optionally by sputtering a layer of metal, coating the substrate with an inorganic or organic primer layer, and the like.

In some embodiments, the emissivity of the substrate is above 75% at 7 μm to 14 μm.

According to one aspect of the invention, the invention also relates to a preparation method of the low-emissivity color-glare film, which comprises the following steps: and sputtering the transparent oxide layer and the functional layer on the substrate in sequence through a magnetron sputtering process.

The magnetron sputtering process utilizes the principle of electric field and magnetic field to uniformly sputter the raw materials of each layer on the base material at high speed and high strength, so that each layer of the manufactured colorful film is more uniform, the adhesive force is better, the colorful characteristic and the low radiation performance are further improved due to thinner particles and more compact structure.

The magnetron sputtering process can be carried out using conventional procedures commonly used in the art, such as:

1) bringing the reactor to a substantially vacuum condition, generally at 10 deg.f^-2Pa～10^-6Pa；

2) Filling gas (such as argon, nitrogen, oxygen or air, and taking argon as an example below) into the reactor, and starting the reactor;

3) argon ionisation, e.g. Ar → Ar⁺+e^-；

4) Under the action of the electric field, electrons can accelerate to fly to the anode;

5) under the action of the electric field, Ar + accelerates the target material flying to the cathode, target material particles and secondary electrons are knocked out, the former reaches the surface of the substrate to carry out film growth, and the latter is accelerated to promote more ionization on the way to the cathode.

In the process, the unreeling speed can be 0.5-500 m/min; the coating power can be 1-100 KW.

According to one aspect of the invention, the invention also relates to a glass window, a glass door, a glass wall or a glass roof with the low-emissivity color-glare film attached to the surface.

The above-mentioned glass product can be used in various fields such as architectural glass, decorative glass, window glass and the like.

Embodiments of the present invention will be described in detail with reference to examples.

Example 1

In the coated product provided by this embodiment, the substrate is made of a transparent flexible plastic material, and the transparent oxide layer and the functional layer are sequentially and alternately sputtered on the substrate by a magnetron sputtering process.

The transparent oxide layer is Nb₂O₅Layer, 3 layers in total; the functional layer is Ag alloy, and has 2 layers, wherein the mass fraction of Ag is 97%, and other metals in the alloy are Pd;

the coating material is Nb₂O₅/Ag/Nb₂O₅/Ag/Nb₂O₅The film thickness is respectively 80nm/5nm/120nm/4nm/100nm, the prepared product has excellent dazzling color characteristics, and a spectral curve is shown in figure 1 after Lambda950 test. The results of Lambda950 test of a commercially available 3M glare film (3M dichroic window ablation film) are shown in FIG. 2. As can be seen from fig. 1, the coated product prepared in this embodiment has a plurality of absorption peaks in a visible light band, which indicates that the coated product has a dazzling effect, and compared with fig. 2, the coated product prepared in this embodiment has a higher reflectance for light in a wavelength band of 700nm to 2500nm, the reflectance is 71%, and the coated product can form a good barrier to heat in sunlight.

Example 2

The transparent oxide layer is made of TiO₂4 layers in total; the functional layer is Ag alloy, and comprises 3 layers, wherein the mass fraction of Ag is 98%, and the mass fraction of indium in the alloy is 2%;

the coating material is TiO₂/Ag/TiO₂/Ag/TiO₂/Ag/TiO₂The film thickness is 50nm/3nm/80nm/3nm/80nm/3nm/100nm, and the spectral curve is shown in FIG. 3 after Lambda950 test. From FIG. 3, it can be seen that the prepared product has a plurality of absorption peaks in the visible light band, havingThe sample has excellent dazzling color characteristic, has very high reflectivity to light with a wave band of 700nm-2500nm, the reflectivity is 88%, and can form good obstruction to heat in sunlight.

Example 3

In the coated product provided by this embodiment, the substrate is made of transparent glass, and the transparent oxide layer and the functional layer are sequentially and alternately sputtered on the substrate by a magnetron sputtering process.

The transparent oxide layer adopts a ZnO layer, and the number of the ZnO layers is 4; the functional layer comprises 3 layers In total, wherein the mass fraction of Ag is 83%, and the compositions and mass fractions of other metals In the alloy are respectively Al 5%, Zn 10%, Pt 1% and In 1%;

the coating material is ZnO/Ag/ZnO/Ag/ZnO/Ag/ZnO, the film thickness is respectively 200nm/0.1nm/100nm/30nm/80nm/5nm/100nm, the prepared product has a plurality of absorption peaks in a visible light band and has excellent dazzling characteristic, and a sample has high reflectivity up to 85% in a 700nm-2500nm band

Example 4

The transparent oxide layer is ZnO layer 1 or TiO₂Layer 2; the functional layer comprises 2 layers in total, wherein the mass fraction of Ag is 85%, and the compositions and the contents of other metals in the alloy are respectively Cu 2%, Pd 0.6%, Zn 2% and Pt 0.4%;

the coating material is selected from ZnO/Ag/TiO₂/Ag/TiO₂The film thickness is 50nm/0.5nm/10nm/15nm/80nm respectively. The prepared product has a plurality of absorption peaks in a visible light wave band, has excellent dazzling characteristic, and the sample has high reflectivity up to 65% in a wave band of 700nm-2500 nm.

Example 5

The coated product provided by this embodiment is different from embodiment 1 only in that the transparent oxide layer is gallium-doped zinc oxide. The prepared product has a plurality of absorption peaks in a visible light wave band, has excellent dazzling characteristic, and the sample has higher reflectivity up to 63% in a wave band of 700nm-2500 nm.

Example 6

The coated product provided by this example is different from example 1 only in that the transparent oxide layer is aluminum-doped zinc oxide. The prepared product has a plurality of absorption peaks in a visible light wave band, has excellent dazzling characteristic, and the sample has higher reflectivity in a wave band of 700nm-2500nm, which can reach 68%.

Example 7

The coated product provided in this example is different from example 1 only in that the functional layer is pure Ag. The prepared product has a plurality of absorption peaks in a visible light wave band, has excellent dazzling characteristic, and the sample has high reflectivity up to 73% in a wave band of 700nm-2500 nm.

Comparative example

Comparative example was prepared in the same manner as in example 1 except that Nb was selected as the coating material₂O₅/Ag/Nb₂O₅Ag, the film thickness is 50nm/3nm/80nm/3nm respectively, the prepared product loses the dazzling characteristic, and the spectral curve is shown in figure 4 after the Lambda950 test.

As can be seen by comparing fig. 4 with the spectrograms of fig. 1, the reflectivity of the sample prepared in fig. 4 in the visible light band is reduced, and no obvious absorption peak is present, so that it can be seen that the dazzling effect of the sample prepared in fig. 4 is inferior to that of the sample prepared in example 1.

The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.

The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims

1. The low-emissivity color-glare film is characterized by comprising a base material capable of transmitting visible light, and a transparent oxide layer and a functional layer which are sequentially and alternately stacked and adhered on the base material;

2. The low emissivity color film of claim 1, wherein each layer of the transparent oxide layer has a thickness independently selected from the group consisting of 50nm to 150 nm.

3. The low emissivity color film of claim 1, wherein each layer of the functional layer has a thickness independently selected from the group consisting of 5nm to 10 nm.

4. The low emissivity color film of claim 1, wherein the other metals In the alloy are selected from one or more of Al, Cu, Zn, Cu, In, Pt, Pd, and Au.

5. The low emissivity color film according to any one of claims 1 to 4, wherein the metal in the functional layer is partially oxidized.

6. The low-emissivity color glare film according to any one of claims 1 to 4, wherein the main component of the transparent oxide layer is a metal oxide and/or a metal dopant.

7. The low emissivity color film of claim 6, wherein the metal oxide is selected from the group consisting of TiO₂、SnO₂、ZnO、Nb₂O₅And Ta₂O₅One or more of (a).

8. The low emissivity color film according to claim 7, wherein the metal dopant is a doped material selected from at least one of Al, Ga, Zr, B, In, Y, Sb, and Mo, and the doped metal oxide is selected from tin oxide and/or zinc oxide.

9. The low emissivity color-glare film according to any one of claims 1 to 4, 7 and 8, wherein the substrate is selected from glass or a flexible plastic material.

10. The low emissivity color film of claim 9, wherein the substrate has a passive radiation cooling function.

11. The low emissivity color glare film of claim 10, wherein the substrate is doped with inorganic particles, and the substrate has an emissivity of 75% or more at 7 to 14 μm.

12. The method for preparing the low-emissivity color-glare film according to any one of claims 1 to 11, wherein the method comprises the following steps: and sputtering the transparent oxide layer and the functional layer on the substrate in sequence through a magnetron sputtering process.

13. A glass window, a glass door, a glass wall or a glass roof having the low-emissivity color-glare film of any one of claims 1 to 11 attached to the surface.