CN108698920A - The method for being etched selectively to layer or stacked body on the glass substrate - Google Patents
The method for being etched selectively to layer or stacked body on the glass substrate Download PDFInfo
- Publication number
- CN108698920A CN108698920A CN201780013216.3A CN201780013216A CN108698920A CN 108698920 A CN108698920 A CN 108698920A CN 201780013216 A CN201780013216 A CN 201780013216A CN 108698920 A CN108698920 A CN 108698920A
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- China
- Prior art keywords
- decorative layer
- essentially inorganic
- inorganic decorative
- organic coating
- stacked body
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- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 41
- 239000011521 glass Substances 0.000 title claims abstract description 30
- 239000000758 substrate Substances 0.000 title claims abstract description 9
- 239000011248 coating agent Substances 0.000 claims abstract description 37
- 238000000576 coating method Methods 0.000 claims abstract description 37
- 238000000151 deposition Methods 0.000 claims abstract description 18
- 230000008021 deposition Effects 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 6
- 239000004744 fabric Substances 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000000178 monomer Substances 0.000 claims description 9
- 238000007639 printing Methods 0.000 claims description 9
- 238000010791 quenching Methods 0.000 claims description 8
- 230000000171 quenching effect Effects 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910003437 indium oxide Inorganic materials 0.000 claims description 5
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 5
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 5
- 238000004544 sputter deposition Methods 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000007641 inkjet printing Methods 0.000 claims description 4
- 238000007650 screen-printing Methods 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- -1 acrylic ester Chemical class 0.000 claims description 3
- 238000005452 bending Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 3
- 229910052752 metalloid Inorganic materials 0.000 claims description 3
- 150000002738 metalloids Chemical class 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229920003986 novolac Polymers 0.000 claims description 2
- 238000007645 offset printing Methods 0.000 claims description 2
- 239000011368 organic material Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 230000002285 radioactive effect Effects 0.000 claims description 2
- 229940071182 stannate Drugs 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims 2
- 150000001336 alkenes Chemical class 0.000 claims 1
- 239000012954 diazonium Substances 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 1
- 239000004814 polyurethane Substances 0.000 claims 1
- 229920002635 polyurethane Polymers 0.000 claims 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims 1
- 238000005096 rolling process Methods 0.000 claims 1
- 239000013067 intermediate product Substances 0.000 abstract description 2
- 230000000717 retained effect Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 73
- 239000002966 varnish Substances 0.000 description 11
- 238000005530 etching Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 4
- 238000005034 decoration Methods 0.000 description 4
- 238000005240 physical vapour deposition Methods 0.000 description 4
- 241001074085 Scophthalmus aquosus Species 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000001459 lithography Methods 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 230000032258 transport Effects 0.000 description 2
- NNNLYDWXTKOQQX-UHFFFAOYSA-N 1,1-di(prop-2-enoyloxy)propyl prop-2-enoate Chemical compound C=CC(=O)OC(CC)(OC(=O)C=C)OC(=O)C=C NNNLYDWXTKOQQX-UHFFFAOYSA-N 0.000 description 1
- 239000004923 Acrylic lacquer Substances 0.000 description 1
- 241001076973 Aroma Species 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910003087 TiOx Inorganic materials 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- VEBCLRKUSAGCDF-UHFFFAOYSA-N ac1mi23b Chemical compound C1C2C3C(COC(=O)C=C)CCC3C1C(COC(=O)C=C)C2 VEBCLRKUSAGCDF-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3657—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having optical properties
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3649—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer made of metals other than silver
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/72—Decorative coatings
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/30—Aspects of methods for coating glass not covered above
- C03C2218/32—After-treatment
- C03C2218/328—Partly or completely removing a coating
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/30—Aspects of methods for coating glass not covered above
- C03C2218/34—Masking
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
The present invention relates to the methods for depositing one or more inorganic decorating layers on the glass substrate, it includes the following steps:According to pattern in its surface part but upper deposition organic coating is not all of on base material, in the deposited on substrates one or more inorganic decorating layer so coated, make the entirety through heat-treated, so that organic coating burns, then-by use cloth to wipe with wipe and/or removed by air-flow and/or by washing the coating and cover its inorganic decorating layer, so that the inorganic decorating layer heap stack retained is arranged in pattern, which corresponds to the negative film of the pattern generated with organic coating.Purposes the invention further relates to the intermediate products of this method and the glass of the acquisition as the decorating mirror with clear area.
Description
The present invention relates to a kind of glass panes, pass through physical vapour deposition (PVD) (PVD) technique (mainly magnetron auxiliary on it
Cathodic sputtering), plasma enhanced chemical vapor deposition (PECVD) or evaporation or wet deposition process deposition it is one or more thin
Layer, the thin layer has can be from several centimeters to the space structure of the scale less than 10 microns.
Target product is decorative:Change optical property, layer (minute surface or the antireflection of the reflection levels in visible light
Layer etc.), the coloring for changing the transmissivity in visible light or absorbed layer for aesthetic purposes, electrochromic layer, electroluminescent hair
Photosphere, anti-iris layer.
Particularly, the present invention relates to clear area (the i.e. etching regions according to pattern of these layers, certain in these layers
In the case of may require several microns of even tens nanometers of very fine resolution ratio) industrial production.
Decorative effect transports the glass pane of building, interior decoration, urban facilities even (ground, air are waterborne)
The application of the vehicles is also sought.
Target product especially by magnetron sputter deposition stacked body.The present invention is more particularly directed to reflecting layer (reflections
Mirror), the reflecting layer being such as particularly described in document EP0962429A1.
Presently, there are many solutions to be used for discontinuous layer, that is, the pattern layer for including etching region is integrated into glass pane
In.According to the first solution, people know that thermal control function is not provided by thin conductive layer, but by polyvinyl alcohol contracting fourth
Aldehyde (PVB) interlayer provides or other nano particles containing conductive compound, and such as (ITO is used for the indium oxide of such as tin dope
Tin indium oxide) polyvinyl butyral (PVB) interlayer provide.In this case, pass through reflected light by absorbing
The energy part of spectrum ensures thermal control.This solution is only feasible for daylight control, it is solved relative to reflection
Scheme is relatively low effective, and needs laminated windowpanes.
Second of solution is after deposition to be etched to be optionally removed sufficiently thin Ag containing layer
The silver that the item of (100 μm) takes, so that eyes are difficult to discover and promote wavelength of its transmission that them is made to divide each other according to hope
Open several millimeters.Complicated pattern can be used for this application.The representative of this technology especially can in document WO9954961A1 and
It is found in WO2014033007A1.
In addition, the efficiency of heating surface of conductive layer depends on its sheet resistance R2, the voltage between electrode, additionally depend on electrode it
Between distance.For Application in Building, this dependence is a problem, because for identical power supply, glass pane is for each
The heating zone of size must have there are one resistance.A solution can be to etch such as layer based on Ag again, so as to
Its overall sheet resistance is adjusted, to allow it compatible in interelectrode distance and the surface heating power pursued.
On the other hand, silver-based glass pane can carry out function and turn to antenna form, as long as the layer is for example electric with body of a motor car
Magnetic uncoupling.This operation is also to be ensured by etching.
The method for selective etching of replacement is substantially from microelectronics industry.Some use temporary layer, and other are used
Directly etch.
In microelectronics industry, lithography:It is used as the mask of selective acid etching using temporary layer.Lithography
Allow to generate very delicate pattern (being industrially 45-90nm at present), but is still limited by mask size and (is now subjected to optics
The size of device limits).
Ensure that the laser-induced thermal etching of conductive layer, the laser make stack of thin by the scanning of light beam by dotted etching laser
Body distils.This operation has low productivity on large scale glass pane, and needs to carry out for handled surface
Great amount of investment.
There is limitation identical with laser-induced thermal etching by the productivity aspect that is etched in of the shock of ion or electronics.
Other engraving methods come from traditional printing.
Currently, for the size more than 10 square metres, inkjet printing technology is still limited by the time-write interval more than minute.
When being desirably less than 50 μm of resolution-scale, other technologies can be relative to silk-screen printing (screen
Printing it is) preferred:In fact, this method provides relatively mediocre edge quality under these small scales.
Therefore, the purpose of the present invention is to provide decorative windowpanes as defined above, have the etching according to pattern
Transparent region, pattern is with the resolution ratio that can be very delicate several μm or even tens nm.
For this purpose, the theme of the present invention is a kind of essentially inorganic decorative layer or substantially of depositing on the glass substrate
The method of inorganic decorative layer stacked body, it is characterised in that it includes the following steps:
In its surface part but it is not all of the upper substantially organic coating of deposition on base material according to pattern,
In the essentially inorganic decorative layer of the deposited on substrates so coated or essentially inorganic decorative layer stacked body,
Make the entirety through heat-treated, so that substantially organic coating burns, then
It is such as used cloth to wipe with by wiping and wipes and/or removed by air-flow and/or by washing substantially organic coating and covering
Its essentially inorganic decorative layer or essentially inorganic decorative layer stacked body, to obtain according to the essentially inorganic of pattern
Decorative layer or essentially inorganic decorative layer stacked body, the pattern correspond to the pattern generated with substantially organic coating
Negative film.
Organic coating burning product be a kind of powder being not adhere on base material so that it at this moment can with cover its
One or more inorganic layers are removed together, (especially do not print organic coating simultaneously without will produce any easily damaged base material
The quality (clarity, resolution ratio) of the edges of regions covered by one or more of inorganic layers) brush erosion, friction or abrasion class
The mechanism of type.
This method allows in industrial production line on large area substrates, at 1m to 10 μm or even smaller size
The pattern of substantially organic coating is obtained in surface range.The cycle time of shortening allows its characteristic being industrially applicable in obtain
Verification.
The method of the present invention can be by decorative layer or decorative layer stacked body (when the decorative layer is reflexive)
Top or the reflecting layer disposed thereon dope layer for covering these inorganic decorating layers at another layer are terminated.Inorganic decorating layer.This
Kind measure is conventional in mirror production.
The method of the present invention may also include the discontinuous metal layer to be formed and be combined with one or more dielectric layers, such as in text
It offers described in WO2015177474A1.The function of these layers is the absorption spectrum for changing mirror in visible light, to generate it
The reflected image that color is changed.
Preferably, substantially organic coating passes through liquid approach and means, directly or indirectly engraving according to the deposition of pattern
Roller method, such as hectographic printing, flexographic offset printing, pass through ink jet printing method, by mask method, lithographic printing or silk screen
Printing is implemented.The roller that width can be used to be at least 3210mm (Pleine Largeur Float-PLF), rag
(gravure) desirable pattern will be reproduced.In the case that this accurate, it is related to a kind of repeat patterns, but this still with
Such as the improvement of electromagnetic transmission is compatible.
Preferably, substantially organic coating is selected from acrylate monomer and/or oligomer, epoxy acrylic ester monomer
And/or oligomer, polyester acrylate monomers and/or oligomer, urethane acrylate monomer and/or oligomer, polyethylene
Pyrrolidones+EDTA compositions, polyamide, polyvinyl butyral, diazo naphthoquinone-novolac type positive light-sensitive resin
Individually or it is form of mixtures a variety of in them with crosslinked any organic material under infrared or ultraviolet radioactive.
Preferably, substantially organic coating, which has, is at most equal to 30, and by the incremental sequence of priority, is at most equal to
20 and 10 μm, particularly preferably about 5 μm of thickness.However, the thickness of 1 μm of even hundreds of nm is not excluded in addition to the present invention.It is printing
Except region (it corresponds to the pattern of 1m to 10 μm or smaller area size) brushed with this organic coating, need not face
When organic coating not make to be intended to that there is the inorganic decorating in the region of complete inorganic stacked body to stack after quenching at these
Body degrades.
Preferably, before depositing essentially inorganic decorative layer or essentially inorganic decorative layer stacked body, substantially
The preparation of organic coating includes by heat treatment and/or in the case where radiating such as ultraviolet (UV) radiation and/or the crosslinking of drying, then
Wash the entirety.Substantially organic coating can be advantageously crosslinked at UV, to limit for drying required space.So
And will ensure that the flowing of the substantially organic coating (varnish, resin etc.) before crosslinking is restricted, to avoid pattern accuracy
Loss.
Varnish or resin will be appropriately dried before the washer by coating machine, then be carried out one or more
The deposition operation of (thin) essentially inorganic decorative layer.It is also contemplated that being washed before the part of organic coating deposition (printing)
The glass is washed, this printing is then carried out and optionally followed by crosslinking, then immediately proceeds to coating machine (without washing in advance
It washs).
Preferably, essentially inorganic decorative layer or essentially inorganic decorative layer stacked body are heavy by physical vacuum gas phase
Product (PVD) method, such as cathodic sputtering, especially magnetron enhance cathodic sputtering, and evaporation or plasma enhanced chemical vapor are heavy
Product (PECVD), or formed by wet method.
Preferably, essentially inorganic decorative layer or essentially inorganic decorative layer stacked body are made up of:Ag, Cr,
Ti, Al, Nb, Cu, Au, Ga or metalloid, metal oxide, such as Ti, Si, Sn, the oxide of Zn etc., transparent conductive oxide
(TCO), such as the indium oxide of tin dope (ITO), the indium oxide (IZO) of zinc doping, ZnO:The compound of Al, cadmium stannate, N and Si,
Such as undoped Si3N4, or with the Si of the doping such as Al3N4, relevant dielectric stack stack, individual or combination a variety of in them.
It cannot be cut due to glass once quenching, in some applications, such as in Application in Building, it can quenched
It is stored, is then cut before, finishing etc..This glass pane can be sold as former state, mainly, in this case, tool
Have then in converter (transformateur) by quenching the layer being removed.
Preferably, heat treatment forms a part for the thermal quenching of glass baseplate.During quenching, varnish or resin pass through combustion
It burns and disappears, and in fact remove essentially inorganic decorative layer or essentially inorganic decorative layer stacked body from the position of pattern,
To realize desirable selective etch.
In one particular embodiment, heat treatment forms the bending operation of glass baseplate, especially by the curved of compacting
A part for song operation.In this case, the pre-heat treatment causes the disappearance of varnish or resin.If using operated pressing tool with into
Row bending, then will ensure that the burning that substantially organic coating occurs before this pressing stage.
According to this method variant, essentially inorganic decorative layer or essentially inorganic decoration layer heap deposited
After stack, redeposited at least one substantially organic essentially inorganic decorative layer of coating-or essentially inorganic dress
Adorn the sequence of layer heap stack.This deposition preferably carries out before the heat treatment, so that substantially organically applying closest to base material
Layer burning, and subsequent heat treatment will cause the burning and then removal for the substantially organic coating for realizing multiple superpositions
Multiple their essentially inorganic decorative layers of covering or essentially inorganic decorative layer stacked body.However, make it is first basic
It goes up the heat treatment of organic coating burns and wipes or remove its organic residue by air-flow and cover the inorganic residual of them
After staying object, since the second sequence, the substantially organic essentially inorganic decorative layer of coating-or essentially inorganic decoration
The deposition of the sequence of layer heap stack also constitutes the part of the present invention.Therefore, the different transparent region pattern groups of mirror can be made
It closes, or this transparent region is combined with the region of different colours.
The glass baseplate that method through the invention obtains can be also integrated into laminated windowpanes or other laminations are multiple
It closes in product and/or in multiple glazing.
The present invention other themes include:
Glass baseplate, its surface a part but be not all of and have at least one sequence according to pattern covers, the sequence
By not easily passing through with the removable substantially organic coating of the washing of water (being optionally acidified or alkalization) or organic solvent
Composition, then covered with essentially inorganic decorative layer or essentially inorganic decorative layer stacked body;Therefore, it is present invention side
The intermediate products of method (for selling on the market);
The glass pane obtained by method as described above is used as the application of decorating mirror, and the decorating mirror has along pattern
Transparent region;It can be the glass pane with following various layers:It is (anti-to change optical property, the layer of the reflection levels of visible light
Penetrate minute surface or anti-reflecting layer etc.), the coloring for changing the transmissivity of visible light or absorbed layer for aesthetic purposes, electrochromism
Layer, electroluminescence layer, anti-rainbow layer are used for building, interior decoration, and urban facilities even (ground, in the air, waterborne) transport is handed over
Logical tool.
The present invention will be better understood according to following embodiment.
Embodiment 1
Refer to the attached drawing 1, method of the invention can be in four views corresponding to three continuous key steps (in the accompanying drawings from a left side
To the right side) in illustrate.
Using with formula as below at UV cross-linking acrylic lacquer, wherein the ratio is in mass:57%
Six acrylate oligomer of aliphatic carbamate (CN9276 produced by Sartomer), 38% monomer, more accurately
19% Tricyclodecane Dimethanol diacrylate (TCDDMDA or the SR833S from Sartomer) and 19% three hydroxyl first
Base propane triacrylate (TMPTA or the SR351 from Sartomer) and last 5% ketone type photoinitiator, more precisely
It says, is the mixture (Speedcure 500 from BASF or Irgacure 500) of benzophenone and ketone.By using leaf
All these compounds of piece blender mechanical mixture (resin and photoinitiator) prepare this varnish.After stirring a few hours,
If being protected from light and avoiding the strong variations of temperature, varnish can be stored some months.
In order to implement the deposition, a certain amount of varnish is applied on appropriate glass using indirect roller engraving method and is in
Sharp edge shape, as shown in the step 1 of attached drawing 1.After passing through below roller, the varnish of base material+deposition is exposed to UV (mercury type lamp).Tool
The thickness of figuratum varnish coat is 5 μm.
In step 2 by cathodic sputtering on glass+acrylate varnish system conformally stringer stacked body.This
Kind stack of thin body has consisting of (since glass baseplate), and wherein thickness is as unit of nm:SnO2 20 / Cr 27 /
Si3N4: Al 11.7 / TiOx2.3.The stacked body of this reflection visible light is hardenable.
In quenching Step (3 in Fig. 1), usually in 730 DEG C of convection oven, every millimeter of glass continues 35 seconds
(glass for 4mm thickness is 140 seconds), organic layer degradation, so as to cause the magnetron sputtering layer in their existing regions
Stripping.Final system is made of above-mentioned stack of thin body, according to the figure for the negative film for corresponding to the pattern generated using resin
Case carries out structuring.
Ink jet printing by allowing to be formed the layer of 10 μ m-thicks also obtains excellent result using the varnish.
Embodiment 2
The embodiment and previous embodiment are the difference is that substantially organic coating.Herein, it is related to by Marabu
Ink that company sells in its Ultra-Jet DUV A series (especially cyan or magenta) it is inkjet deposited.It obtains several
Hundred nanometers to several microns of thickness.Ink (pattern) is crosslinked at UV.
The resolution ratio obtained by the method for the invention is only dependent upon the printing process for organic coating.During quenching,
There is no or almost no be changed for it.The transparent pattern width that track with 25 μm of fineness produces 25 μm (reflects visible
The etching line of the stacked body of light).
Claims (13)
1. a kind of method depositing essentially inorganic decorative layer or essentially inorganic decorative layer stacked body on the glass substrate,
It is characterized in that it includes the following steps:
In its surface part but it is not all of the upper substantially organic coating of deposition on base material according to pattern,
In the essentially inorganic decorative layer of the deposited on substrates so coated or essentially inorganic decorative layer stacked body,
Make the entirety through heat-treated, so that substantially organic coating burns, then
It is such as used cloth to wipe with by wiping and wipes and/or removed by air-flow and/or by washing substantially organic coating and covering
Its essentially inorganic decorative layer or essentially inorganic decorative layer stacked body, to obtain according to the essentially inorganic of pattern
Decorative layer or essentially inorganic decorative layer stacked body, the pattern correspond to the pattern generated with substantially organic coating
Negative film.
2. the method as described in claim 1, which is characterized in that substantially organic coating passes through liquid according to the deposition of pattern
Body approach and means, direct or indirect engraved roll method, such as hectographic printing, flexographic offset printing are led to by ink jet printing method
Mask method is crossed, lithographic printing or silk-screen printing are implemented.
3. method as claimed in claim 2, which is characterized in that the substantially organic coating is selected from acrylate monomer
And/or oligomer, epoxy acrylic ester monomer and/or oligomer, polyester acrylate monomers and/or oligomer, polyurethane third
Olefin(e) acid ester monomer and/or oligomer, polyvinylpyrrolidone+EDTA compositions, polyamide, polyvinyl butyral, diazonium naphthalene
Quinone-novolac type positive light-sensitive resin, crosslinked any organic material under infrared or ultraviolet radioactive individually or are
A variety of form of mixtures in them.
4. method as described in any one of the preceding claims, which is characterized in that the substantially organic coating has extremely
It is equal to 30 μm, and by the incremental sequence of priority more, be at most equal to 20 μm and is at most equal to 10 μm, particularly preferably about 5 μm
Thickness.
5. method as described in any one of the preceding claims, which is characterized in that deposit essentially inorganic decorative layer or
Before essentially inorganic decorative layer stacked body, the preparation of substantially organic coating includes by heat treatment and/or radiating
As being crosslinked under ultraviolet light and/or by drying, it is washed out the entirety.
6. method as described in any one of the preceding claims, which is characterized in that essentially inorganic decorative layer or substantially
Inorganic decorative layer stacked body enhances cathode by vacuum PVD method (PVD) such as cathodic sputtering, especially magnetron
Sputtering, evaporation or plasma enhanced chemical vapor deposition (PECVD), or formed by wet method.
7. method as claimed in claim 6, which is characterized in that essentially inorganic decorative layer or essentially inorganic decorative layer
Stacked body is made up of:Ag, Cr, Ti, Al, Nb, Cu, Au, Ga or metalloid, metal oxide, such as Ti, Si, Sn, Zn or
The oxide of metalloid, transparent conductive oxide (TCO), such as the indium oxide (ITO) of tin dope, the indium oxide of zinc doping
(IZO), ZnO:The compound of Al, cadmium stannate, Si and N, such as undoped Si3N4Or the Si with Al or other doping3N4, individually
Or combination a variety of in them.
8. method as described in any one of the preceding claims, which is characterized in that the heat treatment forms the glass baseplate
Thermal quenching a part.
9. such as preceding claims any one of them method, which is characterized in that heat treatment forms the bending operation of glass baseplate
A part.
10. method as claimed in claim 9, which is characterized in that described to curve through compacting and implemented.
11. method as described in any one of the preceding claims, which is characterized in that deposited essentially inorganic decorative layer
Or essentially inorganic decorative layer stacked body and then the essentially inorganic dress of at least one substantially organic coating-of deposition
Adorn the sequence of layer or essentially inorganic decorative layer stacked body.
12. a kind of glass baseplate, its surface a part but be not all of and have at least one sequence according to pattern covers, should
Sequence is formed by not easily passing through with the removable substantially organic coating of the washing of water or organic solvent, then with substantially
Inorganic decorative layer or the covering of essentially inorganic decorative layer stacked body.
13. by the application for the glass pane that the method described in any one of claim 1 to 11 obtains, it is used as decorating mirror, tool
The clear area of with good grounds pattern.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1651630 | 2016-02-26 | ||
| FR1651630A FR3048245B1 (en) | 2016-02-26 | 2016-02-26 | METHOD FOR SELECTIVELY ENGRAVING LAYER OR LAYER STACK ON GLASS SUBSTRATE |
| PCT/FR2017/050406 WO2017144824A1 (en) | 2016-02-26 | 2017-02-23 | Method for the selective etching of a layer or a stack of layers on a glass substrate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108698920A true CN108698920A (en) | 2018-10-23 |
Family
ID=56117864
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201780013216.3A Pending CN108698920A (en) | 2016-02-26 | 2017-02-23 | The method for being etched selectively to layer or stacked body on the glass substrate |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP3419945A1 (en) |
| KR (1) | KR20180101585A (en) |
| CN (1) | CN108698920A (en) |
| FR (1) | FR3048245B1 (en) |
| MX (1) | MX2018010200A (en) |
| WO (1) | WO2017144824A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112969671A (en) * | 2018-11-14 | 2021-06-15 | 法国圣戈班玻璃厂 | Method for selectively etching a layer or stack on a glass substrate |
| CN113677638A (en) * | 2019-04-11 | 2021-11-19 | 法国圣戈班玻璃厂 | Method for evaluating sensitivity of glazing to quench mark formation |
| CN114174237A (en) * | 2019-06-28 | 2022-03-11 | 维特罗平板玻璃有限责任公司 | Substrate with burnable coating mask |
| US11639470B2 (en) | 2020-12-28 | 2023-05-02 | Samsung Display Co., Ltd. | Etching composition for thin film containing silver, method for forming pattern and method for manufacturing a display device using the same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI776067B (en) | 2018-06-29 | 2022-09-01 | 美商維托平面玻璃有限責任公司 | Burn-off protective coating |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2807111A (en) * | 1953-09-18 | 1957-09-24 | Turner Mfg Company | Ornamented mirrors and method of making same |
| DE19817712C1 (en) | 1998-04-21 | 2000-02-03 | Sekurit Saint Gobain Deutsch | Transparent plate, in particular glass pane with a coating and a radiation window |
| DE19825424C1 (en) | 1998-06-06 | 2000-01-05 | Ver Glaswerke Gmbh | Glass pane with a metallic reflective layer system |
| US20080213482A1 (en) * | 2007-03-01 | 2008-09-04 | Stephan Lvovich Logunov | Method of making a mask for sealing a glass package |
| EA029588B1 (en) | 2012-08-28 | 2018-04-30 | Сэн-Гобэн Гласс Франс | Coated pane having areas in which the coating is partially removed |
| FR3021414B1 (en) | 2014-05-21 | 2022-09-09 | Saint Gobain | COLORED MIRROR |
-
2016
- 2016-02-26 FR FR1651630A patent/FR3048245B1/en not_active Expired - Fee Related
-
2017
- 2017-02-23 EP EP17710353.8A patent/EP3419945A1/en not_active Withdrawn
- 2017-02-23 WO PCT/FR2017/050406 patent/WO2017144824A1/en active Application Filing
- 2017-02-23 KR KR1020187024209A patent/KR20180101585A/en not_active Ceased
- 2017-02-23 MX MX2018010200A patent/MX2018010200A/en unknown
- 2017-02-23 CN CN201780013216.3A patent/CN108698920A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112969671A (en) * | 2018-11-14 | 2021-06-15 | 法国圣戈班玻璃厂 | Method for selectively etching a layer or stack on a glass substrate |
| CN113677638A (en) * | 2019-04-11 | 2021-11-19 | 法国圣戈班玻璃厂 | Method for evaluating sensitivity of glazing to quench mark formation |
| CN113677638B (en) * | 2019-04-11 | 2024-05-24 | 法国圣戈班玻璃厂 | Method for evaluating sensitivity of glazing to formation of quench marks |
| CN114174237A (en) * | 2019-06-28 | 2022-03-11 | 维特罗平板玻璃有限责任公司 | Substrate with burnable coating mask |
| US11639470B2 (en) | 2020-12-28 | 2023-05-02 | Samsung Display Co., Ltd. | Etching composition for thin film containing silver, method for forming pattern and method for manufacturing a display device using the same |
| US12031076B2 (en) | 2020-12-28 | 2024-07-09 | Samsung Display Co., Ltd. | Etching composition for thin film containing silver, method for forming pattern and method for manufacturing a display device using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20180101585A (en) | 2018-09-12 |
| EP3419945A1 (en) | 2019-01-02 |
| WO2017144824A1 (en) | 2017-08-31 |
| MX2018010200A (en) | 2019-01-14 |
| FR3048245B1 (en) | 2018-03-16 |
| FR3048245A1 (en) | 2017-09-01 |
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| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20181023 |
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| WD01 | Invention patent application deemed withdrawn after publication |