CN108796458A - A kind of Organic-inorganic composite transparent membrane - Google Patents
A kind of Organic-inorganic composite transparent membrane Download PDFInfo
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- CN108796458A CN108796458A CN201710282485.1A CN201710282485A CN108796458A CN 108796458 A CN108796458 A CN 108796458A CN 201710282485 A CN201710282485 A CN 201710282485A CN 108796458 A CN108796458 A CN 108796458A
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- transparent membrane
- composite transparent
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- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 239000012528 membrane Substances 0.000 title claims abstract description 26
- 238000000576 coating method Methods 0.000 claims abstract description 57
- 239000011248 coating agent Substances 0.000 claims abstract description 56
- 239000010408 film Substances 0.000 claims abstract description 48
- 239000010409 thin film Substances 0.000 claims abstract description 28
- 230000007704 transition Effects 0.000 claims abstract description 25
- 238000000151 deposition Methods 0.000 claims description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 230000008021 deposition Effects 0.000 claims description 18
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 14
- -1 acrylic ester Chemical class 0.000 claims description 9
- 229910052681 coesite Inorganic materials 0.000 claims description 9
- 229910052906 cristobalite Inorganic materials 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 229910052682 stishovite Inorganic materials 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052905 tridymite Inorganic materials 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 238000001994 activation Methods 0.000 claims description 7
- 229910052593 corundum Inorganic materials 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 7
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 238000004544 sputter deposition Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 4
- 238000010276 construction Methods 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 29
- 238000012360 testing method Methods 0.000 description 19
- 229920000620 organic polymer Polymers 0.000 description 18
- 238000000034 method Methods 0.000 description 17
- 238000004140 cleaning Methods 0.000 description 14
- 239000007789 gas Substances 0.000 description 9
- 238000001755 magnetron sputter deposition Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000005240 physical vapour deposition Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000004506 ultrasonic cleaning Methods 0.000 description 6
- 239000000758 substrate Substances 0.000 description 5
- 238000001723 curing Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000011241 protective layer Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000009738 saturating Methods 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000002310 reflectometry Methods 0.000 description 2
- 238000009991 scouring Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229920001688 coating polymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Classifications
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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
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
- C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
-
- 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
- C23C14/02—Pretreatment of the material to be coated
- C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
-
- 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
- C23C14/0605—Carbon
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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
- C23C14/08—Oxides
- C23C14/081—Oxides of aluminium, magnesium or beryllium
-
- 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
- C23C14/08—Oxides
- C23C14/083—Oxides of refractory metals or yttrium
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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
- C23C14/08—Oxides
- C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
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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
- C23C14/10—Glass or silica
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
Abstract
The present invention provides a kind of Organic-inorganic composite transparent membranes, including contact successively organic thin film layer, in conjunction with transition zone and inorganic coating；The combination transition zone is inorganic carbon-base film.The present invention is increased between organic thin film layer and inorganic coating in conjunction with transition zone, effectively increase the binding force of organic thin film layer and inorganic coating, the laminated film of preparation retain organic coating it is smooth, wear-resisting on the basis of, be provided simultaneously with wear-resisting, the high rigid energy of inorganic coating.The structure can realize the high transparency of composite construction, whole transmitance > 80% and excellent outdoor weathe resistance simultaneously.So that the structure is able to extensive use in multiple fields, for example disappear digital product soon, automobile industry, field of solar energy etc..
Description
Technical field
The present invention relates to composite membrane technology field more particularly to a kind of Organic-inorganic composite transparent membranes.
Background technology
Transparent organic polymer has many excellent performances, optical if processing performance, weatherability, electrical insulating property are good
Can be excellent, and light property is tough, extensively using every field.However transparent organic polymer also has the drawbacks of it is difficult to overcome, such as
Poor solvent resistance, poor heat resistance, water absorption rate are high and wearability is bad.Generally acknowledged maximum defect is that case hardness is low, table
Face wear-resisting property is poor, is easy to be scratched, transparent organic polymer is during usual use, the grit or sand of adsorption
Gravel can make base material generate scratch, cut or groove using surface in wiping process, reduce the light transmittance of base material, seriously affect
Its optical property greatly constrains its application.It is transparent especially in daily necessities field, such as digital product, auto parts and components etc.
The wearability official post product appearance of organic polymer influences very greatly at any time, therefore the wearability for improving them is very urgent.
The mankind are the application range for expanding transparent organic polymer, and processing is modified to it, retains its above advantage, together
When overcome above-mentioned deficiency.There are three types of common means：The first, is added inorganic fine particles in transparent organic polymer, commonly uses
Have SiO2, ZrO2, TiO2Equal particles, to improve the wearability of transparent organic polymer film, but its final performance and inorganic grain
Content, the granularity of son are related, study at present still immature；Second, transparent organic polymer surface be modified, by high temperature, etc.
Gas ions processing deposits new organic coating, improves surface property；The third, is sunk inorganic wearing layer by PVD and CVD technology
For product on organic polymer substrate, this method causes inorganic thin film and organic polymer due to the influence of temperature in deposition process
Between easily peel off, and long-term weatherability is also very poor, it is easy to which demoulding in use does not have protective effect.
Simultaneously because protective layer of the organic polymer as wear-resisting weather-proof, needs the performance (color, the gloss that do not influence bottom
And reflectivity etc.), very high requirement is proposed to the translucency of structure.
Invention content
In view of this, the technical problem to be solved in the present invention is to provide a kind of Organic-inorganic composite transparent membrane, have
Excellent wear-resisting and weatherability.
The present invention provides a kind of Organic-inorganic composite transparent membranes, including contact successively organic thin film layer, combined
Cross layer and inorganic coating；The combination transition zone is inorganic carbon-base film.
Preferably, the combination transition zone is the inorganic carbon-base film prepared using graphite target vacuum sputtering methods.
Preferably, the thickness of the inorganic carbon-base film is 1~50nm.
Preferably, the organic thin film layer is organic coating or organic film.
Preferably, the organic coating is organic silicon-type resin, acrylic ester resin or epoxy resin；
The organic film is PC, PET, PMMA, PEM or acrylic.
Preferably, the thickness of the organic coating is 2~100 microns；The thickness of the organic film is 50~1000 micro-
Rice.
Preferably, the inorganic coating is Al2O3, SiO2, SiONx, ZrO2, TiO2And SnO2One or more of and its
Metal Oxidation Doping forms.
Preferably, the inorganic coating is Al2O3, SiO2, SiONx, ZrO2, TiO2And SnO2One or more of metal
The composite coating that oxide is formed by stacking.
Preferably, the thickness of the inorganic coating is 100~2000nm.
Preferably, before depositing in conjunction with transition zone, activation process is carried out to organic thin film layer.
Compared with prior art, the present invention provides a kind of Organic-inorganic composite transparent membranes, including what is contacted successively have
Machine film layer, in conjunction with transition zone and inorganic coating；The combination transition zone is inorganic carbon-base film.The present invention is in organic thin film layer
The binding force that organic thin film layer and inorganic coating are effectively increased in conjunction with transition zone is increased between inorganic coating, preparation is answered
Close film retain organic coating it is smooth, wear-resisting on the basis of, be provided simultaneously with wear-resisting, the high rigid energy of inorganic coating.Together
When the structure can realize the high transparency of composite construction, whole transmitance > 80% and excellent outdoor weathe resistance.So that should
Structure is able to extensive use in multiple fields, and for example disappear digital product soon, automobile industry, field of solar energy etc..
Description of the drawings
Fig. 1 is the structural schematic diagram of Organic-inorganic composite transparent membrane prepared by embodiment 1；
Fig. 2 is the structural schematic diagram of Organic-inorganic composite transparent membrane prepared by embodiment 2.
Specific implementation mode
The present invention provides a kind of Organic-inorganic composite transparent membranes, including contact successively organic thin film layer, combined
Cross layer and inorganic coating；The combination transition zone is inorganic carbon-base film.
The present invention increases between organic thin film layer and inorganic coating in conjunction with transition zone, effectively increase organic thin film layer and
The binding force of inorganic coating, the laminated film of preparation retain organic coating it is smooth, wear-resisting on the basis of, be provided simultaneously with nothing
Wear-resisting, the high rigid energy of organic coating.The structure can realize the high transparency of composite construction simultaneously, whole transmitance > 80%, with
And excellent outdoor weathe resistance.So that the structure is able to extensive use in multiple fields, for example disappear digital product soon, garage
Industry, field of solar energy etc..
Present invention firstly provides organic thin film layer, the organic thin film layer is preferably organic coating or organic film.
The organic coating is preferably organic silicon-type resin, acrylic ester resin or epoxy resin, and thickness is preferably 2
Micron~100 microns.
The present invention is to the deposition method of the organic coating and is not particularly limited, and can be well known to those skilled in the art
Method, such as spraying, roller coating or dip-coating liquid phase deposition process.
The present invention is to the curing of the organic coating and is not particularly limited, and can be well known to those skilled in the art
Curing, such as heat cure, moisture-curable or UV ultra-violet curings.
Currently preferred, side of the organic coating far from combination transition zone is compounded with base material.The present invention is to described
The material and thickness of base material are simultaneously not particularly limited, and can be base material well known to those skilled in the art and general thickness.
The organic film is preferably organic polymer thin film, more preferably PC, PET, PMMA, PEM or acrylic, thickness
Preferably 50 microns~1000 microns of degree.
The present invention is to the preparation method of the organic film and is not particularly limited, and can be well known to those skilled in the art
Method.
Then transition zone is combined in organic film layer surface deposition.
Combination transition zone of the present invention is inorganic carbon-base film.Preferably, it is using graphite target vacuum sputtering side
Inorganic carbon-base film prepared by method.Atmosphere is preferably Ar, N in the sputtering process2、CH4Or C2H2Deng the inorganic carbon prepared
Base film has light transmission.The thickness of the inorganic carbon-base film is preferably 1~50nm.
The combination transition zone can provide inorganic bonding, and then realize compound between organic thin film layer and inorganic coating
In conjunction with, and the adhesive force of inorganic coating is improved, further realize long-term weatherability and wear-resisting property.
It is currently preferred, before depositing in conjunction with transition zone, activation process is carried out to organic thin film layer.Preferably, it uses
The method of plasma bombardment cleaning carries out activation process, and the atmosphere of the cleaning is preferably Ar, O2、O3、N2Deng.
Then inorganic transparent coating is deposited in the combination transition layer surface, as outer protective layer.
The inorganic coating preferably uses PVD (sputtering, evaporation) physical vapour deposition (PVD)s or CVD chemical vapor depositions to prepare.
The inorganic coating preferably uses Al2O3, SiO2, SiONx, ZrO2, TiO2, SnO2Equal metal oxides and metal oxygen
Change is adulterated.Or use Al2O3, SiO2, SiONx, ZrO2, TiO2And SnO2One or more of metal oxide superposition
It forms.Its thickness is preferably 100nm~2000nm.
Through environmental simulation test (salt spray test, the test of wet hair brush, high temperature and humidity test, high/low temperature loop test), and
Outdoor aging is tested, it was demonstrated that and Organic-inorganic composite transparent membrane prepared by the present invention has reliable and stable wear-resisting and weatherability,
It is a kind of ideal structure as transparent protective layer.
In the present invention, above-mentioned multilayered structure is prepared using spraying, the means such as CVD, PVD (magnetron sputtering, magnetron sputtering), work
Skill repetition stability is good, production efficiency is high, is easy to large-scale industrial production.
Above-mentioned organic coating or organic polymer thin film can reach micron level, it is easy to which industrialization obtains, and can play
The basic protective effect of ground.But since organic material hardness itself is not high, anti-zoned injure wears no resistance, and is wanted as appearance
It asks high, is difficult individually competent under use environment exacting terms.It often will appear scratch, Hua Ping, becoming hair etc. influences bottom performance
The case where (color, gloss, reflectivity etc.), occurs.And for inorganic coating, with the frequent SiO of prior art2For layer, material
Material intrinsic surface hardness is Mohs H7, to reach fine permanent wear-resisting property, and thickness reaches micron level and could be competent at.And it makes
About inorganic layer thicken in addition to deposition rate is slow, it is of high cost be also a big factor.Existing Organic inorganic film is often tied
Failure phenomenon is closed, because the surface tension of organic thin film layer is relatively low, is unfavorable for soaking and bond.The present invention was combined in introducing
It crosses after layer and selectable organic layer plasma cleaning process, the above problem has obtained good solution.What is prepared is compound
Film substantially increases wear-resisting, the weatherability of single protective layer (either organic film or inoranic membrane).The organic and inorganic of the present invention
Transparent composite film, technique repetition stability is good, production efficiency is high, is easy to large-scale industrial production.
In order to further illustrate the present invention, with reference to embodiment to Organic-inorganic composite thin transparent provided by the invention
Film is described in detail.
Embodiment 1
1) substrate cleans：By 1.1mm ultra-clear glasses, 10*10cm square is cut into, is put into cleaning machine, first carries out fur
It brushes and washes, subsequently into section is cleaned by ultrasonic, the temperature of ultrasonic cleaning is 30 DEG C, time 15min, and pure water is carried out after ultrasonic cleaning
Rinsing, is dried up with nitrogen later, ensures the surface of semi-finished cleaning after drying without greasy dirt.
2) prepared by organic coating：It selects TEOS (ethyl orthosilicate) resins as organic coating raw material, type siloxane is made
Organic silicon solution.Using automatic spraying technology by organosilicon liquid even application in ultra-clear glasses substrate surface, control spraying liquid measure
And the spray gun speed of travel will place ventilation 30 minutes at membrane sample at room temperature to perfect condition, wait for its natural levelling.Gained
First constant temperature 30 minutes in 30~50 DEG C of baking ovens of coating, then 80 DEG C are to slowly warm up to, it 8 hours of isothermal curing, naturally cools to
Transparent organic polymer coating is obtained after room temperature.Organic silicon coating thickness control is at 5~45 microns.
3) magnetron sputtering (PVD) deposition combines transition zone：A) sample surfaces prerinse：The sample of organic coating is coated true
In cavity body, vacuum degree reaches 10-3Pa is hereinafter, be passed through the gaseous mixture of oxygen and argon gas, using plasma cleaning process progress table
Surface treatment, bombardment activation 5min；B) deposition combines transition zone：Sample after surface cleaning enters process cavity, and target is purity 4N
Graphite target, atmosphere is Ar/N in chamber2Mixed gas, wherein Ar ratios 80%, operating air pressure 1.0Pa, using DC power supply
Power is 700W (power density 2W/cm2)；The inorganic carbon-base film thickness of print uniform coated, deposition is 20nm.
4) inorganic wear-resistant coating：A) print is continued in vacuum cavity, carries out magnetron sputtering deposition SiO2Film, deposition
80 DEG C of temperature, target are the silicon oxide target of purity 5N, and atmosphere is Ar/O in chamber2Mixed gas, wherein Ar ratios 75%, work gas
Pressure is 1.0Pa, uses radio frequency power for 700W (power density 2W/cm2)；Print uniform coated, the SiO of deposition2It is thin
Film thickness is 300nm.B) continue magnetron sputtering deposition TiO2Film, target are the titanium target of purity 5N, and atmosphere is Ar/ in chamber
O2Mixed gas, wherein Ar ratios 50%, operating air pressure 0.8Pa use DC pulse source power for 350W (power densities
For 1W/cm2)；Print uniform coated, the TiO of deposition2Film thickness is 100nm.
The sample organic coating completed is prepared as basic wearing layer, inorganic coating is that two kinds of inorganic coatings are compound, structure
As shown in Figure 1, Fig. 1 is the structural schematic diagram of the Organic-inorganic composite transparent membrane prepared.
After testing, pencil hardness reaches 7H, transmitance > 90%.It is plated by hundred lattice experimental tests of standard GBT9286-1998
Binding force between layer, the edge of notch are completely smooth, and grid edge does not have any peeling, test result 5B；According to ASTM
2486 standards of D have carried out wet hair brush wear-resisting test, every 10000 progress sample to the inorganic-organic hybrid structure of the present invention
It observes on surface, the results showed that wear-resisting property is enhanced, and wet hair brush tests 50000 times without any scuffing.With organosilicon
Coating the results are shown in Table 1 as reference.
1 wear-resisting property of table is tested
Embodiment 2
1) substrate cleans：By 0.2mm organic polymer thin films (selecting high saturating PET film), 10*10cm square is cut into,
It is put into cleaning machine, first carries out cotton and glue alcohol scouring, subsequently into section is cleaned by ultrasonic, the temperature of ultrasonic cleaning is 50 DEG C, when
Between be 5min, after ultrasonic cleaning carry out pure water rinsing, dried up later with nitrogen, ensure drying after surface of semi-finished cleaning have light
Pool.
2) pretreatment of organic polymer thin film：Clean PET samples are placed in vacuum cavity, and vacuum degree reaches 10- 3Pa is surface-treated using plasma cleaning process hereinafter, be passed through oxygen to 2pa, bombardment activation 5min.
3) magnetron sputtering (PVD) deposition combines transition zone：Sample after surface cleaning enters process cavity, and target is purity 4N
Graphite target, atmosphere is Ar gas in chamber, operating air pressure 1.0Pa, and 50 DEG C of depositing temperature uses radio-frequency power supply power for 350W
(power density 1/cm2)；The inorganic carbon-base film thickness of print uniform coated, deposition is 10nm.
4) inorganic wear-resistant coating：Print is continued in vacuum cavity, magnetron sputtering deposition Al is carried out2O3Film, deposition temperature
60 DEG C of degree, target are the alundum (Al2O3) target of purity 5N, and atmosphere is Ar/O in chamber2Mixed gas, wherein Ar ratios 90%, work
Air pressure is 1.2Pa, uses radio frequency power for 700W (power density 2W/cm2)；Print uniform coated, the nothing of deposition
Machine wear-resistance thin film thickness is 200nm.
The sample completed is prepared as shown in Fig. 2, Fig. 2 is the knot of Organic-inorganic composite transparent membrane manufactured in the present embodiment
Structure schematic diagram.
After testing, pencil hardness reaches 6H, transmitance > 91%.It is plated by hundred lattice experimental tests of standard GBT9286-1998
Binding force between layer, the edge of notch are completely smooth, and grid edge does not have any peeling, test result 5B；According to ASTMD
2486 standards have carried out wet hair brush wear-resisting test, every 10000 progress sample table to the inorganic-organic hybrid structure of the present invention
It observes in face, the results showed that wear-resisting property is enhanced, and wet hair brush tests 50000 times without any scuffing.It is applied with organosilicon
Layer is used as reference, the results are shown in Table 2.
2 wear-resisting property of table is tested
Comparative example 1
1) substrate cleans：By 0.2mm organic polymer thin films (selecting high saturating PET film), 10*10cm square is cut into,
It is put into cleaning machine, first carries out cotton and glue alcohol scouring, subsequently into section is cleaned by ultrasonic, the temperature of ultrasonic cleaning is 50 DEG C, when
Between be 5min, after ultrasonic cleaning carry out pure water rinsing, dried up later with nitrogen, ensure drying after surface of semi-finished cleaning have light
Pool.
2) deposition of the inorganic wear-resistance thin film of organic polymer：Clean PET samples are placed in vacuum cavity, vacuum degree
Reach 10-3Pa is hereinafter, carry out magnetron sputtering deposition SiO2Film, 50 DEG C of depositing temperature, target are the titanium dioxide silicon target of purity 5N,
Atmosphere is Ar/O in chamber2Mixed gas, wherein Ar ratios 95%, operating air pressure 0.8Pa, use radio frequency power for
1000W (power density 3W/cm2)；Print uniform coated, the SiO of deposition2Film thickness is 300nm.
After testing, pencil hardness reaches 3H, transmitance > 90%.It is plated by hundred lattice experimental tests of standard GBT9286-1998
Binding force between layer, has sheet of transparent film layer to fall off, and than more serious, test result 2B at the edge of scribing line；According to
2486 standards of ASTM D have carried out wet hair brush wear-resisting test, every 10000 progress to the inorganic-organic hybrid structure of the present invention
Sample surfaces are observed, and as a result show that sample just has occurred that serious stripping phenomenon in a cycle.The result shows that not having
Inorganic-organic hybrid structure by activation process and the inorganic carbon-base film of deposition is completely not wear-resisting.With organic film matrix,
The comparative example prepare the inorganic-organic hybrid film without transitional bonding layer as a comparison, with organic-nothing provided by the present application
Machine laminated film carries out wear-resisting property comparison, the results are shown in Table 3.
3 wear-resisting property of table is tested
It is to be prepared using high purity graphite target as target using PVD methods in conjunction with transition zone in above-described embodiment,
Plasma cleaning can be used before deposition to handle organic coating or organic film；Organic-the nothing prepared using this method
Machine laminated film has the characteristics that high saturating, high abrasion, high durable, and technique repetition stability is good, production efficiency is high.
The explanation of above example is only intended to facilitate the understanding of the method and its core concept of the invention.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvements and modifications, these improvement and modification are also fallen within the protection scope of the claims of the present invention.
Claims (10)
1. a kind of Organic-inorganic composite transparent membrane, which is characterized in that including contact successively organic thin film layer, in conjunction with transition
Layer and inorganic coating；The combination transition zone is inorganic carbon-base film.
2. Organic-inorganic composite transparent membrane according to claim 1, which is characterized in that the combination transition zone is to adopt
The inorganic carbon-base film prepared with graphite target vacuum sputtering methods.
3. Organic-inorganic composite transparent membrane according to claim 1, which is characterized in that the inorganic carbon-base film
Thickness is 1~50nm.
4. Organic-inorganic composite transparent membrane according to claim 1, which is characterized in that the organic thin film layer is to have
Organic coating or organic film.
5. Organic-inorganic composite transparent membrane according to claim 4, which is characterized in that the organic coating is organic
Silicon system resin, acrylic ester resin or epoxy resin；
The organic film is PC, PET, PMMA, PEM or acrylic.
6. Organic-inorganic composite transparent membrane according to claim 4, which is characterized in that the thickness of the organic coating
It is 2~100 microns；The thickness of the organic film is 50~1000 microns.
7. Organic-inorganic composite transparent membrane according to claim 1, which is characterized in that the inorganic coating is Al2O3,
SiO2, SiONx, ZrO2, TiO2And SnO2One or more of and its metal Oxidation Doping form.
8. Organic-inorganic composite transparent membrane according to claim 1, which is characterized in that the inorganic coating is Al2O3,
SiO2, SiONx, ZrO2, TiO2And SnO2One or more of the composite coating that is formed by stacking of metal oxide.
9. Organic-inorganic composite transparent membrane according to claim 1, which is characterized in that the thickness of the inorganic coating
For 100~2000nm.
10. Organic-inorganic composite transparent membrane according to claim 1, which is characterized in that combine transition zone in deposition
Before, activation process is carried out to organic thin film layer.
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| CN112644133A (en) * | 2020-12-30 | 2021-04-13 | 江苏铁锚玻璃股份有限公司 | Organic transparent device surface hardening technology and organic transparent device surface structure |
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Application publication date: 20181113 |