CN115157815B - Photochromic inner suspension film - Google Patents

Photochromic inner suspension film Download PDF

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Publication number
CN115157815B
CN115157815B CN202210916316.XA CN202210916316A CN115157815B CN 115157815 B CN115157815 B CN 115157815B CN 202210916316 A CN202210916316 A CN 202210916316A CN 115157815 B CN115157815 B CN 115157815B
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layer
inner suspension
silver alloy
suspension film
film
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CN115157815A (en
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吴培服
陆敬权
吴迪
许庚午
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Jiangsu Shuangxing Color Plastic New Materials Co Ltd
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Jiangsu Shuangxing Color Plastic New Materials Co Ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/36Layered products comprising a layer of synthetic resin comprising polyesters
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/06Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • EFIXED CONSTRUCTIONS
    • E06DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
    • E06BFIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
    • E06B3/00Window sashes, door leaves, or like elements for closing wall or like openings; Layout of fixed or moving closures, e.g. windows in wall or like openings; Features of rigidly-mounted outer frames relating to the mounting of wing frames
    • E06B3/30Coverings, e.g. protecting against weather, for decorative purposes
    • EFIXED CONSTRUCTIONS
    • E06DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
    • E06BFIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
    • E06B3/00Window sashes, door leaves, or like elements for closing wall or like openings; Layout of fixed or moving closures, e.g. windows in wall or like openings; Features of rigidly-mounted outer frames relating to the mounting of wing frames
    • E06B3/66Units comprising two or more parallel glass or like panes permanently secured together
    • E06B3/677Evacuating or filling the gap between the panes ; Equilibration of inside and outside pressure; Preventing condensation in the gap between the panes; Cleaning the gap between the panes
    • EFIXED CONSTRUCTIONS
    • E06DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
    • E06BFIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
    • E06B9/00Screening or protective devices for wall or similar openings, with or without operating or securing mechanisms; Closures of similar construction
    • E06B9/24Screens or other constructions affording protection against light, especially against sunshine; Similar screens for privacy or appearance; Slat blinds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00Coating on the layer surface
    • B32B2255/10Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00Coating on the layer surface
    • B32B2255/20Inorganic coating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00Coating on the layer surface
    • B32B2255/20Inorganic coating
    • B32B2255/205Metallic coating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00Coating on the layer surface
    • B32B2255/26Polymeric coating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00Coating on the layer surface
    • B32B2255/28Multiple coating on one surface
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/40Properties of the layers or laminate having particular optical properties
    • B32B2307/402Coloured
    • EFIXED CONSTRUCTIONS
    • E06DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
    • E06BFIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
    • E06B9/00Screening or protective devices for wall or similar openings, with or without operating or securing mechanisms; Closures of similar construction
    • E06B9/24Screens or other constructions affording protection against light, especially against sunshine; Similar screens for privacy or appearance; Slat blinds
    • E06B2009/2405Areas of differing opacity for light transmission control

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  • Engineering & Computer Science (AREA)
  • Structural Engineering (AREA)
  • Civil Engineering (AREA)
  • Architecture (AREA)
  • Laminated Bodies (AREA)

Abstract

The application discloses a photochromic inner suspension film, which comprises an inner suspension film substrate, wherein at least one silver alloy layer is formed on the sunlight irradiation surface of the inner suspension film substrate, and a photochromic layer is formed on the other surface of the inner suspension film substrate opposite to the sunlight irradiation surface; the inner suspension film base material comprises a polyester film, at least one ZnO Al layer is formed on the outermost side of the polyester film facing the silver alloy layer, and an adhesion layer is formed between the ZnO Al layer and the outermost side of the polyester film. By matching the additional layer with the ZnO-Al layer, the application can obviously reduce the surface cracks of the inner suspension film base material and improve the growth speed of the silver alloy layer. In addition, by arranging the photochromic layer on the inner side of the sunlight irradiation surface of the inner suspension film, the material and processing cost can be greatly reduced, and the price of the product can be reduced. Meanwhile, along with the reduction of the dosage of the components such as the photochromic material and the like and the reduction of the thickness of the coating, the influence on the overall light transmittance of the inner suspension film is reduced, and the use experience of a user of the inner suspension film is improved.

Description

Photochromic inner suspension film
Technical Field
The application relates to a hollow heat-insulating glass door and window in the field of energy-saving buildings, in particular to a photochromic inner suspension film.
Background
The energy-saving building field generally adopts hollow glass doors and windows to isolate indoor and outdoor temperature differences and realize light transmission. The sticking of a window film with specific functions on the surface of glass is a prior art means for effectively improving the heat insulation performance of glass doors and windows.
The photochromic window film can reduce the visible light transmittance when the light is strong, has anti-glare and heat insulation effects, and can improve the visible light transmittance when the light is weak. Traditional window film needs to adhere to and paste on glass surface, and because glass's heat transfer coefficient is higher, leads to the window film to need bear harsher cold and hot environment, appears local bubble, layering etc. condition easily.
The basic principle of the energy-saving door and window is that one or more layers of transparent plastic films are added in the inner cavity of the hollow glass, and the inner cavity of the hollow glass is isolated into a plurality of mutually independent spaces through the plastic films, so that the temperature difference between the inside and the outside of the hollow glass can not realize convection, thereby reducing the weight of the structure and simultaneously having excellent energy-saving effect.
The inner suspension film for the inner suspension film door and window is usually made of plastic film with better heat resistance and insulation effects. For example, a plastic film such as a window film commonly used in the field of ordinary buildings may be used as the inner suspension film. For example, in prior art CN 106435497A previously filed by the applicant, a gold-colored low-emissivity energy-saving window film which is gold in sunlight and a method for producing the same are disclosed. The prior art window film materials typically require the formation of a metal oxide layer and a silver-containing metal layer on the surface of the substrate. For example, CN 106435497A describes that the golden window film is: a flexible transparent PET substrate layer; from Si 3 N 4 A first high refractive index layer formed; a first metal oxide layer composed of ZnO and Al; a first silver alloy layer composed of 98% Ag and 2% Pd; a first barrier layer composed of Si; from Nb 2 O 5 A second high refractive index layer; forming a second metal oxide layer from ZnO and Al; a second silver alloy layer composed of 98% Ag and 2% Pd; forming a second barrier layer from Si; from Si 3 N 4 And a third high refractive index layer is formed. The prior art particularly indicates that the color of the golden window film and the functions of effectively reflecting infrared rays and ultraviolet rays and improving the heat insulation performance of the window film are mainly brought by a compact silver alloy layer, the compactness of the silver alloy layer can be realized by ZnO with a thickness of a few nanometers, namely, an Al metal oxide layer, and the ZnO with a thickness of a few nanometers:the Al layer can promote the growth of the subsequent silver alloy layer to enable the subsequent silver alloy layer to grow into a continuous compact structure as soon as possible, so that the thickness of the subsequent silver alloy layer is obviously reduced, and the light transmittance of the window film is improved.
For an inner suspended film door and window, the thermal expansion coefficient of an inner suspended film clamped between two pieces of glass is larger than that of the glass, so that the inner suspended film tends to be gradually loosened in the use process, and the loosened inner suspended film is inconsistent in the refraction direction of light, so that a scene outside the observation room through the glass door and window can generate visual deformation due to refraction. In order to maintain the parallel transmission of light rays to avoid visual distortion, the inner suspension film needs to be installed in a tensioned state between the hollow glasses. The inner suspension film in a tensioned state is deformed in the lateral direction. However, the ZnO film layer formed by growth in a magnetron sputtering mode has the characteristic of high vertical crystallization, is very sensitive to transverse deformation, and is easy to generate longitudinal cracks under the action of transverse tensile force, so that the metal silver film layer attached to the surface of the ZnO film layer is cracked, and the light transmittance and the reflection performance of the window film are affected. Therefore, the window film with the silver-containing metal layer in the prior art can be adhered on a flat and firm glass surface for use, and is difficult to apply to the field of inner suspension films.
Therefore, if a window film having a photochromic function is to be obtained, it is generally required to adhere the window film to the glass surface, and the requirement for the adhesive property of the photochromic window film is high, and it is difficult to reduce the cost. The existing window film stuck on the surface of glass is difficult to adapt to the inner suspension film door and window. It is therefore desirable to develop an inner suspension film having photochromic function and low stretch cracking.
Disclosure of Invention
The technical problem to be solved by the present application is to provide a photochromic inner suspension film, so as to reduce or avoid the aforementioned problems.
In order to solve the technical problems, the application provides a photochromic inner suspension film which is used for being arranged in a tensioning frame clamped between two layers of glass in a tensioning mode, wherein the inner suspension film comprises an inner suspension film substrate, at least one silver alloy layer is formed on a sunlight irradiation surface of the inner suspension film substrate, and a photochromic layer is formed on the other surface of the inner suspension film substrate opposite to the sunlight irradiation surface; the inner suspension film base material comprises a polyester film, wherein at least one ZnO Al layer is formed on the outermost side of the polyester film facing the silver alloy layer, and an adhesion layer is formed between the ZnO Al layer and the outermost side of the polyester film; the silver alloy layer comprises a silver alloy base layer, a metal titanium protective layer is formed on the outer side of the silver alloy base layer, and an indium oxide protective layer is formed on the outer side of the metal titanium protective layer.
Preferably, the adhesion layer is prepared from the following raw materials in parts by weight: 6-8 parts by weight of polydimethylsiloxane; 1-5 parts of polyurethane; 15-30 parts by weight of vinyl trimethoxy silane; 80-120 parts by weight of isopropanol; 10-20 parts of polyethylene glycol; 1-5 parts of zinc oxide; 0.1-0.5 parts by weight of alumina; 0.1 to 0.5 part by weight of magnesium sulfate.
Preferably, the thickness of the silver alloy base layer is 10-15nm; the thickness of the metal titanium protective layer is 3-6nm; the thickness of the indium oxide protective layer is 55-85nm.
Preferably, the thickness of the adhesion layer is 10-20nm; the thickness of the ZnO/Al layer is 3-6nm.
Preferably, two superimposed silver alloy layers are formed on the sunlight irradiation surface of the inner suspension film substrate, and the two silver alloy layers have the same structure and all comprise a silver alloy base layer, a metallic titanium protective layer and an indium oxide protective layer.
Preferably, the inner suspension film comprises two layers of inner suspension film base materials, a photochromic layer is arranged between the two layers of inner suspension film base materials, and a silver alloy layer is formed on the outer sides of the two layers of inner suspension film base materials; the two silver alloy layers have the same structure and comprise a silver alloy base layer, a metallic titanium protective layer and an indium oxide protective layer.
Preferably, the two-layer inner suspension film base material comprises a polyester film, and the two polyester films are provided with an adhesion layer and a ZnO: al layer of two silver alloy layers in mirror symmetry from two sides of the photochromic layer.
By matching the additional layer with the ZnO-Al layer, the application can obviously reduce the surface cracks of the inner suspension film base material and improve the growth speed of the silver alloy layer. In addition, by arranging the photochromic layer on the inner side of the sunlight irradiation surface of the inner suspension film, the material and processing cost can be greatly reduced, and the price of the product can be reduced. Meanwhile, along with the reduction of the dosage of the components such as the photochromic material and the like and the reduction of the thickness of the coating, the influence on the overall light transmittance of the inner suspension film is reduced, and the use experience of a user of the inner suspension film is improved.
Drawings
The following drawings are only for purposes of illustration and explanation of the present application and are not intended to limit the scope of the application.
Fig. 1 shows a partially cut-away schematic illustration of an inner suspended membrane door and window according to an embodiment of the application.
Fig. 2 is a schematic view showing the principle of heat insulation of an inner suspension film according to an embodiment of the present application.
Figures 3a-3c show schematic cross-sectional structures of inner suspension films according to three embodiments of the present application, respectively.
Fig. 4 shows an exploded perspective view of a tensioning frame according to an embodiment of the application.
Fig. 5 shows an enlarged partial exploded view of a tensioning frame according to another embodiment of the application.
Fig. 6 is a schematic structural view of a second frame according to an embodiment of the present application.
Fig. 7 shows a schematic structural view of an elastic tensioner according to an embodiment of the present application.
Fig. 8 shows an exploded perspective view of an elastic tensioning device according to yet another embodiment of the present application.
Detailed Description
For a clearer understanding of technical features, objects, and effects of the present application, a specific embodiment of the present application will be described with reference to the accompanying drawings. Wherein like parts are designated by like reference numerals.
As shown in fig. 1, the present application provides an inner suspension film door and window, at least comprising a tensioning frame 3 sandwiched between two glass layers 1 for tensioning an inner suspension film 2, wherein the tensioning frame 3 of the present application can be installed between two glass layers 1 as a separate component with the inner suspension film 2 tensioned thereon, thus the tensioning problem of the inner suspension film is not required to be considered when the glass door and window is installed, and the installation complexity is reduced.
The inner suspension film 2 is a photochromic inner suspension film with a photochromic function and low stretch cracks according to the present application, and for brevity, the photochromic inner suspension film according to the present application is collectively referred to as an inner suspension film.
Further, in the illustrated embodiment, both sides of the tension frame 3 may be bonded between the two layers of glass 1 by spacer bars 4. For example, the spacer 4 may be an existing composite butyl aluminum spacer, butyl rubber for adhesion is provided on two sides of the spacer 4, and a molecular sieve for adsorbing water vapor may be disposed in a hollow structure inside the spacer 4. The inner suspension film door and window is only provided with one layer of inner suspension film 2, and can be deformed into a structure with two or more layers of inner suspension films by adding the tensioning frame 3 according to the requirement.
The inner suspension film 2 is made of a plastic film with good heat-resistant and insulating effects, and needs to be tensioned between the hollow glass to keep light rays to transmit in parallel to avoid visual deformation.
Fig. 2 is a schematic view showing a heat insulation principle of an inner suspension film according to an embodiment of the present application, and illustrates that the inner suspension film 2 includes an inner suspension film substrate 21, at least one silver alloy layer 22 is formed on a sunlight irradiation surface of the inner suspension film substrate 21, and a photochromic layer 23 is formed on the other surface of the inner suspension film substrate 21 opposite to the sunlight irradiation surface. The silver alloy layer 22 can realize the functions of high visible light transmission and reflection to most of infrared rays so as to effectively isolate heat. The photochromic layer 23 is used to provide the inner suspension film 2 with a photochromic function (which will be described in further detail later).
Fig. 3a-3c further show schematic cross-sectional structures of inner suspension films according to various embodiments of the present application, wherein the inner suspension film substrate 21 of the present application comprises a polyester film 211, and at least one ZnO: al layer 213 (aluminum doped zinc oxide layer, aluminum content not more than 2 wt%) is formed on the outermost side of the polyester film 211 facing the silver alloy layer 22, and an adhesion layer 212 is formed between the ZnO: al layer 213 and the outermost side of the polyester film 211, as shown in the specific embodiment. The ZnO: al layer 213 may be formed on the surface of the adhesion layer 212 by means of single-rotation cathode, direct-current reactive magnetron sputtering.
As described above, the ZnO-Al layer can promote the growth of the subsequent silver alloy layer to make the subsequent silver alloy layer grow into a continuous compact structure as soon as possible, thereby remarkably reducing the thickness of the subsequent silver alloy layer and improving the light transmittance of the window film. However, the defect of the ZnO/Al layer is that the film layer is crystallized by growing along the vertical direction of the film, and cracks are generated in the transversely stretched state. The inventors found that the probability of crack generation in the case of extreme wrinkles can be reduced by reducing the thickness of the ZnO: al layer, but that the growth rate of the silver alloy layer on the ZnO: al layer and the compactness of the film layer can be simultaneously reduced.
According to the same technical conditions as disclosed in CN 106435497A cited in the background art, a ZnO/Al layer of 3nm to 6nm thickness was formed on a polyester film. The test shows that at a bending diameter of 5 mm, the ZnO: al layer does not substantially crack, but at 10% elongation of the inner suspension film, the ZnO: al layer still has significant cracks. Of course, if a thicker silver alloy layer is formed on the surface of the ZnO: al layer, these cracks can be masked to some extent because the silver alloy layer has a good ductility, and no cracks are revealed when the silver alloy layer is surface-inspected. In this case, there is a contradiction that the thickness of the ZnO: al layer may be reduced in order to reduce cracks, which may result in a reduction in the growth rate of the silver alloy layer, but a thicker silver alloy layer thickness is required to mask the inner layer cracks, and further extension of the growth time of the silver alloy layer is required, thereby further increasing the production cost.
In order to overcome the contradiction, the application arranges the adhesion layer 212 on the inner side of the ZnO Al layer 213, so as to reduce the surface cracks of the inner suspension film substrate and the silver alloy layer thereon by matching the adhesion layer 212 with the ZnO Al layer 213, improve the light transmission performance, and simultaneously improve the growth speed of the silver alloy layer and reduce the processing time and the production cost under the condition of not increasing the thickness of the ZnO Al layer.
Fig. 2 shows only a schematic structure of one embodiment of the inner suspension film of the present application, and it should be understood by those skilled in the art that many modifications can be made to the inner suspension film structure of the present application while achieving the above technical effects. For example, as in the prior art, a plurality of silver alloy layers 22 may be formed on the inner suspension base material 21, each silver alloy layer 22 being provided with a ZnO: al layer 213 and an adhesion layer 212 (for example, the structure shown in fig. 3 c). Alternatively, other functional structural layers or the like may be provided between the adhesive layer 212 and the mylar film 211. The silver alloy layer 22 may also be a multi-layer composite structure including other protective layers (as will be described in further detail below).
Specifically, the adhesion layer 212 is cured by coating on the outer surface of the polyester film 211, and the adhesion layer 212 may be prepared from the following raw materials in parts by weight: 6-8 parts by weight of polydimethylsiloxane; 1-5 parts of polyurethane; 15-30 parts by weight of vinyl trimethoxy silane; 80-120 parts by weight of isopropanol; 10-20 parts of polyethylene glycol; 1-5 parts of zinc oxide; 0.1-0.5 parts by weight of alumina; 0.1 to 0.5 part by weight of magnesium sulfate.
In a specific embodiment, the inner suspension film substrate may be prepared by the steps of the following method.
Firstly, uniformly mixing 10-20 parts by weight of polyethylene glycol and 60-80 parts by weight of isopropanol, and respectively adding 1-5 parts by weight of zinc oxide, 0.1-0.5 part by weight of aluminum oxide and 0.1-0.5 part by weight of magnesium sulfate into the mixed solution, mixing and stirring for 30-60 minutes to prepare the component A.
Then, 6-8 parts by weight of polydimethylsiloxane, 1-5 parts by weight of polyurethane, 15-30 parts by weight of vinyltrimethoxysilane and 20-40 parts by weight of isopropanol are mixed, mixed and stirred for 20-30 minutes, and the viscosity is 200-300 centipoise, so that the component B is prepared.
The adhesive layer 212 is prepared by mixing and stirring the A component and the B mixed component for 20-30 minutes, then coating the surface of at least one side of the polyester film by spin coating or spray coating, and curing at 120-130 ℃ for 2-3 hours.
On the prepared adhesion layer 212, a ZnO: al layer 213 was formed by means of single-rotation cathode, direct-current reactive magnetron sputtering, thereby preparing the inner suspension film base material 21 of the present application.
Further, at least one silver alloy layer 22 can be formed on the outer side of the ZnO: al layer 213 of the inner suspension base material 21 by means of single-rotation cathode, direct-current reaction magnetron sputtering, and a photochromic layer 23 can be formed on the other side of the inner suspension base material 21, thereby preparing and obtaining an inner suspension 2 usable in the present application.
Examples 1 to 3
The adhesive layers 212 were prepared on the surfaces of the polyester films 211, respectively, based on the above preparation methods, according to the weight parts of the raw materials in the following table. The polyester film 211 is a PET film with a light transmittance of 89% and a thickness of 25 μm.
Examples 4 to 6
On the adhesion layers prepared in examples 1 to 3, znO Al layer 213 (aluminum content 1.5wt%, znO content 98.5 wt%) and silver alloy layer 22 (98 wt% Ag, 2wt% Pd) were formed, respectively, by magnetron sputtering in this order, corresponding to examples 4 to 6.
Comparative examples D1 to D3
Referring to the preparation steps of examples 1 to 3, the adhesive layers 212 for comparison were prepared on the surfaces of the polyester films 211, respectively, in the proportions by weight of the raw materials of the following table. The polyester film 211 was a PET film having a light transmittance of 89% and a thickness of 25. Mu.m, corresponding to comparative examples D1 to D3.
Comparative examples D4 to D6
Referring to the preparation steps of examples 1 to 3, the adhesive layers 212 for comparison were prepared on the surfaces of the polyester films 211, respectively, in the proportions by weight of the raw materials of the following table. The polyester film 211 was a PET film having a light transmittance of 89% and a thickness of 25. Mu.m, corresponding to comparative examples D4 to D6.
Comparative examples D7 to D12
On the adhesion layers prepared in comparative examples D1 to D6, znO was formed as a comparison by magnetron sputtering, respectively, an Al layer (aluminum content 1.5wt%, znO content 98.5 wt%) and a silver alloy layer 22 (98 wt% Ag, 2wt% Pd) were formed in this order, corresponding to comparative examples D7 to D12.
Through the above comparative experiments, the average growth rate of the silver alloy layer is greatly affected by the oxide composition, and particularly, the growth rate is most affected by a very small amount of magnesium sulfate.
The performance parameters of the respective adhesive layer skin layers of the polyester films of examples 1 to 6 and comparative examples D1 to D12 were measured, respectively.
As can be seen by comparing various performance parameters, the application can obviously reduce the surface crack of the inner suspension film base material and improve the light transmission performance by matching the ZnO: al layer with the additional layer arranged on the inner side, and simultaneously improves the growth speed of the silver alloy layer and reduces the processing time and the production cost under the condition of not increasing the thickness of the ZnO: al layer.
In addition, excessive addition of metal oxide can reduce the transparency of the film, so that cracks are easily generated on the surface of the ZnO-Al layer, and the surface quality of the silver alloy layer and the product quality are further influenced. Further tests show that the addition of a small amount of polyurethane is beneficial to maintaining the bonding strength of the silver alloy layer and the ZnO-Al layer and avoiding layering of the silver alloy layer and the ZnO-Al layer.
Further, as previously described, the silver alloy layer 22 is a multi-layer composite structure that may include other protective layers in the present application.
For example, in the embodiment shown in fig. 3a, in the inner suspension film 2 of the present application, a silver alloy layer 22 is formed on the sunlight irradiation surface of the inner suspension film substrate 21, and a photochromic layer 23 is formed on the other surface of the inner suspension film substrate 21 opposite to the sunlight irradiation surface. The silver alloy layer 22 further includes a silver alloy base layer 221 having a thickness of 10-15nm, a metallic titanium protective layer 222 having a thickness of 3-6nm is formed on the outside of the silver alloy base layer 221, and an indium oxide protective layer 223 having a thickness of 55-85nm is formed on the outside of the metallic titanium protective layer 222. Wherein, the silver alloy base layer 221 can be formed on the outer side surface of the inner suspension film substrate 21, that is, on the outer side surface of the ZnO: al layer 213 by means of single rotation cathode, direct current reaction magnetron sputtering from 98wt% Ag and 2wt% Pd. The metallic titanium protective layer 222 may be formed on the outer surface of the silver alloy base layer 221 by means of single-rotation cathode, direct-current reactive magnetron sputtering. The indium oxide protective layer 223 may be formed on the outer surface of the metallic titanium protective layer 222 by means of dual rotating cathode, intermediate frequency reactive magnetron sputtering. In a preferred embodiment, the indium oxide protective layer 223 may contain 90wt% indium oxide and 10wt% tin oxide.
As described above, since the production efficiency of the silver alloy base layer 221 is ensured and the production cost is saved, the adhesion layer 212 has to be added to cooperate with the ZnO: al layer 213 to increase the growth rate of the silver alloy base layer 221 while reducing the thickness of the ZnO: al layer 213. However, as the thickness of the silver alloy base layer 221 increases, it gradually decreases until it disappears, being promoted by the adhesion layer 212. In the absence of the complete adhesion layer 212, the growth rate of the silver alloy base layer 221 is greatly reduced (see the average growth rate parameter of comparative examples D7 to D9), and therefore the thickness of the silver alloy base layer 221 is preferably not more than 15nm, otherwise the production efficiency is greatly reduced. However, the surface quality of the silver alloy base layer 221 with a lower thickness has a certain defect, so that a thin metal titanium protective layer 222 is added to improve the surface quality of the silver alloy base layer 221. In addition, the silver alloy base layer 221 was originally useful for compensating for the occurrence of surface cracks (see the performance parameters of 5 mm diameter bending surface cracks and 5% surface cracks of film stretching of comparative examples D7 to D11), however, since the thickness of the silver alloy base layer 221 was limited, its covering effect on cracks was artificially reduced. Therefore, in order to compensate for the defect of crack coverage by the thickness of the silver alloy base layer 221 (the thickness of the metallic titanium protective layer 222 is too small, the growth speed is slow, and it is difficult to provide crack coverage by the metallic titanium protective layer), an indium oxide protective layer 223 with a large thickness is added on the outer side of the metallic titanium protective layer 222. The growth speed of the non-crystalline indium oxide is high, and the surface quality of the bottom layer is repaired through the metallic titanium protective layer, so that the indium oxide protective layer can be grown rapidly and simultaneously maintain good surface quality. Meanwhile, the amorphous indium oxide is relatively crystalline ZnO of the bottom layer, namely an Al layer, a silver alloy layer and a metallic titanium layer, and cracks are not easy to generate in a stretching state, so that the cracks of the bottom layer can be covered and prevented by the indium oxide protective layer 223 with large thickness, and meanwhile, the transparent indium oxide protective layer 223 has little influence on the light transmission performance of the film layer.
In the embodiment shown in fig. 3c, in the inner suspension film 2 of the present application, two superimposed silver alloy layers 22 are formed on the sunlight irradiation surface of the inner suspension film substrate 21, and a photochromic layer 23 is formed on the other surface of the inner suspension film substrate 21 opposite to the sunlight irradiation surface. Wherein the two silver alloy layers 22 have the same structure and each comprise a silver alloy base layer 221, a metallic titanium protective layer 222 and an indium oxide protective layer 223.
The inner suspension film 2 of the embodiment shown in fig. 3a and 3c requires attention to the installation direction, and the corresponding side of the silver alloy layer 22 is required to face the sunlight irradiation direction.
In the embodiment shown in fig. 3b, the inner suspension film 2 of the present application comprises two layers of suspension film substrates 21, a photochromic layer 23 is interposed between the two layers of suspension film substrates 21, and a silver alloy layer 22 is formed on the outer sides of the two layers of suspension film substrates 21. In this embodiment, the two inner suspension base materials 21 each comprise a polyester film 211, and the two polyester films 211 are mirror-symmetrically provided with an adhesion layer 212 and a ZnO: al layer 213 of the two silver alloy layers 22 from both sides of the photochromic layer 23, so as to form the inner suspension base materials 21 with high growth rate and low tensile crack defect on both sides. In addition, the two silver alloy layers 22 in this embodiment have the same structure, and each of them includes a silver alloy base layer 221, a metallic titanium protective layer 222, and an indium oxide protective layer 223. The inner suspension film 2 of the embodiment shown in fig. 3b can be installed in any direction when in use, and the problem of the installation direction is not required to be considered.
It should be noted that, the present application has the greatest advantage that the photochromic layer 23 is disposed on the inner side of the sunlight irradiation surface of the inner suspension film 2, and after a part of light is reflected by the silver alloy layer 22 on the outer side, the intensity of the light reaching the photochromic layer 23 is reduced, so that the requirements of various raw material components in the photochromic layer 23 can be reduced to a certain extent, the dosage of components such as photochromic materials can be reduced, the thickness of the photochromic layer 23 can be further reduced, the material and processing cost can be greatly reduced, and the price of the product can be reduced. Meanwhile, as the influence of the cold and hot environment on the photochromic layer 23 is reduced, the requirement on the bonding strength is greatly reduced, and the probability of local bubbles, layering and other conditions of the photochromic layer 23 is greatly reduced. In addition, the reduction of the dosage of the components such as the photochromic material and the reduction of the thickness of the coating reduces the influence on the overall light transmittance of the inner suspension film 2, and is beneficial to improving the use experience of the user of the inner suspension film 2.
Further, the photochromic layer 23 of the present application may be any of the prior art layered structures having a photochromic function and a processing process thereof. For example, a layered structure of a heterocyclic diarylethene compound, a light absorber, and an antioxidant dispersed in a polyester material as disclosed in CN 207291207U can be used by those skilled in the art. Alternatively, a coating structure formed by a mixture of an adhesive, a mixed solvent, an ultraviolet absorber, a photochromic material and a curing agent and a processing technology thereof disclosed in CN 106218172A can be also adopted by those skilled in the art. Similar photochromic structures and processes can also be referred to photochromic structures disclosed using the following prior art: CN 103627334B, CN 102603204B, CN 103627333B, CN 101842451A, etc.
Of course, according to the common general knowledge, the person skilled in the art can control the photochromic requirement under the condition of weakening the illumination intensity, and can reasonably reduce the material consumption and the film thickness on the basis of the scheme disclosed in the prior art, so as to obtain the optimal balance between the photochromic effect and the cost.
In order to more clearly understand the stretching and tensioning state of the inner hanging film, the structure of the inner hanging film door and window of the present application will be further described with reference to fig. 4 to 8.
Because the tensioning operation of the inner suspension film in the prior art is very complicated, four sides of the inner suspension film need to be respectively clamped on a plurality of elastic elements during installation, and in order to prevent the inner suspension film from wrinkling, the tensioning force needs to be locally and repeatedly adjusted. In addition, the inner suspension film repeatedly expands with heat and contracts with cold in the long-term use process, the tension difference can lead the film to be extruded to local positions to form folds, the permeability of the glass door and window can be influenced, and the outdoor scenery can be observed to generate visual deformation due to refraction.
In order to solve the above problems, as seen in the exploded perspective view of the tension frame 3 shown in fig. 4, the four sides of the inner suspension film 2 of the present application are wound on four reels 20, respectively, and both ends of the four reels 20 are mounted inside the tension frame 3 by elastic tensioners 5, respectively.
In one embodiment illustrated, in order to facilitate tensioning of the inner suspension film 2 while exposing both ends of the roll 20, the inner suspension film 2 is rectangular with four corners cut away, so that the four sides of the inner suspension film 2 are narrower in width near the edge positions, and thus when wound on the roll 20, the thicker the winding thickness of the inner suspension film 2 on the roll 20 is near the middle of the roll 20, and the thinner the winding thickness of the inner suspension film near both ends of the roll 20 is. That is, the inner suspension film 2 wound around the reel 20 is formed in a spindle shape having a thick middle and thin ends. Therefore, as the inner suspension film 2 is tightly wound on the reel 20, the tension force at the middle position of the inner suspension film 2 is gradually larger than the tension force at the corner position, so that the film stretching relaxation generated by the thermal expansion of the middle suspended inner suspension film can be counteracted. At the same time, the winding edges of the inner suspension film 2 tend to extend toward the two ends with a thinner thickness, thereby naturally eliminating the phenomenon that the film is locally extruded to generate wrinkles.
As can be seen from the stretching process of the inner suspension film of the present application, the middle suspended portion of the inner suspension film is stretched to the greatest extent during use, and the reel portion does not need to be stretched excessively, but if the growth thickness of the silver alloy layer is too thin or the compactness of the ZnO: al layer is insufficient during winding around the reel 20, cracks easily occur in the portion of the inner suspension film adjacent to the reel, and these cracks easily propagate toward the middle in a long-time stretched state, so that it is necessary to provide structural improvement of the inner suspension film of the present application.
Further, in order to facilitate the winding of the inner suspension film 2 by the spool 20 to generate an even tension, it is preferable that the spool 20 is circular in cross section for winding the middle portion of the inner suspension film 2. In addition, in order to facilitate that the tension force attached to the elastic tensioner 5 after tensioning does not relax, the cross section of the spool 20 for attaching both ends of the elastic tensioner 5 is square, so that the spool 20 is not easily rotated.
According to the application, the four sides of the inner suspension film are respectively wound on the four reels, so that larger tensioning force can be obtained in the middle of the inner suspension film, the heated relaxation of the inner suspension film is counteracted, and the folds are naturally eliminated through winding, so that when the inner suspension film is arranged on the tensioning frame, only the two ends of the reels are required to be tensioned, the tensioning force does not need to be adjusted one by one for every point on the periphery of the inner suspension film, and the complexity of tensioning operation is greatly reduced.
Further, as shown in fig. 5, the tension frame 3 includes a first frame 31 and a second frame 32 which are provided to be clamped between both sides of the inner suspension film 2, and the elastic tension device 5 is provided inside a cavity formed by the first frame 31 and the second frame 32 being fastened. In the particular embodiment illustrated, two elastic tensioners 5 are provided for each reel 20, so that a total of eight elastic tensioners 5 are provided inside the first 31 and second 32 frames, only six elastic tensioners 5 being shown in fig. 4 due to the shielding from view. Every two elastic tensioning devices 5 are combined into a group, and are connected into a whole through a corner connecting sheet 6, and are arranged at the corner positions of the tensioning frame 3.
The first frame 31 may be formed by splicing four profiles, for example as shown in fig. 5, in which a partial structure of two profiles at one corner position is shown. The four profiles can be connected into a whole by welding or bonding, or two adjacent profiles can be connected into a whole by screws through the corner connecting sheet 6. At this time, the corner connecting piece 6 may connect not only a set of two elastic tensioners 5 at the corner position (by welding or screwing, etc.), but also two profiles. In the embodiment shown in fig. 5, the elastic tensioning device 5 is arranged to be mounted on the first frame 31. Of course, it will be appreciated by those skilled in the art that in an embodiment not shown, the elastic tensioning device 5 may also be provided mounted on the second frame 32.
The second frame 32 may be integrally punched from a metal plate, cast from metal, or injection molded from plastic, as shown in fig. 6. Alternatively, the second frame 32 may be formed by splicing four profiles, as in the first frame 31. Alternatively, the first housing 31 may be integrally formed of metal or plastic, as in the second housing 32. Preferably, the frame body for installing the elastic tensioning device 5 is formed by splicing metal profiles, so that the frame body can have larger supporting strength to adapt to tensioning operation; correspondingly, the other frame body can be made of metal or plastic integrally formed parts.
The second frame 32 may be provided inside the first frame 31 as shown in fig. 1, or in an embodiment not shown, the first frame 31 may be provided inside the second frame 32. In addition, in order to avoid the first frame 31 and the second frame 32 from being separated accidentally, the side edges of the first frame 31 and the second frame 32 may be reinforced by screws (screw holes are shown in the figure, and screws are not shown).
As shown in fig. 5 and 6, the first frame 31 and the second frame 32 have a first annular inner flange 311 and a second annular inner flange 321, respectively, which are located opposite to each other, and the first annular inner flange 311 and the second annular inner flange 321 abut against both side surfaces of the inner suspension film 2, respectively (fig. 1). The inner hanging film 2 is clamped by the first annular inner flange 311 and the second annular inner flange 321 which are abutted against the two side surfaces of the inner hanging film 2, so that the cavities at the two sides of the inner hanging film 2 cannot be communicated with the interiors of the first frame 31 and the second frame 32, the cavities at the two sides of the inner hanging film 2 are well isolated, and heat exchange of air flows in the cavities at the two sides is avoided.
Further, in order to further enhance the insulation effect, in an embodiment not shown, it is preferable that the top of the first annular inner flange 311 and the second annular inner flange 321, which are abutted against the inner hanging membrane 2, are mounted with elastic sealing strips.
The specific construction of the elastic tensioner for an inner swing door and window according to the present application will be described in further detail with reference to fig. 7 to 8. As shown in the figure, the elastic tensioning device 5 comprises a fixed base 51, a telescopic clamping seat 52 is arranged below the fixed base 51, and a spring 53 is arranged between the telescopic clamping seat 52 and the fixed base 51. For balanced stress, two springs 53 are arranged side by side between the telescopic clamping seat 52 and the fixed base 51.
Further, the fixing base 51 may be formed by integrally cutting and bending a metal plate, and includes a fixing top plate 511 abutting against a first end of the spring 53, wherein two sides of the fixing top plate 511 are respectively bent to form a fixing guide plate 512, and a bottom of the fixing guide plate 512 is bent to form a mounting plate 513; the fixed top plate 511 is formed with a positioning screw hole 5111 for positioning the spring 53; the mounting plate 513 is formed with a mounting screw hole 5131, and the entire elastic tensioner 5 can be mounted inside the tension frame 3 by a screw penetrating into the mounting screw hole 5131.
Corresponding to the number of springs 53, two positioning screw holes 5111 are provided on the fixed top plate 511, and one positioning screw 5112 is provided in each positioning screw hole 5111. After passing through the set screw 5111, the set screw 5112 is threaded at its distal end into the end of the spring 53 so that the spring 53 does not disengage from the set screw 5112 during compression and fails.
The telescopic clamping seat 52 can also be formed by integrally cutting and bending a metal plate, and comprises a movable top plate 521 propping against the second end of the spring 53, wherein a telescopic guide plate 522 is formed by bending the bottom of the movable top plate 521 towards one side of the fixed top plate 511, a hanging plate 523 is formed by bending the tail end of the telescopic guide plate 522 penetrating through a guide opening 5113 at the bottom of the fixed top plate 511, and a return hook plate 524 is formed at the tail end of the hanging plate 523; the end of the square section of the spool 20 is non-rotatably caught in a concave space formed by the telescopic guide plate 522, the hanging plate 523 and the return hook plate 524.
The fixed guide plate 512 is formed with a guide groove 5121, and both ends of the movable top plate 521 are respectively formed with a protrusion 5211, and the protrusions 5211 are inserted into the guide groove 5121 and can move forward and backward along the guide groove 5121.
When the elastic tensioning device 5 is assembled, the telescopic clamping seat 52 is deflected by a certain angle, the protruding part 5211 is inserted into the guide groove 5121, then the telescopic clamping seat 52 is aligned, the spring 53 is placed between the telescopic clamping seat 52 and the fixed base 51, and finally the positioning screw 5112 is screwed in to fix the position of the spring 53. After the fixing base 51 is mounted on the tension frame 3, the telescopic clamping seat 52 is limited below the fixing base 51 through the guide groove 5121 and the guide opening 5113, and the telescopic clamping seat 52 can only move in parallel along the guide groove 5121, so that a stable elastic force can be provided for the tail end of the scroll 20.
The tail end of the scroll 20 is of a square cross-section structure, and can be clamped in the concave space of the telescopic guide plate 522, the hanging plate 523 and the clip hook plate 524 in a non-rotating manner, so that the buckle structure is simple and effective, and the operation is quite convenient. The elastic tensioning device 5 is simple in structure and high in operation reliability, and the elastic continuous effectiveness of the whole structure is extremely high by converting the compression force of the spring 53 into the tensile elastic force, so that the elastic tensioning device can be used in a maintenance-free operation for life.
It should be understood by those skilled in the art that while the present application has been described in terms of several embodiments, not every embodiment contains only one independent technical solution. The description is given for clearness of understanding only, and those skilled in the art will understand the description as a whole and will recognize that the technical solutions described in the various embodiments may be combined with one another to understand the scope of the present application.
The foregoing is illustrative of the present application and is not to be construed as limiting the scope of the application. Any equivalent alterations, modifications and combinations thereof will be effected by those skilled in the art without departing from the spirit and principles of this application, and it is intended to be within the scope of the application.

Claims (5)

1. A photochromic inner suspension film for tensioning and installing in a tensioning frame (3) clamped between two layers of glass (1), which is characterized in that the inner suspension film (2) comprises an inner suspension film base material (21), at least one silver alloy layer (22) is formed on the sunlight irradiation surface of the inner suspension film base material (21), and a photochromic layer (23) is formed on the other surface of the inner suspension film base material (21) opposite to the sunlight irradiation surface; the inner suspension film base material (21) comprises a polyester film (211), wherein at least one ZnO: al layer (213) is formed on the outermost side of the polyester film (211) facing the silver alloy layer (22), and an adhesion layer (212) is formed between the ZnO: al layer (213) and the outermost side of the polyester film (211); the silver alloy layer (22) comprises a silver alloy base layer (221), a metal titanium protective layer (222) is formed on the outer side of the silver alloy base layer (221), and an indium oxide protective layer (223) is formed on the outer side of the metal titanium protective layer (222); the adhesion layer (212) is prepared from the following raw materials in parts by weight: 6-8 parts by weight of polydimethylsiloxane; 1-5 parts of polyurethane; 15-30 parts by weight of vinyl trimethoxy silane; 80-120 parts by weight of isopropanol; 10-20 parts of polyethylene glycol; 1-5 parts of zinc oxide; 0.1-0.5 parts by weight of alumina; 0.1 to 0.5 part by weight of magnesium sulfate.
2. The photochromic endo-suspension film according to claim 1, wherein the silver alloy base layer (221) has a thickness of 10-15nm; the thickness of the metal titanium protective layer (222) is 3-6nm; the thickness of the indium oxide protective layer (223) is 55-85nm.
3. The photochromic endo-suspension film according to claim 1, wherein the thickness of the adhesion layer (212) is 10-20nm; the thickness of the ZnO/Al layer (213) is 3-6nm.
4. A photochromic inner suspension film according to any one of claims 1-3, wherein two superimposed silver alloy layers (22) are formed on the solar radiation surface of the inner suspension film substrate (21), and the two silver alloy layers (22) have the same structure and each comprise a silver alloy base layer (221), a metallic titanium protective layer (222) and an indium oxide protective layer (223).
5. A photochromic inner suspension film according to any one of claims 1 to 3, wherein the inner suspension film (2) comprises two inner suspension film substrates (21), a photochromic layer (23) is interposed between the two inner suspension film substrates (21), and a silver alloy layer (22) is formed on the outer sides of the two inner suspension film substrates (21); the two silver alloy layers (22) have the same structure and comprise a silver alloy base layer (221), a metallic titanium protective layer (222) and an indium oxide protective layer (223).
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106435497A (en) * 2016-09-08 2017-02-22 江苏双星彩塑新材料股份有限公司 Gold low-radiation energy-saving window film and preparation method thereof
CN106435496A (en) * 2016-09-08 2017-02-22 江苏双星彩塑新材料股份有限公司 Grass-green double-silver low-radiation energy-saving window film and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106435497A (en) * 2016-09-08 2017-02-22 江苏双星彩塑新材料股份有限公司 Gold low-radiation energy-saving window film and preparation method thereof
CN106435496A (en) * 2016-09-08 2017-02-22 江苏双星彩塑新材料股份有限公司 Grass-green double-silver low-radiation energy-saving window film and preparation method thereof

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