CN106435496A - Grass-green double-silver low-radiation energy-saving window film and preparation method thereof - Google Patents
Grass-green double-silver low-radiation energy-saving window film and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
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- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0015—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterized by the colour of the layer
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/04—Coating on selected surface areas, e.g. using masks
- C23C14/042—Coating on selected surface areas, e.g. using masks using masks
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/083—Oxides of refractory metals or yttrium
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
- C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
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Abstract
The invention discloses a grass-green double-silver low-radiation energy-saving window film and a preparation method thereof. The window film is grass-green in the sunshine, and a film layer structure of the grass-green window film sequentially comprises a flexible transparent PET base material layer, a first high-refractive-index layer, a first metal oxide layer, a first silver alloy layer, a first blocking layer, a second high-refractive-index layer, a second metal oxide layer, a second silver alloy layer, a second blocking layer and a third high-refractive-index layer from the inside to outside. The window film disclosed by the invention forms a refractive-index matching relationship with the three high-refractive-index layers through reflection of the double silver alloy layers for an infrared light, and moreover, the window film has a colour observed to be grass-green in the sunshine through matching of thickness parameters, and has a great visual effect. Meanwhile, the grass-green window film further has excellent light-transmitting, heat-isolating and oxidation-resistant performance, and is long in service and easy to produce.
Description
Technical field
The present invention relates to the pad pasting being attached on the glass pane of automobile, building etc., it is in grass green under especially a kind of sunlight
The fenestrated membrane of color, particularly to double silver low radiation energy-conservation fenestrated membrane of a kind of grass green and preparation method thereof.
Background technology
It is frequently necessary on the glass pane of automobile, building etc. attach pad pasting, commonly referred to fenestrated membrane, to provide heat-insulated, anti-purple
The functions such as outside line.Meanwhile, the fenestrated membrane of excellent performance may also provide good visible light transmittance rate, can be from the inner side of glass pane
Clear observation is outside window.Wherein, Low emissivity fenestrated membrane, also known as Low-E fenestrated membrane, is to deposit Low emissivity film layer in flexible and transparent substrate surface
Form；Low emissivity fenestrated membrane has higher light transmittance to visible ray, meanwhile, has very high reflectivity to infrared ray and ultraviolet,
Be a kind of have concurrently high printing opacity, high heat-insulated the advantages of film product.
At present, it is single that traditional Low emissivity energy-conservation fenestrated membrane has a color, some shortcomings such as heat-proof quality difference, and has
The double silver low radiation energy-conservation fenestrated membrane of the grass green of very strong decorative effect is even more rare.Most fenestrated membrane is all that energy saving is poor at present
Heat-reflective coating fenestrated membrane, its structural stability is poor, and effect of heat insulation is not good, and service life is shorter, is unfavorable for that product pushes away on a large scale
Extensively.
In the industrial production of Low emissivity energy-conservation fenestrated membrane, magnetic control fenestrated membrane produce the later stage also need to be coated technique carry out multiple
Close, this make fenestrated membrane inevitably with air contact, thus cause its oxidation, and in transportation temperature change,
Also the oxidation of fenestrated membrane will be accelerated, directly affect its service life.
Content of the invention
The technical problem to be solved in the present invention is to provide double silver low radiation energy-conservation fenestrated membrane of a kind of grass green and preparation method thereof,
So that noted earlier problem is reduced or avoided.
For solving above-mentioned technical problem, the present invention proposes a kind of double silver low radiation energy-conservation fenestrated membrane of grass green, in the sun
In grass green, the film layer structure of described fenestrated membrane is followed successively by from inside to outside：Flexible and transparent PET base material layer, thickness is 23 microns～50
Micron, its visible light transmittance rate >=89%, mist degree≤1.5；First high refractive index layer, thickness is 33nm～35nm, and refractive index is
2.36, described first high refractive index layer is by Nb2O5Constitute；First metal oxide layer, thickness is 3nm～6nm, described first gold medal
Belong to oxide skin(coating) by ZnO:Al is constituted；First ag alloy layer, thickness is 9nm～11nm, and described first ag alloy layer is by 96%
Ag, 4% Cu is constituted；First barrier layer, thickness is 0.5nm～0.8nm, and described first barrier layer is made up of Ti；Second high folding
Penetrate rate layer, thickness is 66nm～70nm, refractive index is 2.36, and described second high refractive index layer is by Nb2O5Constitute；Second metal oxygen
Compound layer, thickness is 6nm～8nm, and described second metal oxide layer is by ZnO:Al is constituted；Second ag alloy layer, thickness is
14.5nm～16.5nm, described second ag alloy layer by 98% Ag, 2% Pd constitutes；Second barrier layer, thickness is 0.7nm
～1nm, described second barrier layer is made up of Ti；3rd high refractive index layer, thickness is 29nm～32nm, and refractive index is 2.36, institute
State the 3rd high refractive index layer by Nb2O5Constitute.
Preferably, the thickness of described first metal oxide layer is less than or equal to the 2/3 of the thickness of described first ag alloy layer；
The thickness of described second metal oxide layer is less than or equal to the 2/3 of the thickness of described second ag alloy layer.
Preferably, the thickness of described first barrier layer is less than or equal to the 1/5 of the thickness of described first ag alloy layer；Described
The thickness of two barrier layers is less than or equal to the 1/5 of the thickness of described second ag alloy layer.
Preferably, the thickness of described flexible and transparent PET base material layer is 23 microns；The thickness of described first high refractive index layer is
34nm；The thickness of described first metal oxide layer is 5nm；The thickness of described first ag alloy layer is 10nm；Described first resistance
The thickness of interlayer is 0.6nm；The thickness of described second high refractive index layer is 68nm；The thickness of described second metal oxide layer is
7nm；Described second ag alloy layer thickness is 14.7nm；The thickness of described second barrier layer is 0.9nm；Described 3rd high index of refraction
The thickness of layer is 30nm.
Preferably, the double silver low radiation energy-conservation fenestrated membrane of described grass green the light transmittance of visible-range be 74.3%, in ripple
The light transmittance of the infrared region of a length of 780nm～2500nm is 9.3%, is the infrared barrier rate at 950nm wavelength in wavelength
It is 95% for 82.5%, in wavelength for the infrared barrier rate at 1400nm wavelength.
Present invention also offers a kind of preparation method of the double silver low radiation energy-conservation fenestrated membrane of above-mentioned grass green, walk including following
Suddenly：
(1) provide flexible and transparent PET film as described flexible and transparent PET base material layer；
(2) deposited in described flexible and transparent PET base material layer by way of dual rotary negative electrode, MF reactive magnetron sputtering
Described first high refractive index layer；
(3) institute is deposited by way of single rotating cathode, direct current reaction magnetron sputtering on described first high refractive index layer
State the first metal oxide layer；
(4) deposited on described first metal oxide layer by way of monoplane negative electrode, direct current reaction magnetron sputtering
Described first ag alloy layer；
(5) described in being deposited on described first ag alloy layer by way of monoplane negative electrode, direct current reaction magnetron sputtering
First barrier layer；
(6) deposit described by way of dual rotary negative electrode, MF reactive magnetron sputtering on described first barrier layer
Two high refractive index layers；
(7) institute is deposited by way of single rotating cathode, direct current reaction magnetron sputtering on described second high refractive index layer
State the second metal oxide layer；
(8) deposited on described second metal oxide layer by way of monoplane negative electrode, direct current reaction magnetron sputtering
Described second ag alloy layer；
(9) described in being deposited on described second ag alloy layer by way of monoplane negative electrode, direct current reaction magnetron sputtering
Second barrier layer；
(10) deposit described by way of dual rotary negative electrode, MF reactive magnetron sputtering on described second barrier layer
Three high refractive index layers.
Preferably, in magnetron sputtering deposition plated film, the temperature of all within the chambers respectively constant at -15 DEG C～15 DEG C.
Preferably, described step (2), step (3), step (6), step (7), step (10) all include：In corresponding chambers
Being passed through volume ratio is 10:1～100:1 argon gas and the mixed gas of oxygen, set sputtering vacuum 10-6Torr, plated film is stable
Air pressure is 10-3Torr；Dual rotary negative electrode, MF reactive magnetron sputtering power are 20Kw～50Kw；Single rotating cathode, direct current reaction
Magnetron sputtering power is 2Kw～5Kw.
Preferably, described step (4), step (5), step (8), step (9) all include：It is passed through purity not in corresponding chambers
Argon gas less than 99.99%, sets sputtering vacuum 10-6Torr, it is 10 that plated film stablizes air pressure-3Torr；Monoplane negative electrode, straight
Stream reaction magnetocontrol sputtering power is 0.5Kw～8Kw.
Preferably, described step 4 further includes, by way of arranging the UV mask of horizontal parallel arrangement, in institute
State described first ag alloy layer of the striated that horizontal direction parallel arrangement is formed on the first metal oxide layer.Described step 8
Further include, by way of the UV mask of horizontal parallel arrangement is set, described second metal oxide layer is formed
Described second ag alloy layer of the striated of horizontal direction parallel arrangement.The horizontal direction parallel arrangement of described second ag alloy layer
The striped of the horizontal direction parallel arrangement of striped and described first ag alloy layer be preferably staggeredly arranged.
Beneficial effects of the present invention
Compared with prior art, the invention provides a kind of double silver low radiation section of grass green with 9 layers of coating structure
Energy fenestrated membrane structure improvement, stable performance, can effectively overcome the disadvantage of prior art, so that the function of ag alloy layer is obtained effectively
Performance, infrared emittance while holding higher visible light transmittance rate is greatly reduced.The double silver of grass green that the present invention provides
Low emissivity Energy Saving Windows membrane preparation method process is simple, easy and simple to handle, it is easy to accomplish mass production.
The double silver low radiation energy-conservation fenestrated membrane of grass green that the present invention provides, replaces traditional silver layer using ag alloy layer, has
Preferably non-oxidizability.
The double silver low radiation energy-conservation fenestrated membrane of grass green that the present invention provides, makees place mat using oxide skin(coating) for ag alloy layer；
Oxide skin(coating) can promote the growth of silver alloy film to make it grow up to continuous structure as early as possible, and so very thin metal level just can have very
High infrared reflectivity and preferably visible light transmissivity.
The double silver low radiation energy-conservation fenestrated membrane of grass green that the present invention provides, is protected to ag alloy layer using barrier layer,
Ensure that the reflectivity of infrared light will not reduce with the prolongation of use time, extend the service life of fenestrated membrane, have and hold
Long high effect of heat insulation.
The double silver low radiation energy-conservation fenestrated membrane of grass green that the present invention provides, by the appropriate design of 9 layers of thicknesses of layers, coating material
The interference between film layer of the characteristic of material itself and light is it is achieved that intercept ultraviolet and infrared while the high transmission of visible ray
Line, and improve its colour cast effect it is achieved that graminaceous face color.
In a word, the fenestrated membrane of the present invention passes through the double-deck reflection to infrared light for the ag alloy layer, forms folding with three floor height refracting layers
Penetrate rate matching relationship, and by the cooperation of thickness parameter, its color is viewed as grass green under sunshine, has excellent regarding
Feel effect.Meanwhile, this grass green fenestrated membrane also has excellent printing opacity, heat-insulated and antioxygenic property, and long service life is it is easy to give birth to
Produce.
Brief description
The following drawings is only intended to, in doing schematic illustration and explanation to the present invention, not delimit the scope of the invention.Wherein,
Fig. 1 is shown that the layer knot of the double silver low radiation energy-conservation fenestrated membrane of the grass green of a specific embodiment according to the present invention
Structure schematic diagram；
Fig. 2 is shown that the light transmittance curve figure of the double silver low radiation energy-conservation fenestrated membrane of grass green shown in Fig. 1；
Fig. 3 is shown that the reflectance curve figure of the double silver low radiation energy-conservation fenestrated membrane of grass green shown in Fig. 1.
Specific embodiment
In order to be more clearly understood to the technical characteristic of the present invention, purpose and effect, now comparison brief description this
Bright specific embodiment.Wherein, identical part adopts identical label.
The Rotating fields schematic diagram of the double silver low radiation energy-conservation fenestrated membrane of the grass green of the present invention as shown in Figure 1, film layer structure by
It is followed successively by from inside to outside：Flexible and transparent PET base material layer 1, thickness is 23 microns～50 microns, its visible light transmittance rate >=89%, mist
Degree≤1.5, preferred thickness is 23 microns；First high refractive index layer 2, thickness is 33nm～35nm, and refractive index is 2.36, described the
One high refractive index layer 2 is by Nb2O5Constitute, preferred thickness is 34nm；First metal oxide layer 3, thickness is 3nm～6nm, described
First metal oxide layer 3 is by ZnO:Al is constituted, and preferred thickness is 5nm；First ag alloy layer 4, thickness is 9nm～11nm, institute
State the Ag that the first ag alloy layer 4 is by 96%, 4% Cu is constituted, and preferred thickness is 10nm；First barrier layer 5, thickness is 0.5nm
～0.8nm, described first barrier layer 5 is made up of Ti, and preferred thickness is 0.6nm；Second high refractive index layer 6, thickness be 66nm～
70nm, refractive index is 2.36, and described second high refractive index layer 6 is by Nb2O5Constitute, preferred thickness is 68nm；Second metal oxide
Layer 7, thickness is 6nm～8nm, and described second metal oxide layer 7 is by ZnO:Al is constituted, and preferred thickness is 7nm；Second silver alloy
Layer 8, thickness is 14.5nm～16.5nm, described second ag alloy layer 8 by 98% Ag, 2% Pd constitutes, and preferred thickness is
14.7nm；Second barrier layer 9, thickness is 0.7nm～1nm, and described second barrier layer 9 is made up of Ti, and preferred thickness is 0.9nm；
3rd high refractive index layer 10, thickness is 29nm～32nm, and refractive index is 2.36, and described 3rd high refractive index layer 10 is by Nb2O5Structure
Become, preferred thickness is 30nm.
Preparation process the following detailed description of the double silver low radiation energy-conservation fenestrated membrane of grass green of the present invention：
(1) provide flexible and transparent PET film first as described flexible and transparent PET base material layer 1.In a specific embodiment
In, visible light transmittance rate >=89% of described flexible and transparent PET base material layer 1, mist in order to obtain more excellent light transmittance, can be selected
Degree≤1.5.
(2) by way of dual rotary negative electrode, MF reactive magnetron sputtering, in this PET base material layer 1, deposition first is high rolls over
Penetrate rate layer 2, the refractive index of preferably described first high refractive index layer 2 is 2.36.The present invention is by way of magnetron sputtering in PET film
Upper Direct precipitation the first high refractive index layer 2, due to Nb2O5There is and PET film between good adhesive force, using Nb2O5Can be straight
Connect deposition on a pet film, PET film need not be carried out with extra metal coating and process to improve adhesive force, such that it is able to reduce layer
Number improves translucency, if adopt metal coating to process simultaneously, can destroy the color of the fenestrated membrane of the present invention it is impossible to obtain expectation
Grass green.
(3) deposit first by way of single rotating cathode, direct current reaction magnetron sputtering on this first high refractive index layer 2
Metal oxide layer 3.Two-layer ZnO is employed in the grass green fenestrated membrane of the present invention:Al layer (zinc oxide film of aluminium doping), referring to step
Rapid 7.ZnO:The thickness very little of Al layer, only several nanometers, but the ZnO of these nano thickness:Al layer can promote subsequently
The growth of ag alloy layer makes it grow up to continuous compact texture as early as possible, thus significantly reduces the thickness of follow-up ag alloy layer, improves
The translucency of fenestrated membrane.Fine and close ag alloy layer can effectively reflect infrared ray and ultraviolet simultaneously, improves the heat-proof quality of fenestrated membrane.
In a preferred embodiment, every layer of ZnO:The thickness of Al layer is less than or equal to the 2/3 of the thickness of follow-up ag alloy layer, you can obtain
Preferably translucency and heat-proof quality.That is, the thickness of the first metal oxide layer 3 is less than or equal to the first ag alloy layer 4
The 2/3 of thickness；The thickness of the second metal oxide layer 7 is less than or equal to the 2/3 of the thickness of the second ag alloy layer 8.
(4) by way of monoplane negative electrode, direct current reaction magnetron sputtering on this first metal oxide layer 3 deposition the
One ag alloy layer 4.Preferably described ag alloy layer includes 96% Ag, balance of 4% Cu, can relatively fine silver obtain more preferably
Antioxygenic property and moisture protection, certainly, the setting of ag alloy layer is mainly used for infrared ray and ultraviolet are carried out instead
Penetrate to provide excellent heat-proof quality.Simultaneously it should be pointed out that because the thickness of ag alloy layer is more than or equal to ZnO below:Al
The 3/2 of the thickness of layer, and the consistency of the ag alloy layer being formed is higher, thus the color of the fenestrated membrane of the present invention is subject to silver alloy
The impact of the thickness of layer is larger, certainly, for the setting of the double-deck ag alloy layer of the present invention, between two-layer ag alloy layer
Spacing and the index matching relation of three floor height refracting layers, be also obtain grass green fenestrated membrane color indispensable because
Element, after to this detailed description.
In a preferred embodiment, in step 4, can by arrange horizontal parallel arrangement UV mask by way of,
First ag alloy layer 4 is deposited on the first metal oxide layer 3, then UV mask is removed, form horizontal direction parallel arrangement
Striated the first ag alloy layer 4.The generation type of such as UV mask can be to spray one in the first metal oxide layer 3
Layer UV glue, then utilizes UV light irradiation UV glue after horizontally arranged stripe grating, so that the UV glue of the part being illuminated is consolidated
Change, uncured UV glue is removed, form the UV mask of horizontal parallel arrangement.
Horizontal direction parallel arrangement striated the first ag alloy layer 4 can be formed in the vertical different light transmittances and
Reflectivity, but have no effect on the sight line of parallel direction, thus when user outwards observes near glass pane inside glass pane
When, user's sight line nearly horizontal perpendicular to stripe direction, thus outside sight line can't be affected.And outside glass pane
Personnel when observed, generally distant, thus be easily subject to the shadow of longitudinally upper different light transmittances and reflectivity
Ring, lead to blurred vision, image mottled, such that it is able to prevent from peeping.
(5) deposition first resistance on this first ag alloy layer 4 by way of monoplane negative electrode, direct current reaction magnetron sputtering
Interlayer 5.First barrier layer 5 is used for the first ag alloy layer 4 is protected, it is to avoid the first ag alloy layer 4 aoxidize and printing opacity and
Reflecting properties reduce it is ensured that the reflectivity of the infrared light of ag alloy layer will not reduce with the prolongation of use time, extend
The service life of fenestrated membrane, has lasting high effect of heat insulation.In a preferred embodiment, the thickness of the first barrier layer 5 is less than
It is equal to the 1/5 of the thickness of the first ag alloy layer 4 below, this thickness proportion can utilize the first barrier layer 5 of minimum thickness
Obtain the antioxygenic property needing, thus optimum effect of heat insulation can be obtained with minimum thickness, improve the entirety of fenestrated membrane
Light transmission.
(6) by way of dual rotary negative electrode, MF reactive magnetron sputtering, on this first barrier layer 5, deposition second is high rolls over
Penetrate rate layer 6, the refractive index of preferably described second high refractive index layer 6 is 2.36.The thickness of the second high refractive index layer 6 of this step and
The relatively other high refractive index layer of refractive index will be big, that is, for the double-deck ag alloy layer of the present invention, two-layer silver alloy
Second high refractive index layer 6 of bigger refractive index is set between layer, it is possible to use the interval shape between less two-layer ag alloy layer
Become the bireflectance structure of reflection infrared ray and ultraviolet, thus the thickness of the second high refractive index layer 6 can be reduced, improve fenestrated membrane
Integral light-transmitting performance.
(7) deposit second by way of single rotating cathode, direct current reaction magnetron sputtering on this second high refractive index layer 6
Metal oxide layer 7.In this step, the thickness of the second metal oxide layer 7 of deposition is than the first metal oxygen in abovementioned steps 3
The thickness of compound layer 3 is bigger, in order to more infrared rays and ultraviolet are reflected by the second ag alloy layer 8 of thicker outer layer,
Can pass through outer layer the second ag alloy layer 8 reduced, thus the first ag alloy layer 4 of internal layer can arrange thinner one
A bit, the thickness of corresponding first metal oxide layer 3 can also diminish.By the first metal oxide layer 3 and the second metal oxygen
The thickness matching of compound layer 7, can improve the optical homogeneity of fenestrated membrane, but obvious action is can be to the window of the present invention
The colourity of film is adjusted, i.e. the grass green of the grass green fenestrated membrane of the present invention, mainly by the first metal oxide layer 3 and second
The thickness proportion relation of metal oxide layer 7 and the first ag alloy layer 4 thereon and the second ag alloy layer 8 is determined.This is
The present invention is different from the best parameter group of other technology, and prior art there is no any scheme to provide the ginseng obtaining grass green fenestrated membrane
Number combinatorial principle, this parameter combination right and wrong is it will be apparent that possessing prominent substantive distinguishing features and significantly improving.
(8) by way of monoplane negative electrode, direct current reaction magnetron sputtering on this second metal oxide layer 7 deposition the
Two ag alloy layers 8.Preferably described ag alloy layer includes 98% Ag, balance of 2% Pd.The setting of the second ag alloy layer 8
Define the bireflectance structure of reflection infrared ray and ultraviolet, reduce fenestrated membrane thickness, improve light transmission, strengthen simultaneously
Heat-proof quality.
Similar, as in step 4, in a preferred embodiment, in the magnetron sputtering process of step 8,
The second ag alloy layer can be deposited by way of the UV mask of horizontal parallel arrangement is set on the second metal oxide layer 7
8, then UV mask is removed, form the second ag alloy layer 8 of the striated of horizontal direction parallel arrangement.Form the side of UV mask
Formula is as it was previously stated, be not repeated.
However, the striped of horizontal direction parallel arrangement of the second ag alloy layer 8 of this step formation and the first ag alloy layer 4
Horizontal direction parallel arrangement striped be preferably staggeredly arranged, i.e. the striped of the second ag alloy layer 8 is just to the first silver alloy
The gap of the striped of layer 4, the gap of the striped of the second ag alloy layer 8 striped just to the first ag alloy layer 4.Preferred at another
In embodiment, can arrange that width of fringe is identical with interval width, so be easy to the setting of striped mask, also allow for two-layer simultaneously
Striped is just staggeredly arranged, and can be easy to process with Simplified flowsheet.
By the striped being staggeredly arranged, respective gap is covered up, heat-insulated and reflecting effect can be avoided due to gap
Presence and reduce.Meanwhile, the striped that is staggeredly arranged so that near glass pane observe when (within 1 meter), its light transmittance and
Reflectivity is almost identical, that is, is barely detectable the presence of striped from outside to inside and from inside to outside, and from 1 meter with
When outer observation, the presence due to sight line angle can produce anti-peeping effect.Meanwhile, the ag alloy layer of striated reduces
Range of defilade, improves light transmittance, the function simultaneously for fenestrated membrane and the impact of color homogeneity are comparatively small.
(9) by way of monoplane negative electrode, direct current reaction magnetron sputtering on this second ag alloy layer 8 deposition the two the
One barrier layer 9, in order to the second ag alloy layer 8 formed protection, anti-oxidation it is ensured that the reflectivity of the infrared light of ag alloy layer not
Can reduce with the prolongation of use time, extend the service life of fenestrated membrane, there is lasting high effect of heat insulation.Excellent at one
The thickness selecting in embodiment the two the first barrier layers 9 is less than or equal to the 1/5 of the thickness of the second ag alloy layer 8 below, this thickness
Degree ratio can utilize the two the first barrier layers 9 of minimum thickness to obtain the antioxygenic property needing, thus can be with minimum
Thickness obtains optimum effect of heat insulation, improves the integral light-transmitting performance of fenestrated membrane.
(10) by way of dual rotary negative electrode, MF reactive magnetron sputtering on the two the first barrier layers 9 deposition the
Three high refractive index layers 10, the refractive index of preferably described 3rd high refractive index layer 10 is 2.36.Outermost 3rd high refractive index layer
10 select the infrared light in sunlight is effectively reflected, and further increase the heat-proof quality of fenestrated membrane.Meanwhile, three floor height refraction
The refraction of rate layer is superimposed with two-layer ag alloy layer reflection light, ultimately forms the grass green fenestrated membrane needed for the present invention.
Wherein, during magnetron sputtering deposition plated film, the temperature constant of all within the chambers, and all within the chamber steady temperature models
Enclose for -15 DEG C～15 DEG C.
Preferably, described step (2), step (3), step (6), step (7), step (10) all include：In corresponding chambers
Being passed through volume ratio is 10:1～100:1 argon gas and the mixed gas of oxygen, set sputtering vacuum 10-6Torr, plated film is stable
Air pressure is 10-3Torr；Dual rotary negative electrode, MF reactive magnetron sputtering power are 20Kw～50Kw；Single rotating cathode, direct current reaction
Magnetron sputtering power is 2Kw～5Kw.
Preferably, described step (4), step (5), step (8), step (9) all include：It is passed through purity not in corresponding chambers
Argon gas less than 99.99%, sets sputtering vacuum 10-6Torr, it is 10 that plated film stablizes air pressure-3Torr；Monoplane negative electrode, straight
Stream reaction magnetocontrol sputtering power is 0.5Kw～8Kw.
The double silver low radiation energy-conservation fenestrated membrane of grass green that the present invention is provided is placed in test in solar film tester, and result is as schemed
Shown in 2-3, it is shown that the light transmittance curve figure of the double silver low radiation energy-conservation fenestrated membrane of grass green shown in Fig. 1 and reflectivity are bent respectively
Line chart, in figure shows, the double silver low radiation energy-conservation fenestrated membrane of the grass green that the present invention provides in the light transmittance of visible-range is
74.3%；It is 9.3% in the light transmittance of the infrared region for 780nm～2500nm for the wavelength.In addition, through test, the present invention
There is provided grass green fenestrated membrane wavelength for the infrared barrier rate at 950nm wavelength be 82.5%；At wavelength is for 1400nm wavelength
Infrared barrier rate be 95%, show that the double silver low radiation energy-conservation fenestrated membrane of grass green that the present invention provides has good optical property
And heat-proof quality.
The double silver low radiation energy-conservation fenestrated membrane of this grass green that the present invention is provided is placed in spectrophotometer tests its color.
Color through color, reflected colour is to be characterized by CIELAB color space index system, and wherein L* represents brightness, the big table of numerical value
Show bright, numerical value is little to represent dark；A* represents red green degree, wherein a* bear represent green, numerical value bigger represent greener, a* just representing red, number
Value is bigger to represent redder；B* represents champac degree, and wherein b* bears and represents indigo plant, and numerical value is bigger to represent more blue, and b* is just representing Huang, and numerical value is got over
Big expression is more yellow.It is the color that can see during external scene in terms of glass after in automobile, in building through pad pasting through color；
Reflected colour is the color that can see during internal scenery in terms of glass after automobile, outside building through pad pasting.Through test, this
Through multiple spot retest in spectrophotometer, it passes through the a* of color to the double silver low radiation energy-conservation fenestrated membrane of grass green that invention provides
=-1.88, b*=1.17, a*=4.69, the b*=-0.49 of reflected colour, its color is viewed as grass green, black matrix under sunshine
Upper observation is no anti-purple, glare phenomenon, and its reflected spectral range is 500nm～625nm, has excellent visual effect.
In sum, the fenestrated membrane of the present invention passes through the double-deck reflection to infrared light for the ag alloy layer, with three floor height refracting layer shapes
Become index matching relation, and by the cooperation of thickness parameter, its color is viewed as grass green under sunshine, has excellent
Visual effect.Meanwhile, this grass green fenestrated membrane also has excellent printing opacity, a heat-insulated and antioxygenic property, long service life, easily
In produce and promote the use of.
It will be appreciated by those skilled in the art that although the present invention is to be described according to the mode of multiple embodiments,
It is that not each embodiment only comprises an independent technical scheme.For the sake of in specification, so narration is just for the sake of understanding,
Specification should be understood by those skilled in the art as an entirety, and by involved technical scheme in each embodiment
Regard as and can be mutually combined into the mode of different embodiments to understand protection scope of the present invention.
The foregoing is only the schematic specific embodiment of the present invention, be not limited to the scope of the present invention.Any
Those skilled in the art, the equivalent variations made on the premise of the design without departing from the present invention and principle, modification and combination,
The scope of protection of the invention all should be belonged to.
Claims (9)
1. the double silver low radiation energy-conservation fenestrated membrane of a kind of grass green is in grass green in the sun it is characterised in that the film layer of described fenestrated membrane
Structure is followed successively by from inside to outside：
Flexible and transparent PET base material layer (1), thickness is 23 microns～50 microns, its visible light transmittance rate >=89%, mist degree≤1.5；
First high refractive index layer (2), thickness be 33nm～35nm, refractive index be 2.36, described first high refractive index layer (2) by
Nb2O5Constitute；
First metal oxide layer (3), thickness is 3nm～6nm, and described first metal oxide layer (3) is by ZnO:Al is constituted；
First ag alloy layer (4), thickness be 9nm～11nm, described first ag alloy layer (4) by 96% Ag, 4% Cu structure
Become；
First barrier layer (5), thickness is 0.5nm～0.8nm, and described first barrier layer (5) is made up of Ti；
Second high refractive index layer (6), thickness be 66nm～70nm, refractive index be 2.36, described second high refractive index layer (6) by
Nb2O5Constitute；
Second metal oxide layer (7), thickness is 6nm～8nm, and described second metal oxide layer (7) is by ZnO:Al is constituted；
Second ag alloy layer (8), thickness is 14.5nm～16.5nm, described second ag alloy layer (8) by 98% Ag, 2%
Pd is constituted；
Second barrier layer (9), thickness is 0.7nm～1nm, and described second barrier layer (9) is made up of Ti；
3rd high refractive index layer (10), thickness be 29nm～32nm, refractive index be 2.36, described 3rd high refractive index layer (10) by
Nb2O5Constitute.
2. the double silver low radiation energy-conservation fenestrated membrane of grass green according to claim 1 is it is characterised in that described first metal aoxidizes
The thickness of nitride layer (3) is less than or equal to the 2/3 of the thickness of described first ag alloy layer (4)；Described second metal oxide layer (7)
Thickness is less than or equal to the 2/3 of the thickness of described second ag alloy layer (8).
3. the double silver low radiation energy-conservation fenestrated membranes of grass green according to claim 1 are it is characterised in that described first barrier layer
(5) thickness is less than or equal to the 1/5 of the thickness of described first ag alloy layer (4)；The thickness of described second barrier layer (9) be less than etc.
In the thickness of described second ag alloy layer (8) 1/5.
4. the double silver low radiation energy-conservation fenestrated membranes of grass green according to claim 1 are it is characterised in that described flexible and transparent PET
The thickness of substrate layer (1) is 23 microns；The thickness of described first high refractive index layer (2) is 34nm；Described first metal oxide
The thickness of layer (3) is 5nm；The thickness of described first ag alloy layer (4) is 10nm；The thickness of described first barrier layer (5) is
0.6nm；The thickness of described second high refractive index layer (6) is 68nm；The thickness of described second metal oxide layer (7) is 7nm；Institute
Stating the second ag alloy layer (8) thickness is 14.7nm；The thickness of described second barrier layer (9) is 0.9nm；Described 3rd high index of refraction
The thickness of layer (10) is 30nm.
5. the double silver low radiation energy-conservation fenestrated membranes of grass green according to claim 4 are it is characterised in that the double silver of described grass green is low
Radiation energy-saving fenestrated membrane the light transmittance of visible-range be 74.3%, the infrared region for 780nm～2500nm in wavelength
Light transmittance is 9.3%, wavelength for the infrared barrier rate at 950nm wavelength be 82.5%, at wavelength is for 1400nm wavelength
Infrared barrier rate is 95%.
6. the preparation method of the double silver low radiation energy-conservation fenestrated membrane of a kind of grass green according to any one of Claims 1 to 5, its
It is characterised by, comprise the steps：
(1) provide flexible and transparent PET film as described flexible and transparent PET base material layer (1)；
(2) in the upper deposition of described flexible and transparent PET base material layer (1) by way of dual rotary negative electrode, MF reactive magnetron sputtering
Described first high refractive index layer (2)；
(3) described in the upper deposition of described first high refractive index layer (2) by way of single rotating cathode, direct current reaction magnetron sputtering
First metal oxide layer (3)；
(4) in described first metal oxide layer (3) upper deposition institute by way of monoplane negative electrode, direct current reaction magnetron sputtering
State the first ag alloy layer (4)；
(5) in the upper deposition of described first ag alloy layer (4) described the by way of monoplane negative electrode, direct current reaction magnetron sputtering
One barrier layer (5)；
(6) in the upper deposition described second of described first barrier layer (5) by way of dual rotary negative electrode, MF reactive magnetron sputtering
High refractive index layer (6)；
(7) described in the upper deposition of described second high refractive index layer (6) by way of single rotating cathode, direct current reaction magnetron sputtering
Second metal oxide layer (7)；
(8) in described second metal oxide layer (7) upper deposition institute by way of monoplane negative electrode, direct current reaction magnetron sputtering
State the second ag alloy layer (8)；
(9) in the upper deposition of described second ag alloy layer (8) described the by way of monoplane negative electrode, direct current reaction magnetron sputtering
Two barrier layers (9)；
(10) in the upper deposition of described second barrier layer (9) described the by way of dual rotary negative electrode, MF reactive magnetron sputtering
Three high refractive index layers (10).
7. the preparation method of the double silver low radiation energy-conservation fenestrated membrane of grass green according to claim 6 is it is characterised in that in magnetic control
During sputtering sedimentation plated film, the temperature of all within the chambers respectively constant at -15 DEG C～15 DEG C.
8. the preparation method of the double silver low radiation energy-conservation fenestrated membrane of grass green according to claim 6 is it is characterised in that described step
Suddenly (2), step (3), step (6), step (7), step (10) all include：Being passed through volume ratio in corresponding chambers is 10:1～100:
1 argon gas and the mixed gas of oxygen, set sputtering vacuum 10-6Torr, it is 10 that plated film stablizes air pressure-3Torr；Bispin is turned out cloudy
Pole, MF reactive magnetron sputtering power are 20Kw～50Kw；Single rotating cathode, direct current reaction magnetron sputtering power be 2Kw～
5Kw.
9. the preparation method of the double silver low radiation energy-conservation fenestrated membrane of grass green according to claim 6 is it is characterised in that described step
Suddenly (4), step (5), step (8), step (9) all include：It is passed through the argon gas that purity is not less than 99.99% in corresponding chambers, if
Surely sputter vacuum 10-6Torr, it is 10 that plated film stablizes air pressure-3Torr；Monoplane negative electrode, direct current reaction magnetron sputtering power are
0.5Kw～8Kw.
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| CN115857234A (en) * | 2022-11-15 | 2023-03-28 | 佛山纳诺特科技有限公司 | Color light adjusting film and preparation method thereof |
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