CN103770393B - A kind of fenestrated membrane - Google Patents
A kind of fenestrated membrane Download PDFInfo
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- CN103770393B CN103770393B CN201410042012.0A CN201410042012A CN103770393B CN 103770393 B CN103770393 B CN 103770393B CN 201410042012 A CN201410042012 A CN 201410042012A CN 103770393 B CN103770393 B CN 103770393B
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Abstract
A kind of fenestrated membrane, including substrate, it is positioned at the antireflection structure of substrate side, it is positioned at the optics layers of two-sided of substrate opposite side, described antireflection structure includes two resonator cavitys, described each resonator cavity includes that wherein said anti-oxidant metal layer is zinc or titanium at the two layer medium layer in outside up and down, the conductive metal layer in centre and the two-layer anti-oxidant metal layer being clipped in respectively between conductive metal layer and two layer medium layer.This fenestrated membrane two five-layer structures of combination become dual resonant cavity, it is achieved that excellent optical property, and can select flexible parent metal, by the method for volume to volume magnetron sputtering, it is achieved extensive, large area produces.
Description
Technical field
Fenestrated membrane field of the present invention, particularly relates to a kind of high-transparency fenestrated membrane, can be applicable to automobile front windshield
On.
Background technology
Automobile window films is the functionalized polyester composite film material of a kind of multilamellar, and it is original glassy that it has change
Can effect, including change plexiglass tint, adjust light transmission, trap heat radiation, prevent UV-permeable,
Explosion-proof etc..Fenestrated membrane truly is to enter Chinese market, at that time from about the 96 of last century years
Fenestrated membrane has gone through coating, tea paper, deep layer dyeing, interlayer, thermal evaporation stage.Currently marketed
Automobile window films has evolved to the magnetron sputtering stage.
Current fenestrated membrane product category is various, if mountain, Changzhou is by the invention of Di Shan protective material Manufacturing Co., Ltd
The thermal-insulation window film of design, is integrated by MULTILAYER COMPOSITE, including anti-scratching wearproof layer/flexible parent metal/heat insulation acrylic acid
Adhesive layer/obstruct UV layer/obstruct ultraviolet light acrylate glue adhensive layer/mould release membrance, its light transmittance is permissible
Reach 71%(application number: 201110125866.1).And for example the one of Wuhan Yi Yang Science and Technology Ltd. design
Planting thermal insulation ceramics fenestrated membrane, it is by pressure sensitive adhesive, mould release membrance, ceramic membrane, thermoplastic polymer film multilamellar
Being composited, with low cost and visible light transmissivity is 75%(application number: 201220730172).Beautiful
The exterior window film of CP Film, Inc.'s design of state, its structure is protectiveness hard conating/undercoating/polyester film/metal
Change film layer/adhesive layer, but its transmitance maximum has reached 85%(application number: 200980102102.1).
High-performance transparent glass heat-insulating designed by Shanghai Huzheng Nano-Tech Co., Ltd. is used for high-performance window
Film, first it prepare blue WOx, ATO and ITO mix scattered transparent mixed slurry, then with transparent
Polyurethane resin mix and blend filters and obtains, it is seen that light transmission rate has reached 75%(application number:
201110367312.2).One seminar of Shanghai Communications University proposes dielectric layer/metal level/electricity and is situated between
Matter layer three-decker, it has outstanding permeability, but, owing to metal level is easily oxidized, make
The highest with the life-span, in actual production and use, there is also the biggest problem (number of patent application: 03116461.7).
Fenestrated membrane product common problem in the market is that visible light transmissivity is low, causes visual field mould
Sticking with paste, vehicle window lack of defination, direct reflection phenomenon is serious, and therefore complicated process of preparation finds new material,
Design prepares that a kind of high-permeability, technique is simple, the novel fenestrated membrane of low cost is that current fenestrated membrane industry is sent out
The major trend of exhibition.
Summary of the invention
In view of this, it is an object of the invention to provide a kind of new fenestrated membrane, this fenestrated membrane not only has good
Light transmission performance, processing technology is simple, low cost.
A kind of fenestrated membrane proposed according to the present invention, including substrate, is positioned at the antireflection structure of substrate side, position
In the optics layers of two-sided of substrate opposite side, described antireflection structure includes two resonator cavitys, described each humorous
The chamber that shakes includes being positioned at the two layer medium layer in outside up and down, the conductive metal layer being positioned at centre and being clipped in respectively and leads
Two-layer anti-oxidant metal layer between metal layer and two layer medium layer, wherein said anti-oxidant metal layer is
Zinc or titanium.
Preferably, in described single resonator cavity, the total optical thickness of two layer medium layer is 1 optical unit,
And the optical thickness of this two layer medium layer is with middle conductive metal layer as specular.
Preferably, the thickness of described conductive metal layer is less than 10nm, and the thickness of anti-oxidant metal layer is at 1-10
Between nm, and this two-layer anti-oxidant metal layer is with middle conductive metal layer as specular.
Preferably, the refractive index of described two layer medium layer is respectively greater than 2.
Preferably, described conductive metal layer is golden or silver-colored.
Preferably, the material of described dielectric layer is TiOx、NbOx、ZrOx、ZnOx、CeOx、TaOx、
One in ZnSe or ZnS.
Preferably, described substrate is flexible and transparent material.
Preferably, described protective layer is optical cement.
Compared with prior art, the present invention has a following technical advantage:
1, the fenestrated membrane of present invention one side reflectance in visible-range is less than 5%, and reflectance curve is
W type, has outstanding visible light anti-reflection performance.
2, the fenestrated membrane of the present invention can be prepared by the method for winding magnetic control sputtering, can give birth in a large number
Produce, make large area industrialization be possibly realized.
3, by adding anti-oxidant metal layer, traditional sandwich structure nesa coating is optimized
Design, oxidized to preventing conductive metal layer, improve and play an important role service life.
Accompanying drawing explanation
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to reality
Execute the required accompanying drawing used in example or description of the prior art to be briefly described, it should be apparent that below,
Accompanying drawing in description is only some embodiments of the present invention, for those of ordinary skill in the art,
On the premise of not paying creative work, it is also possible to obtain other accompanying drawing according to these accompanying drawings.
Fig. 1 is 5 layers of antireflection structure schematic diagram of the present invention.
Fig. 2 is the reflectivity curve race of the optics antireflective film that the thickness of intermediate metal layer changes from 6-10nm.
Fig. 3 is the structural representation of the fenestrated membrane of the present invention.
Fig. 4 is the dual resonant cavity fenestrated membrane structural representation that the present invention designs
Fig. 5 is to limit the optical performance test curve chart that concrete optical parametric obtains.
Detailed description of the invention
As described in the background art, existing automobile window films, common problem is visible light-transmissive
Rate is low, causes the visual field to obscure, vehicle window lack of defination, and direct reflection phenomenon is serious, simultaneously because fenestrated membrane
Need to meet that wearability is good, the high requirement of light transmission so that the structure within film system is complicated, generally requires
Mixed a variety of materials, cause complicated process of preparation, and cost is high.
Therefore, the present invention proposes a kind of novel high-transparency fenestrated membrane.This fenestrated membrane uses by multilayer dielectricity with many
The dual resonant cavity antireflection structure of layer metal interaction cascading, film system gross thickness is less than 200 nanometers,
It is significantly less thick than existing fenestrated membrane in automobile window films field.Owing to the assembly of thin films antireflection structure of the present invention uses
Stepped construction, coordinates flexible substrates, can use winding magnetic control sputtering technique one-shot forming, be substantially reduced
The complexity of processing technology, is suitable for extensive, large area and produces, thus reduce production cost.Lead to again
Cross film covering method and coat double faced adhesive tape at base material another side, easy to use.
The multi-layer film structure at present with relatively high-permeability is generally metal-oxide/metal level/burning
This so-called sandwich structure of thing, embodied in patent that number of patent application is 03116461.7,
But, the main inferior position of this structure is: metal layer A g is easy to by the oxygen atom in metal-oxide
Aoxidized with the oxygen atom in external environment.In order to solve this problem, we select one layer relatively to hold with oxygen
The anti-oxidant metal layer easily reacted, is incorporated into this anti-oxidant metal layer in sandwich structure, permissible
Make the oxygen atom in metal-oxide react with this anti-oxidant metal layer, form fine and close oxide-film, to
The conductive metal layer of internal layer plays splendid protective effect.And the metallic bond formed is also for improving metal oxygen
Compound plays an important role with the adhesive force of anti-oxidant metal layer.We select Zn and Ti both gold
Belonging to as anti-oxidant metal layer, this is the most active due to Zn and Ti, it is easy to oxidation generates densification
Oxide-film, and the performance of oxide-film is highly stable, is difficult to oxidized, and chemical property is the most stable, can
Effectively to protect the metal Ag layer of innermost layer.
The present invention, based on conventional dielectric layer/metal level/dielectric layer sandwich structure, resists by introducing one layer
Metal oxide layer, it is proposed that the nesa coating of a kind of five layers of antireflection structure, this antireflection structure by dielectric layer-
Anti-oxidant metal layer-conductive metal layer-anti-oxidant metal layer-dielectric layer composition, then by 2 five layers of anti-reflection knots
Structure superposition, forms dual resonant cavity fenestrated membrane structure, it is used for shelves before automobile window films, with existing fenestrated membrane phase
Ratio, it is high that the present invention has visible light transmissivity, it is easy to the advantages such as large area industrialization production.
Referring to Fig. 1, the schematic diagram for five layers of antireflection structure of display, this antireflection structure includes being positioned at up and down
Outside two layer medium layer 111 and 115, be positioned at centre conductive metal layer 113 and be clipped in conductive gold respectively
Belong to the two-layer anti-oxidant metal layer 112 and 114 between layer and two layer medium layer.Wherein conductive metal layer 113
Thickness less than 10nm, electric property considered by its material, golden or silver-colored.Anti-oxidant metal layer
112 and 114 1 aspects " can catch " oxonium ion in dielectric layer 111 and 115, makes dielectric layer in owing
Oxygen condition, and then form so-called tunneling effect raising electric conductivity, on the one hand it is possible to prevent conductive metal layer
Lost efficacy, simultaneously between conductive metal layer is because of the too small appearance of thickness by the extraneous and oxidation of medium of oxides layer
It is filled with during gap, thus increases electric conductivity.Its thickness between 1-10nm, preferably zinc or
Titanium.In view of the impact on light anti-reflection effect of the thickness of deielectric-coating, we take two layer medium film 111 He
The total optical thickness of 115 is 1 optical unit.In the present invention, in order to effectively reduce the total of five-layer structure
Body thickness, we take the refractive index high refractive index medium material more than 2 as this two layer medium layer 111 He
The material of 115.Such as TiOx、NbOx、ZrOx、ZnOx、CeOx、TaOx, ZnSe, ZnS etc..
So, be a λ/4(that is optical unit at the total optical thickness meeting two layer medium layer) situation
Under, the physical thickness of every layer of dielectric layer can be the lowest.With TiO2As a example by, its refractive index n=2.32,
When the wavelength of incident illumination is 550nm, understand (wherein according to computing formula nd=λ/4 of optical thickness
N is the refractive index of dielectric layer, and d is the physical thickness of dielectric layer, and λ/4 are an optical unit), monolayer
The thickness of dielectric layer is about 27nm, and now the general thickness of this antireflection structure can control at 70nm left
The right side, well below the thickness of other antireflective films existing.It is pointed out that for two layer medium layer 111,
115 and two-layer anti-oxidant metal layer 112,114, identical material can be selected respectively, it is also possible to be not
Same material, but the optical thickness of two layer medium layer, and the physical thickness of two-layer anti-oxidant metal layer is all
With middle conductive metal layer as specular.
The optics anti-reflection changed from 6-10nm referring again to the thickness that Fig. 2, Fig. 2 are middle conductive metal layer
The reflectivity curve race of film, wherein curve 1 represents that the thickness of intermediate metal layer is 6nm, during curve 2 represents
Between the thickness of metal level be 7nm, curve 3 represents that the thickness of intermediate metal layer is 8nm, and curve 4 represents
The thickness of intermediate metal layer is 9nm, and curve 5 represents that the thickness of intermediate metal layer is 10nm.From figure
It can be seen that in most cases, the antireflection structure of the present invention all presents relatively at whole visible light wave range
Low reflection characteristic.Wherein when the thickness of metal level is at 6nm, effect is best, shows W type anti-
Penetrate rate curve.
Following table is to change the thickness of different anti-oxidant metal layer, the reflectance of five layers of designed antireflection structure,
And decocting in water half an hour after adhesive force experimental result.Wherein table one is metal Zn, and table two is metal
Ti.It can be seen that the thickness at two kinds of anti-oxidant metal layers is that between 1-10nm, reflectance exists always
Less than 4%, there is outstanding reflection preventing ability, decocting in water halfhour weatherability test adhesive force is good, tool
There is good weatherability.Estimable, compared to the antireflective film product on market, film structure letter
Single, thickness the thinnest (only about an optical thickness), there is the biggest industrialization advantage.
Table one. the optical property of the antireflection structure of different anti-oxidation metal layer thicknesses and weatherability test structure (Zn)
Table two. the optical property of the antireflection structure of different anti-oxidation metal layer thicknesses and weatherability test structure (Ti)
Below, more in particular embodiments to the structure of above-mentioned fenestrated membrane it is described in detail.
Refer to the structural representation that Fig. 3, Fig. 3 are the fenestrated membranes of the present invention.As it can be seen, this fenestrated membrane includes
Substrate 100, is positioned at the antireflection structure 110 of substrate 100 side, is positioned at the optics double faced adhesive tape of substrate opposite side
Layer 120.Wherein, substrate 100 is flexible clear materials, and its material is the polymeric materials such as PET.Light
The material learning layers of two-sided 120 includes but not limited to OCA(Optically Clear Adhesive) etc..
Refer to the stratiform schematic diagram that Fig. 4, Fig. 4 are antireflection structures 110 in Fig. 3.As it can be seen, this subtracts
Antistructure includes two resonator cavitys 11 and 12, and each resonator cavity includes dielectric layer-anti-oxidant metal layer-conduction
Metal level-anti-oxidant metal layer-dielectric layer five tunic.Concrete, dielectric layer H preferred index is more than 2
High refractive index medium material, such as TiOx、NbOx、ZrOx、ZnOx、CeOx、TaOx、ZnSe、
ZnS etc..Anti-oxidant metal layer M ' is except playing refractive index match effect, it is also possible to greatly carry
High antioxidant, increases the service life of fenestrated membrane.The thickness of middle conductive metal film M is less than 10nm,
The thickness of anti-oxidant metal layer is between 1-10nm.In single resonator cavity, all high refractive index medium layers
Total optical thickness is at least 1 optical unit.So, the physical thickness of whole fenestrated membrane can control
Within 200nm, so that the fenestrated membrane thickness of the present invention has thinner excellent of other fenestrated membrane the most existing
Gesture.
Further, since the base material of the fenestrated membrane of invention all uses flexible material, its manufacture method can use
Winding magnetic control sputtering technique, the advantage of this technique is by just depositing on substrate in disposable technique
Multilayer film, thus have the advantage simple, with low cost of making, also is adapted for large area, extensive simultaneously
Production.
Being in the structure of Fig. 4 referring again to Fig. 5, Fig. 5, limit that concrete optical parametric obtains is optical
Can test curve figure.Wherein curve 1 is the transmission curve of this structure, and curve 2 is that the reflection of this structure is bent
Line.The design parameter of this model is that gross thickness is less than 200nm, and structure is PET/HM ' MM '
H/HM ' MM ' H/air, wherein H represents high refractive index medium layer NbOx, M ' is anti-oxidant metal layer Zn,
M is conductive metal layer Ag.It can be seen that at 400-760nm visible light wave range, reflectivity curve is W
Type and the most common V-type, average transmittance is 89.4%, and average reflectance is 1.87%, shows that this is new
Type fenestrated membrane has outstanding anti-reflective effect.
In sum, the novel fenestrated membrane of the present invention, utilize the sandwich knot that negative index interfacial structure is formed
Structure, in the case of general thickness is far smaller than existing optics antireflective film, it is achieved excellent optical property,
Again by being combined into resonator cavity, select flexible parent metal, the method utilizing volume to volume magnetron sputtering, it is achieved big
Scale, large area produce.
Described above to the disclosed embodiments, makes professional and technical personnel in the field be capable of or uses
The present invention.Multiple amendment to these embodiments will be aobvious and easy for those skilled in the art
See, generic principles defined herein can without departing from the spirit or scope of the present invention,
Realize in other embodiments.Therefore, the present invention is not intended to be limited to embodiment illustrated herein, and
It is to fit to the widest scope consistent with principles disclosed herein and features of novelty.
Claims (4)
1. a fenestrated membrane, it is characterised in that: include substrate, be positioned at the antireflection structure of substrate side, be positioned at
The optics layers of two-sided of substrate opposite side, described antireflection structure includes two resonator cavitys, described each resonance
Chamber is by being positioned at the two layer medium layer in outside up and down, being positioned at the conductive metal layer of centre and be clipped in conductive gold respectively
Belonging to the two-layer anti-oxidant metal layer composition between layer and two layer medium layer, the thickness of described conductive metal layer is little
In 10nm, the thickness of anti-oxidant metal layer between 1-10nm, and this two-layer anti-oxidant metal layer with in
Between conductive metal layer be specular, wherein said anti-oxidant metal layer is zinc, described single resonator cavity
The total optical thickness of middle two layer medium layer is 1 optical unit, and this 1 optical unit is λ/4, and λ is incident
The wavelength of light, and the optical thickness of this two layer medium layer is with middle conductive metal layer as specular, often
The refractive index of layer dielectric layer is all higher than 2.
2. fenestrated membrane as claimed in claim 1, it is characterised in that: described conductive metal layer is golden or silver-colored.
3. fenestrated membrane as claimed in claim 1, it is characterised in that: the material of described dielectric layer is TiOx、
NbOx、ZrOx、ZnOx、CeOx、TaOx, one in ZnSe or ZnS.
4. fenestrated membrane as claimed in claim 1, it is characterised in that: described substrate is flexible and transparent material.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104309195A (en) * | 2014-10-20 | 2015-01-28 | 朱玮 | Window film core functional layer and method for manufacturing window film core functional layer |
| CN104441817A (en) * | 2014-11-25 | 2015-03-25 | 合肥嘉伟装饰工程有限责任公司 | Self-cleaning surface flexible transparent solar film |
| CN106032065A (en) * | 2015-03-17 | 2016-10-19 | 鼎基化学工业股份有限公司 | Film adhering manufacturing method and film adhering manufacturing apparatus |
| US10906340B2 (en) | 2017-09-26 | 2021-02-02 | Hp Indigo B.V. | Scratch-off structure production |
| CN107765490A (en) * | 2017-11-27 | 2018-03-06 | 怡通科技有限公司 | A kind of heat-insulated intelligent fenestrated membrane of flexible electrochromism and its preparation technology |
| CN109664583A (en) * | 2018-11-29 | 2019-04-23 | 信利光电股份有限公司 | A kind of vehicle window film of insulating water-proof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87105971A (en) * | 1986-12-29 | 1988-08-31 | Ppg工业公司 | The low radiation film of pyroprocess |
| US6322881B1 (en) * | 1996-12-12 | 2001-11-27 | Saint-Gobain Vitrage | Glazing assembly comprising a substrate provided with a stack of thin layers for solar protection and/or thermal insulation |
-
2014
- 2014-01-28 CN CN201410042012.0A patent/CN103770393B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87105971A (en) * | 1986-12-29 | 1988-08-31 | Ppg工业公司 | The low radiation film of pyroprocess |
| US6322881B1 (en) * | 1996-12-12 | 2001-11-27 | Saint-Gobain Vitrage | Glazing assembly comprising a substrate provided with a stack of thin layers for solar protection and/or thermal insulation |
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