EP1345863A1 - Procede pour la fabrication d'un produit multicouche, utilisation d'un promoteur d'adhesion associe et application du procede - Google Patents
Procede pour la fabrication d'un produit multicouche, utilisation d'un promoteur d'adhesion associe et application du procedeInfo
- Publication number
- EP1345863A1 EP1345863A1 EP01271098A EP01271098A EP1345863A1 EP 1345863 A1 EP1345863 A1 EP 1345863A1 EP 01271098 A EP01271098 A EP 01271098A EP 01271098 A EP01271098 A EP 01271098A EP 1345863 A1 EP1345863 A1 EP 1345863A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- inorganic
- layer
- substrate
- glass
- product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000002318 adhesion promoter Substances 0.000 title claims abstract description 7
- 239000000758 substrate Substances 0.000 claims abstract description 29
- 239000011521 glass Substances 0.000 claims abstract description 26
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical class S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000011248 coating agent Substances 0.000 claims abstract description 14
- 238000000576 coating method Methods 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000008021 deposition Effects 0.000 claims abstract description 4
- 230000001235 sensitizing effect Effects 0.000 claims abstract 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 19
- 229910052709 silver Inorganic materials 0.000 claims description 19
- 239000004332 silver Substances 0.000 claims description 19
- 238000011282 treatment Methods 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000005507 spraying Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 206010070834 Sensitisation Diseases 0.000 claims description 4
- 230000008313 sensitization Effects 0.000 claims description 4
- 238000005282 brightening Methods 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 19
- 239000000047 product Substances 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 230000004913 activation Effects 0.000 description 6
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 230000006872 improvement Effects 0.000 description 4
- HAAYBYDROVFKPU-UHFFFAOYSA-N silver;azane;nitrate Chemical compound N.N.[Ag+].[O-][N+]([O-])=O HAAYBYDROVFKPU-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 241000353345 Odontesthes regia Species 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 238000006124 Pilkington process Methods 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011325 microbead Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007921 spray Substances 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
- C03C17/38—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 at least one coating being a coating of an organic material
-
- 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
- C03C17/42—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 of an organic material and at least one non-metal coating
Definitions
- the present invention relates generally to multilayer elements formed from at least one inorganic substrate, in particular made of glass, coated with an inorganic product, in particular a metallic layer.
- the invention relates to the manufacture of a mirror formed from a glass substrate coated with a metallic layer, for example silver.
- silver mirrors are produced in the following way: the glass substrate is first polished and then its surface is treated with an aqueous solution of SnCI 2 . This treatment is commonly called sensitization treatment. After rinsing, the glass surface is usually activated by means of an ammoniacal silver nitrate treatment. The silvering solution is then applied to form an opaque silver coating. The silver coating is then usually covered with a protective layer of copper and then with one or more layers of paint to produce the finished mirror.
- the silver coating does not always adhere sufficiently to the glass substrate. In the case of certain prior products, it has been observed that the silver coating peels off spontaneously from the glass substrate. This is the case, for example, when the silver layer is formed from traditionally manufactured silver microbeads incorporated into a plastic matrix.
- French patent FR 2 719 839 is known, for example, which describes a method for obtaining good adhesion of a silver coating on the surface of a glassy substrate.
- the activation step is carried out by bringing the glassy substrate into contact not with ammoniacal silver nitrate but with a particular activation solution such as an aqueous solution of palladium chloride.
- a particular activation solution such as an aqueous solution of palladium chloride.
- this document teaches that the awareness step must precede the activation step.
- the activation step here aims to obtain on the glass surface, palladium chloride nodules strongly linked to the glass and which serve as a sort of attachment points for the silver layer which is then deposited.
- the present invention relates to a process for manufacturing a multilayer product comprising an inorganic substrate, in particular made of soda-lime-silica glass (glass obtained by the float process) coated with an inorganic product such as a metallic layer.
- the method consists in using an adhesion promoter to achieve adhesion between an inorganic substrate and an inorganic product, said promoter being chosen from the family of mercaptosilanes having a covalent double bond.
- the present invention relates to the use of an adhesion promoter to achieve adhesion between an inorganic substrate and an inorganic product.
- the inorganic substrate is a glass substrate and the inorganic product is a metal, in particular a metallic layer. More specifically, said metallic layer can be a silver layer.
- the mercaptosilane is chosen from the mercaptosilanes of general formula:
- the surface of the glass substrate is treated and sensitized before using the mercaptosilane.
- the deposition of mercaptosilane is carried out by spraying an aqueous solution or emulsion containing it, onto the glass substrate. Furthermore, the treatment of the glass surface consists of washing and brightening (or polishing).
- awareness consists in forming a layer based on tin.
- the present invention proposes, as part of a process for manufacturing a multilayer product, an improvement in the interface between two of the layers. and more particularly between a metal-based layer and a layer and / or a glass substrate.
- the invention particularly relates to a process for manufacturing a multilayer product comprising an inorganic substrate, in particular glass, said substrate undergoing the following treatments:
- an adhesion promoter being chosen from, the family of mercaptosilanes having a covalent double bond
- the treatment according to the invention is preferably applied to glass substrates on which a silver coating is applied to form a mirror.
- the silver coating formed during a so-called silvering step, commonly has a thickness of between 70 nm and 100 nm.
- the usual step of activating the glass is in fact a treatment of the glass with a given and adapted activation solution and often presents implementation difficulties.
- this step is replaced by a treatment of said surface with a particular silane, more precisely by a mercaptosilane which is easy to use as will be explained below.
- Mercaptosilanes are known for their ability to adhere an inorganic element such as a metal to an organic element.
- the present invention aims to use a mercaptosilane not to adhere an organic element to an inorganic element, but to adhere an inorganic to an inorganic and this very effectively.
- mirrors - samples - were subjected to attack by hydrochloric acid vapors; the mirrors are placed on the cover of a closed enclosure containing a bath of 37% hydrochloric acid. The silver side of the mirrors is placed towards the bath so that the hydrochloric acid vapors directly attack the silver side of the mirrors.
- the second ⁇ is a mirror in which the glass has been sensitized
- the third ® mirror is sensitized and then activated with zero silver ', that is to say with a solution of ammoniacal silver nitrate;
- the fourth ⁇ D sample is a mirror which has also undergone sensitization and then activation with palladium chloride;
- the samples were thus exposed for 18 hours in a closed enclosure.
- a so-called “dishesion by ultrasound tank in HCI bath” test was carried out with the samples ⁇ (D® and ⁇ described above; the test consists in preferably simultaneously immersing the samples in a tank containing a bath hydrochloric acid, and emit ultrasound in the bath. We note the times necessary to completely take off the money on each of the samples.
- the detachment times are comparable for the ® and ⁇ cases.
- the bonds created according to the invention are by their nature different from those known previously: the bonds according to the invention are covalent bonds (therefore strong) and numerous with both the inorganic substrate and the inorganic coating product, whereas according to the prior art the bonds are rather of metallic type.
- the present invention allows real cost reductions since the mercaptosilanes cost a few francs per kilo whereas palladium chloride currently costs around 200 francs per kilo, ie three times the price of gold.
- a technical advantage is linked to the invention; more specifically, the use of mercaptosilane is easier than that of palladium chloride. Indeed, the palladium chloride precipitates as soon as it is diluted so that when it is then a question of spraying it, there are obstructions of nozzles carrying out the spraying; this leads to lower quality spraying and to the formation of a more or less homogeneous layer. No concern of this nature is possible with the mercaptosilane according to the invention.
- the metal layer can be based on copper or gold.
- concentration of mercaptosilane is of the order of 2% in a solution which is preferably aqueous but which could be alcoholic.
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)
- Surface Treatment Of Glass (AREA)
- Chemically Coating (AREA)
- Laminated Bodies (AREA)
- Optical Elements Other Than Lenses (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0016648A FR2818271B1 (fr) | 2000-12-20 | 2000-12-20 | Procede pour la fabrication d'un produit multitouche, application du procede et utilisation d'un promoteur d'adhesion associee |
FR0016648 | 2000-12-20 | ||
PCT/FR2001/003956 WO2002049979A1 (fr) | 2000-12-20 | 2001-12-12 | Procede pour la fabrication d'un produit multicouche, utilisation d'un promoteur d'adhesion associe et application du procede |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1345863A1 true EP1345863A1 (fr) | 2003-09-24 |
Family
ID=8857915
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP01271098A Withdrawn EP1345863A1 (fr) | 2000-12-20 | 2001-12-12 | Procede pour la fabrication d'un produit multicouche, utilisation d'un promoteur d'adhesion associe et application du procede |
Country Status (9)
Country | Link |
---|---|
EP (1) | EP1345863A1 (cs) |
JP (1) | JP2004516215A (cs) |
KR (1) | KR20030069180A (cs) |
CN (1) | CN1481341A (cs) |
AU (1) | AU2002219289A1 (cs) |
CZ (1) | CZ20031755A3 (cs) |
FR (1) | FR2818271B1 (cs) |
PL (1) | PL360948A1 (cs) |
WO (1) | WO2002049979A1 (cs) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1880416B1 (en) | 2005-05-10 | 2012-01-18 | Dow Corning Corporation | Process for minimizing electromigration in an electronic device |
FR2943144B1 (fr) * | 2009-03-13 | 2012-12-14 | Jet Metal Technologies | Miroir anticorrosion, son procede de fabrication et ses applications dans la recuperation de l'energie solaire |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL8204783A (nl) * | 1982-12-10 | 1984-07-02 | Philips Nv | Werkwijze voor het aanbrengen van een metaallaag op een substraat. |
US5008153A (en) * | 1988-12-08 | 1991-04-16 | Ppg Industries, Inc. | Corrosion inhibitive pretreatment for "copper-free" mirrors |
GB9409538D0 (en) | 1994-05-12 | 1994-06-29 | Glaverbel | Forming a silver coating on a vitreous substrate |
GB9418289D0 (en) * | 1994-09-10 | 1994-10-26 | Univ Liverpool | Solutions or dispersions and a method of synthesising materials having controlled electronic and optical properties therefrom |
-
2000
- 2000-12-20 FR FR0016648A patent/FR2818271B1/fr not_active Expired - Fee Related
-
2001
- 2001-12-12 EP EP01271098A patent/EP1345863A1/fr not_active Withdrawn
- 2001-12-12 WO PCT/FR2001/003956 patent/WO2002049979A1/fr not_active Application Discontinuation
- 2001-12-12 KR KR10-2003-7007687A patent/KR20030069180A/ko not_active Withdrawn
- 2001-12-12 AU AU2002219289A patent/AU2002219289A1/en not_active Abandoned
- 2001-12-12 CN CNA018209858A patent/CN1481341A/zh active Pending
- 2001-12-12 CZ CZ20031755A patent/CZ20031755A3/cs unknown
- 2001-12-12 JP JP2002551484A patent/JP2004516215A/ja active Pending
- 2001-12-12 PL PL01360948A patent/PL360948A1/xx not_active Application Discontinuation
Non-Patent Citations (1)
Title |
---|
See references of WO0249979A1 * |
Also Published As
Publication number | Publication date |
---|---|
WO2002049979A1 (fr) | 2002-06-27 |
FR2818271A1 (fr) | 2002-06-21 |
AU2002219289A1 (en) | 2002-07-01 |
CZ20031755A3 (cs) | 2004-09-15 |
CN1481341A (zh) | 2004-03-10 |
JP2004516215A (ja) | 2004-06-03 |
FR2818271B1 (fr) | 2003-08-29 |
KR20030069180A (ko) | 2003-08-25 |
PL360948A1 (en) | 2004-09-20 |
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Legal Events
Date | Code | Title | Description |
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Free format text: ORIGINAL CODE: 0009012 |
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17P | Request for examination filed |
Effective date: 20030602 |
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AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR |
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AX | Request for extension of the european patent |
Extension state: AL LT LV MK RO SI |
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STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
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18D | Application deemed to be withdrawn |
Effective date: 20050701 |