GB2070070A - Improved Adhesion of Metal Coatings to Solid Substrates - Google Patents
Improved Adhesion of Metal Coatings to Solid Substrates Download PDFInfo
- Publication number
- GB2070070A GB2070070A GB8012664A GB8012664A GB2070070A GB 2070070 A GB2070070 A GB 2070070A GB 8012664 A GB8012664 A GB 8012664A GB 8012664 A GB8012664 A GB 8012664A GB 2070070 A GB2070070 A GB 2070070A
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- United Kingdom
- Prior art keywords
- silane
- radical
- commat
- carbon atoms
- substrate
- Prior art date
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- Granted
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 58
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 52
- 239000002184 metal Substances 0.000 title claims abstract description 52
- 238000000576 coating method Methods 0.000 title claims abstract description 43
- 239000007787 solid Substances 0.000 title claims abstract description 26
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 61
- 229910000077 silane Inorganic materials 0.000 claims abstract description 61
- 238000000034 method Methods 0.000 claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 34
- 239000011248 coating agent Substances 0.000 claims abstract description 26
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 21
- 239000000413 hydrolysate Substances 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 230000001464 adherent effect Effects 0.000 claims abstract description 8
- 238000000151 deposition Methods 0.000 claims abstract description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 7
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 43
- 229910052709 silver Inorganic materials 0.000 claims description 39
- 239000004332 silver Substances 0.000 claims description 39
- 239000011521 glass Substances 0.000 claims description 35
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- 150000002739 metals Chemical class 0.000 claims description 12
- 229920001296 polysiloxane Polymers 0.000 claims description 9
- 229910000679 solder Inorganic materials 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 229920002050 silicone resin Polymers 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000003039 volatile agent Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229920003023 plastic Polymers 0.000 claims description 3
- 239000004033 plastic Substances 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 239000011135 tin Substances 0.000 claims description 3
- 239000002023 wood Substances 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011111 cardboard Substances 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229920002379 silicone rubber Polymers 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 43
- 150000004756 silanes Chemical class 0.000 description 43
- 239000010408 film Substances 0.000 description 19
- -1 alkyl methacrylate Chemical compound 0.000 description 16
- 238000006460 hydrolysis reaction Methods 0.000 description 14
- 230000007062 hydrolysis Effects 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical compound [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 239000004411 aluminium Substances 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 7
- 239000004417 polycarbonate Substances 0.000 description 7
- 229920000515 polycarbonate Polymers 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 150000001282 organosilanes Chemical class 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229920004142 LEXAN™ Polymers 0.000 description 3
- 239000004418 Lexan Substances 0.000 description 3
- DGEYTDCFMQMLTH-UHFFFAOYSA-N methanol;propan-2-ol Chemical compound OC.CC(C)O DGEYTDCFMQMLTH-UHFFFAOYSA-N 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920006068 Minlon® Polymers 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004727 Noryl Substances 0.000 description 2
- 229920001207 Noryl Polymers 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 229920006397 acrylic thermoplastic Polymers 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 238000007733 ion plating Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005041 Mylar™ Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
- 229920013632 Ryton Polymers 0.000 description 1
- 239000004736 Ryton® Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000010961 commercial manufacture process Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 229920003020 cross-linked polyethylene Polymers 0.000 description 1
- 239000004703 cross-linked polyethylene Substances 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 229910001651 emery Inorganic materials 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- OGFYIDCVDSATDC-UHFFFAOYSA-N silver silver Chemical compound [Ag].[Ag] OGFYIDCVDSATDC-UHFFFAOYSA-N 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
Classifications
-
- 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
-
- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
- F24S23/00—Arrangements for concentrating solar-rays for solar heat collectors
- F24S23/70—Arrangements for concentrating solar-rays for solar heat collectors with reflectors
- F24S23/82—Arrangements for concentrating solar-rays for solar heat collectors with reflectors characterised by the material or the construction of the reflector
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/40—Solar thermal energy, e.g. solar towers
Abstract
A method of forming an adherent metal surface on a substrate comprises: (i) treating a solid substrate with at least one organofunctionalsilane, or a partial hydrolysate(s) thereof, having the general formula (I): <IMAGE> or a mixture of such an organofunctional silane or the partial hydrolysate(s) thereof with a second silane, or a partial hydrolysate(s) thereof, which has the general formula (II): (RO)bSiR_4-b (II> in which formulae R is an alkyl radical of 1-4 carbon atoms, R% is a difunctional hydrocarbon radical having from 1-12 carbon atoms or a -CH2CH2CH2NHCH2CH2- radical, X is an -NH2 <IMAGE> -SH, OH or Cl radical, R_ is a phenyl radical, or an alkyl radical of 1-4 carbon atoms, and a and b each have a value of 2 or 3, c has a value of 0 or 1 and a+c=3; (ii) drying the silane treated surface until the majority of volatile materials have been removed; and, thereafter, (iii) depositing a metal on the silane treated surface to form a thin continuous film or coating thereon.
Description
SPECIFICATION
Improved Adhesion of Metals to Solid Substrates
This invention relates to improved adhesion of metals to solid substrates.
There are many applications where it is desirable to form thin metallic films or coatings on various solid substrates. An example of such an application is the formation of silvered mirrors wherein very thin films or coatings of silver metal are deposited from chemical solution onto glass or similar substrates. Also, large reflectors for solar applications have been formed from vapor deposited silver or aluminum on solid substrates.
Some of the problems associated with prior art methods of forming thin metallic coatings on solid substrates have been the cumbersome application methods, for example, in producing silvered mirrors from chemical solution and, the inability to retain the metallic coating on the solid substrate for long periods of time. Also, in vapor deposition, vacuum metallizing, ion plating, spraying and similar methods, the metallized surface can only retain its aesthetic value if the substrate has been pre-treated with some composition which can mask or eliminate the scratches, pits and voids in the solid substrate. Such materials are generally curable organic coatings which are first coated onto the solid substrates at such thicknesses that they will physically fill the scratches, pits and voids, and are then cured. The metallizing is then carried out on the surface of the organic coating.Unfortunately, because of the presence of these organic "basecoats", the manufacturer is faced with a variety of adhesion problems between the basecoats and the solid substrate and the basecoat and the thin metallic film or coating. This problem is enhanced considerably when the manufactured item is intended to be used outdoors and is subject to the ravages of the weather.
What is needed therefore is an improved method of forming adherent metallic films or coatings on solid substrates and improved metallic coated materials.
According to the present invention there is disclosed an improved method of adhering a thin metallic film or coating to a solid substrate. The improved method utilizes a specific silane or mixtures of silanes to strongly adhere the thin metallic film or coating to solid substrates.
It has been known for a number of years that silanes are useful for bonding many materials to many various surfaces. It is generally recognized that silane coupling agents are not universal coupling agents such that any given silane will bond all materials to all substrates. Instead, it is generally accepted that specific silanes can be used for adhesion of specific materials to specific substrates, that is, the silane must be matched to the application and it cannot be assumed that all silanes will work in all applications.
In a recent British patent, Number 1,550,532, issued August 15, 1979, it is disclosed that thin films or coatings of metals can be adhered to plastic substrates by the use of a combination of alkoxysilanes, alkylsilicates and copolymers of alkyl acrylate or alkyl methacrylate with hydroxyalkyl acrylates or hydroxyalkyl methacrylates. This patent discloses that the inventive composition therein serves two purposes i.e. the polymeric material is a film former and the silane enhances adhesion of metal overcoat. The alkoxy silanes shown there are of the formula RnSi(OR')4~n wherein n is 1, 2 or 3, R is a C,--C, hydrocarbon group and R' is a C1-C4 alkyl group. This prior art material and method appears to work quite well so long as articles for use indoors are contemplated.It has been observed that this material does not have adequate adhesion of the deposited metal to the polymeric film which results in loss of adhesion of the thin metallic film.
It has now been found that the adhesion of thin metal films to various substrates can be enhanced by the use of certain silanes and silane mixtures on certain substrates such that the articles prepared using the inventive method are durable, weatherable and have brilliance and enhanced specularity.
What is disclosed herein is a method of forming an adherent continuous thin metal surface on a substrate and the articles prepared thereby.
Thus, what is disclosed is a method of forming an adherent metal surface on a substrate by (i) treating a solid substrate with at least one organofunctional silane, or the partial hydrolysate thereof, having the general formula:
or a mixture of such an organofunctional silane or the partial hydrolysate thereof with a second silane, or the partial hydrolysate thereof, which has the general formula (RO)bSiRb in which formulae R is an alkyl radical of 1-4 carbon atoms, R' is a difunctional hydrocarbon radical having from 1-12 carbon atoms or a -CH2CH2CH2NHCH2CH2- radical, X is an -NH2,
-SH, OH or Cl radical, R1, is a phenyl radical, or an alkyl radical of 1-4 carbon atoms and a and beach have a value of 2 or 3, c has a value of O or 1 and a+c=3; (ii) drying the silane treated surface until the majority of volatile materials have been removed; and, thereafter, (iii) depositing a metal on the silane treated surface to form a thin continuous film or coating thereon.
The organofunctionalsilanes used in step (i) have the general formula:
wherein R is an alkyl radical of 1-4 carbon atoms, R' is a difunctional hydrocarbon radical having from 1-12 carbon atoms or a -CH2CH2CH2NHCH2CH2- radical, X is an -NH2,
-SH, OH or Cl radical, R being preferably the methyl radical, a has a value of 2 or 3; c has a value of O or 1 and a+c=3.Thus, contemplated within the scope of the formula:
are such organofunctional silanes as (CH3O)Si(CH2)3NH(CH2)2NH2,
(CH3O)3Si(CH2)3SH, (CH3O)3Si(CH2)3C1, (CH3O)3Si(CH2)30H, CH3(CH3O)2Si(CH2)3NH(CH2)2NH2,
CH3(CH3O)2Si(CH2)3SH, CH3(CH3O)2Si(CH2)3C1 and CH(CH3O)2Si(CH2)3OH.
It should be noted that, contemplated within the scope of this invention, are the partial hydrolysates of these organofunctional silanes. By "partial hydrolysate", as used herein we mean the water soluble or water-miscible product formed when the organofunctional silane is treated with water to hydrolyse all or a part of the alkoxy groups on the molecule. Sometimes, in order to effect the hydrolysis, a small amount of acid is required together with the water. Whenever "hydrolysate" or "partial hydrolysate" is used herein, it shall mean that it contains the hydrolysed silane or silanes, water for hydrolysis and the alcohol solvent formed by the cleavage of the alkoxy groups from the silane.
The treatment of the substrate can be carried out with the organofunctional silane or its partial hydrolysate alone but, contemplated within the scope of this invention, is a mixture of the organofunctional silane or its partial hydrolysate with an organosilane having the general formula (RO)bSiR"4~b wherein R has the same meaning as R above, R" can be a phenyl radical, or an alkyl radical of 1-4 carbon atoms and b has a value of 2 or 3. As indicated above for the formula:
the partial hydrolysates of (R0)bSiR114b are also part of this invention, R being preferably methyl.
The organofunctional silanes and the organosilanes are well-known commercial silanes and it is believed that their manufacture is adequately set out in the art and need not be repeated herein.
Whenever it is required to use a mixture of the silanes this is done by a simple mixing technique.
The neat silanes may be mixed and then cohydrolysed or they may be hydrolysed separately and the hydrolysates mixed thereafter.
For the purpose of this invention, whenever a mixture of silanes is required, it is generally preferred that they be mixed in a ratio of 1:10 to 10:1 of organofunctional silane to organosilane on a weight basis. The ratio applies to the weight of the silanes before hydrolysis.
As indicated above, some of the silanes require the presence of a small amount of acid to enhance hydrolysis. Such acids are, for example, hydrochloric and acetic. This acid requirement is wellknawn in the silane hydrolysis art.
It is generally preferred that the silanes be hydrolysed prior to mixing. After the silanes have been hydrolysed, simple hand shaking of the hydrolysis vessel i.e. a bottle or flask will suffice to force the hydrolysis reaction Generally, the hydrolysis mixture is used at this point without further modification or purification.
The amount of total silane in the hydrolysis mixture may be from 0.01 to 35 weight percent.
Whenever the silanes are to be used neat, they can be dissolved in solvents which are soluble with or miscible with water such as isopropanol, methanol, butanol, methylcellosolve or the like.
Mixtures of such types of solvents are contemplated within the scope of this invention. These solvents may also be used with the hydrolysed silanes to enhance film forming abilities, for example.
The silanes or silane solutions may be applied to the substrate by any method which is convenient for the user. Such methods as dipping, flowing and spraying are most satisfactory for this invention.
The substrates useful in this invention are those which are solid substrates. Thus almost every useful solid substance which makes up an article can be the substrate of this invention. Such substrates may be, for example, plastics such as acrylonitrile-butadiene-styrene copplymers, sioplas (trade mark), crosslinked polyethylene (Dow Corning Corporation, Midland, Michigan), polycarbonates, polyethylene terephthalates such as Mylar (trade mark), (E. I. DuPont, Wilmington, Delaware), polyimides such as Kapton (trade mark), (E. I. DuPont), polyphenylene oxides such as Noryl (trade mark), (General Electric Co., Pittsfield, Massachusetts), polyphenylene sulfides such as Ryton (trade mark) (Phillips Chemical Co., Chicago, Illinois) and mineral filled nylons such as Minlon (trade mark) (E.
I. DuPont), acrylics, urethanes epoxys and polyesters, just to name a few. Wood, cardboard, glass, metals, silicone rubbers and resins, urethane foams and polyvinylchloride foams are examples of other useful substrates.
One method taught herein consists in treating a solid substrate with an organofunctional silane, or a mixture of an organofunctional silane and an organosilane, and then allowing the silane treated surface to dry until the majority of the volatile materials have been removed from the treated surface.
What is meant by volatile materials are the solvents, water and low molecular weight products that have been formed upon hydrolysis. What is meant by the "majority" of volatile materials is that the surface should be tack free or nearly tack free to the finger touch. This can be accomplished in a number of ways. For example, the treated surfaces can be left at room temperature for a period of time, perhaps days, to allow slow evaporation of the volatile materials into the atmosphere. Since time is usually a factor in commercial manufacture, however, the articles can be heated to remove volatiles.
Vacuum can be applied to reduce the pressure and enhance volatilisation. We have has used a number of methods to cause the removal of volatiles in a short period of time, such as 1-5 seconds, by heating and applying vacuum simultaneously.
Any method of volatile material removal that fits the manufacturers mode of manufacture is contemplated herein.
After the volatile materials have been removed, the thin metal coating is applied. Generally, any method by which thin, continuous metal coatings can be applied will suffice for this invention. Methods such as vapor deposition, electroplating, sputtering, ion plating and spraying are preferred. However, applying the thin, continuous metal coating can be accomplished from current methods of chemical solution application without detrimental effects on the adhesion promoting coating.
Metals that are useful in this invention are any metals that can be vapor deposited, electroplated, sputtered, ion plated, sprayed or applied from chemical solution. Such metals as copper, nickel, tin, silver, silver solder, gold, aluminum, platinum, titanium, zinc and chrome are preferred.
For the purpose of this invention, "thin" means the thickness of the metal film that is required to give a continuous, coherent film or coating. Generally, these coatings are less than 30 microns thick.
The articles prepared in this invention can be covered by clear protective coatings such as the silicone resins set forth in U.S. Patent 3,986,997. These materials are generally referred to as "topcoats" and are well-known in the art.
As indicated earlier, the surfaces of some substrates are sufficiently soft for them to be blemished by gouges or scratches during the manufacture of the article and in order to end up with a product that is aesthetically pleasing, the blemishes must be eliminated since simple metal plating over them with thin coatings or films allows the blemishes to show through.
A common method of covering over the blemishes is to basecoat the substrate with a material such as curable organic polymers. The organic polymer fills the blemishes and gives a smooth, flat, blemish-free surface over which the thin metal coating can be applied.
Another invention herein therefore contemplates the use of such basecoat materials in conjunction with the method of, and materials of, this invention. Thus, this invention also deals with the treatment of a substrate with a basecoat and the application of the silane or silanes of this invention to said'basecoat. The metal is then applied to the silane treated basecoat. Preferred for this invention are certain silicone basecoats. More specifically, the preferred basecoat is one that is selected from the siloxane coatings disclosed in U.S. Patent Number 3,986,997 issued to Harold A. Clark October 19, 1 976. The siloxane coatings disclosed in that patent are herein incorporated by reference.
In using a base coat, the substrate is cleaned by any conventional process and then the basecoat is applied and cured. Generally, for the Clark coating, 6-8 hours at 1 500C are required. Some basecoats require only a few minutes air dry time. In certain circumstances, depending on the substrate and the basecoat, a primer may be required. The silanes of this invention, for example, may be used as such primers. The cured basecoat is then top treated with the silane or mixtures of silanes, dried, and overcoated with the metal of choice. Thus, we contemplated within the scope of the claims of our invention substrates named herein overcoated with organic or silicone basecoats and then treated with the inventive silanes or silane mixtures.
A third aspect of this invention is the use of the silanes of this invention in conjunction with certain curable coatings to enhance the adhesion of the thin metal films or coatings. Whereas the essence of this invention where first presented herein is the treatment of certain substrates or the treatment of certain substrates basecoated with organic or silicone curable coatings, this further aspect of our invention deals with the metal coating of curable organic or silicone basecoats which have included in them, before cure, the inventive silane or silanes disclosed herein.
This invention therefore also consists in incorporating in the curable basecoat the silanes of this invention, and then depositing metals to form films or coatings thereon. The invention therefore also consists in a method of forming an adherent metal surface on a substrate by (i) treating a solid substrate with a curable organic or silicone basecoat which contains at least one organofunctional silane, or the partial hydrolysate thereof, having the general formula
or a mixture of such an organofunctional silane, or the partial hydrolysate thereof, with a second silane, or the partial hydrolysate thereof, which has the general formula (RO)bSiR"4~b in which formula R is an alkyl radical or 1 4 carbon atoms, R' is a difunctional hydrocarbon radical having from 1-12 carbon atoms or a -CH2CH2CH2NKCH2CH2- radical, X is an -NH2,
-SH, OH or Cl radical, Rn is a phenyl radical, or an alkyl radical of 1 4 carbon atoms and a and beach have a value of 2 or 3, c has a value of 0 or 1 and a+c=3; (ii) drying the basecoat until the majority of volatiles have been removed, and, thereafter; (iii) depositing a metal on the basecoat to form a thin continuous film or coating thereon.
The organic basecoats useful herein are those currently being used as basecoats for metal deposition on solid articles. These materials are air dry acrylics or urethanes which can be used with or without heat cure. Such a material, for example, is EB-1 , the trade name for an acrylic polymer manufactured by Red Spot Paint and Varnish Co., Inc, Evansville, Indiana.
The amount of silane or silanes incorporated in the basecoat is 0.1 to 10 weight percent based on the weight of silane(s) and basecoat Simple mixing of the silane into the basecoat is all that is required. It should be noted that such mixing need not be done under anhydrous conditions as the adhesive effect is enjoyed whether the silanes are used neat or in the pre-hydrolysed condition. The basecoat is dried and/or cured, depending on the application where it is being used, and then the metal top coat is applied by one of the method indicated above.
Articles which are manufactured by the methods of the invention herein have enhanced adhesion, weathering, durability and enhanced efficiency and specularity whenever the metal surface is a mirrored surface.
The following examples are not to be construed as limiting the invention which is set forth in the claims.
Several silanes were evaluated in this invention by observing the adhesion of the metal coating.
An appearance determination was made which was subjective and was based upon such characteristics as continuum of film, brilliance, specularity and the presence or absence of voids, pockmarks and the like. An excellent film is one which is continuous, without voids and/or pockmarks and has brilliance and high specularity. Specularity is a term used in the mirrored surfaces art which means the degree of light transmitted from the surface of a mirror, i.e. how good are the mirror properties. Adhesion was measured subjectively by rubbing the metal surface with a cloth saturated with acetone, methanol or isopropanol using moderate pressure unless a different method is indicated.
The degree to which the metal surface survived this treatment is reported. No removal of the coating is considered "Excellent". "Good" is when some slight abrasion occurred. "Fair" means noticeable removal of metal. "Poor" means the removal of essentially all of the metallic coating. "None" means all the coating was removed.
Example 1
The following samples were prepared to observe which silanes or combinations of silanes would give the best enhanced adhesion between a given substrate and certain metals, Silanes or combinations of silanes were made at the concentrations shown by a method which involved the hydrolysis of each silane and the eventual combinations of the silanes to give the adhesion promoter used on the substrate. Table I in this example shows the various silanes tested.
Silane A is (CH3O)3Si(CH2)3NH(CH2)2NH2. Silane B is (CH3O)3Si(CH2)3SH. Silane C is
Silane D is (CH3O)3Si(CH2)3CI, Silane E is phenylSi(OCH3)3, Silane F is propylSi(OCH3)3, Silane G is
CH2=CHSi(OCH3)3 and Silane H is HO(CH2)3Si(OCH3)3.
Results are on Table II. IPA is isopropanol. MeOH is methanol. gms is grams.
Primer Preparation-Silane A (8 gms), IPA (8 gms) and 1.12 gms of water were mixed with agitation in a small 1 ounce glass bottle with a screw-top lid. The bottle was allowed to stand overnight (about 1 6-20 hrs). The material was then diluted with 800 gms of IPA upon transferring to a larger bottle.
Silane B (12.35 gms), IPA (717.65 gms), Glacial acetic acid (30 gms) and 40 gms of water were mixed together in the order given herein.
Silane C (24 gms) and 1.2 gms of water were mixed together and allowed to stand overnight (16-20 hrs). The material wasthen diluted by 800 gms of MeOH.
Silanes D, E, F and G were all handled in the same way. Three gms of the silane were treated with 27 gms of MeOH and then a small amount of acetic acid and enough water for complete hydrolysis was added, the mixture was shaken until clear and then was used without extensive aging.
H was used at 20 weight % in MeOH by using the same method as for D, E, F and G.
All primers were filtered before use.
All samples were hand dipped in the primer solutions and the excess material was allowed to drip off. The samples were then dried as shown in the tables.
Table I shows the silanes or combination of silanes that were used in the examples. "Sample #" is the reference number for the runs that were carried out for these examples. "Silane #1" is the organofunctional silane used in the sample. "Silane #2" is the organosilane used in the sample. "Acid added" and "H2O added" means that the material was used as a hydrolysate, in the hydrolysis water, with the alcohol by-produced upon hydrolysis. In those cases where the silane was used neat, that is without prior hydrolysis, it is so indicated.
In Table II, the sample # from Table I indicates the silane(s) used in that particular run. If more than one run was made using the same silane but a different substrate or deposited metal, the run was designated a, b, c, etc. For example, from Table I, sample 4 is a primer made up of silanes C and B.
Table II, sample 4a shows that the silanes were used in a ratio of 2.4:1, there was present 1.3 weight percent total silane in the primer, the substrate in the run was glass and the deposited metal was silver solder. Sample 4b of Table II shows the primer of sample 4 of Table I, having the same ratio of silanes at the same weight percent solids but the substrate is now acrylic sheet and the deposited metal is aluminum.
All samples in Table II were vapor deposited using a Mikros Vacuum Evaporator Model VE-10 manufactured by Thermionics Laboratories, Hayward, CA.
Example 2
In order to compare the material of U.K. Patent 1,550,532 against the present invention, the following material was prepared., One hundred and eighty gms of a silicate-based polymer containing methyltrimethoxysilane were mixed with 20 gms of Acryloid OL-42 (Rohm 8 Haas Co., Philadelpha,
PA). Acryloid OL-42 is an acrylic polymer similar to that found in the U.K. patent in Example 1. The
Acryloid is 80% solids in cellosolve acetate. One gram of hexamethylenetetramine catalyst was also added with agitation.
A primer (P) was prepared for use herein which consisted of 8 gms of HS(CH2)3Si(OCH3)3 diluted with 800 gms of IPA, and 24 gms of 40% in MeOH of
diluted with 800 gms of additional MeOH. Seventy-five gms of the dilute HS(CH2)3Si(OCH3)3 were mixed with 25 gms of the dilute
and a small amount of acetic acid and water and the mixture was stirred until clear.
A Lexan (trade mark) (General Electric Co., Schenectady, NY) polycarbonate slide was abraded with emery paper to simulate an abused article from manufacturing. After the slide was cleaned, it was measured off in 4 equal sections and marked and one section was dipped in the solution of primer (P) from above and then allowed to air dry for 20 minutes at room temperature.
The solution of acrylate polymer, silicate and alkoxysilane analogous to that found in Example 1 of U.K. patent 1,550,532 was then applied to 3/4 of the slide and the 1/4 primed area was overcoated thereby and air dried. The coating was then cured 15 min. at 700C and 20 min. at 100 C. Next, 1/2 of the slide was dipped in a solution of P and allowed to air dry for 10 minutes at room temperature.
Finally, the whole slide was vapor deposited with silver metal and cured for 1 5 min. at 100 C. If one were to lay the slide on its edge and to note the coatings or layers on the top of the slide, the left-most 1/4 section (denoted A) would have a silver coating only. Moving to the right, the next 1/4 section (denoted B) would have a top layer of silver covering a layer of the "1,550,532" polymer which in turn covers the polycarbonate slide. The third 1/4 section (denoted C) would have a top layer of silver covering a layer of P primer which in turn covers the 1,550,532 polymer which in turn covers the polycarbonate slide. The last 1/4 section (denoted D) consists of a top layer of silver, a second layer of the primer P, a third layer of the 1,550,532 polymer and finally a fourth layer of primer P.
Sections B, C, and D were scored into crosshatched squares by a sharp instrument to give 25 equal squares. Scotch Brand adhesive tape #650 (3M Co., St. Paul, Minnesota) was then pressed onto the crosshatched squares and removed forcibly. Recognizing that the most optimum conditions were not observed, the test was deemed to have been passed if at least 50% or more of the silver metal remained intact. Table III shows the results.
Example 3
A silicone resin was prepared according to Example 2 of U.S. Patent 4,173,553 with the exception that the HS(CH2)3Si(OCH3)3 was present at 10 weight percent CH3Si(OCH3)3 at 40 weight percent and colloidal silica at 50 weight percent based on the weight of all three components. This material is shown herein as "A". Another sample of silicone resin was prepared as shown in Example 1 of U.S. Patent 3,986,997, that is, the same material as above but without HS(CH)2Si(OCH3)3 and this was designated "B". The two materials were compared side-by-side for their ability to accept and adhere metals which were deposited thereon. Both materials were diluted to approximately 10% solids with isopropanol.
A clean square of Lexan (trade name) polycarbonate was dipped 1/2 into "A". The remaining 1/2 was dipped in "B". The sample was then air dried for 40 minutes at 250C. The sample was then vapour deposited with silver. The sample then cured 1 hour at 1 250C. The samples both had excellent specularity. The samples were subjected to a methanol rub to test the adhesion of the silver The material "A" was clearly superior in retaining the silver metal.
Example 4
The silicone resin designated "B" in Example 3 above, was coated onto a clean Lexan (trade mark) polycarbonate square and cured 25 minutes at 100owe. One-half of the coated slide was then dipped into a primer designated earlier as primer P of Example 2 and this was allowed to dry for 2 minutes at 25 CC. The square was then vapor deposited with silver and cured 1 hour at 1 250C. The 1/2 side of the slide that had been primed with primer P of Example 2 showed superior retention of the silver deposited thereon.
The means of metal deposition described in this specification and claims are conventional means for depositing metals and it is believed that elaborate descriptions of such methods are not required by those skilled in the art Table I
Solvent Solvent H2O Acid
Sample # Silane #1 Silane #2 for #1 for #2 added added 1 A - IPA - yes No 2 B - IPA - yes yes 3 C - MeOH - yes 4 C B MeOH IPA yes yes 5 B E IPA MeOH yes yes 6 B F IPA MeOH yes yes 7 B G IPA MeOH yes yes 8 A B MeOH IPA yes yes 9 - E - MeOH yes yes 10 - F - MeOH yes yes 11 - G - MeOH yes yes 12 - H - MeOH yes
TABLE II
Deposited Dry/Cure Ratio of Total Weight
Sample #Substrate Metal Coating Conditions Adhesion * Silanes #1:2 % Silane(s) 1 glass silver solder 30 min. @ 250 C/30 min. @ 150 C Fair A - 1 2 glass silver solder 30 min. @ 25 C/30 min @ 150 C Excellent A - 1.5 3 glass silver solder 30 min. @ 25 C/30 min @ 150 C Good A - 0.4 4a glass silver solder 35 min. @ 25 C/30 min @ 150 C Excellent A 2.4:1 1.3 4b acrylic sheet Aluminium None/None Fair A 2.4:1 1.3 4c ABSTM Aluminium 30 min @ 25 C/1 hr. @ 80 C Good A 2.4:1 1.3 (Borg-Warner Chemicals,
Parkersbury, W.Va) 4d Ryton-R8 Aluminium 30 min @ 25 C/1 hr. @ 80 C Good A 2.4:1 1.3 4e Noryl Aluminium 30 min @ 25 C/1 hr. @ 80 C Good A 2.4:1 1.3 4f Minlon Aluminium 30 min @ 25 C/1 hr. @ 80 C Good A 2.4:1 1.3 4g Aluminum panel chromium 30 min. @ 25 C/1 hr. @ 80 C Excellent A 0.8:1 1.35 4h steel silver 30 min. @ 25 C/65 min @ 100 C Excellent A 0.6:1 1.1 4i SioplasR crosslinked Aluminium 5. min. @ 25 /60 min 75 C Excellent A 2.4:1 1.3 polyethylene 4j polyethylene Aluminium 5 min. @ 25 C/60 min. @ 75 C Excellent A 2.4:1 1.3 4k LexanR polycarbonate silver 5 min. @ 25 C/10min. @ 100 C Excellent I 0.6:1 1.1 *A=acetone
I=IPA
M=MeOH **no acid, no water *** used alone-not within scope of this invention.
Table II (cont.).
Deposited Dry/Cure Ratio of Total Weight
Sample # Substrate Metal Coating Conditions Adhesion * Silanes #1:2 % Silane(s) 4l wood silver 60 min @ 25 C/38 min. @ 75 C poor A 0.6:1 1.1 4m paper silver 10 min. @ 25 C/38 min. @ 75 C good A 0.6:1 1.1 4n silicone circuit silver 60 min. @ 25 C/38 min. @ 75 C Excellent A 0.6:1 1.1 board 4o silicone epoxy silver 60 min. @ 25 C/38 min. @ 75 C Good A 0.6:1 1.1 circuit board 4p TeflonR (E.I. silver 2 min. @ 25 C/48 min. @ 100 C None / 0.6:1 1.1
DuPont) cloth 4q polyester silver 30 min. @ 25 C/30 min. @ 100 C Excellent A 0.6:1 1.1 4r glass Aluminium 30 min. @ 25 C/60 min. @ 80 C Good A 0.8:1 1.3 4s glass copper 30 min. @ 25 C/30 min. @ 150 C Excellent A 0.8:1 1.35 4t glass chromium 30 min. @ 25 C/30 min. @ 150 C Excellent A 0.8:1 1.35 4u glass nickel 30 min. @ 25 C/30 min. @ 150 C Excellent A 0.8:1 1.35 4v glass tin 30 min. @ 25 C/60 min. @ 100 C Excellent A 0.6:1 1.1 4w glass silver 30 min. @ 25 C/60 min. @ 80 C Excellent A 2.4:1 1.3 4x glass gold 30 sec. @ 25 C/30 min. @ 100 C Excellent A 0.8:1 1.35 2a** glass silver 30 min. @ 25 C/10 min. @ 120 C Excellent A - 10.0 2b** glass silver 30 min. @ 25 C/10 min. @ 120 C Good A - 100 2c** glass silver 30 min. @ 25 C/10 min. @ 120 C Fair A - 0.1 2d** glass silver 30 min. @ 25 C/10 min. @ 120 C Fair A - 0.01 3a** glass silver 30 min. @ 25 C/10 min. @ 120 C Good A - 100.0 3b** glass silver 30 min. @ 25 C/10 min. @ 120 C Good A - 10.0 3c** glass silver 30 min. @ 25 C/10 min. @ 120 C Poor A - 1.0 3d** glass silver 30 min. @ 25 C/10 min. @ 120 C None A - .1 3e** glass silver 30 min. @ 25 C/10 min. @ 120 C None A - 0.01 4y glass silver 30 min. @ 25 C/10 min. @ 120 C Fair A 2.4:1 1.1 4z glass silver 30 min. @ 25 C/10 min. @ 120 C Fair A 0.6:1 1.1 5 glass silver 1 min. @ 25 C/60 min. @ 100 C Good A 1:1 2.0 6 glass silver 5 min. @ 25 C/30 min. @ 100 C Excellent I 1:1 20.0 7 glass silver 5 min. @ 25 C/30 min. @ 100 C Poor I 1:1 20.0 8 glass silver 2 min. @ 25 C/30 min. @ 100 C Excellent I 1:1 2.0 9*** glass silver 30 min. @ 25 C/30 min. @ 100 C None A - 10.0 10*** glass silver 30 min. @ 25 C/30 min. @ 100 C None A - 10.0 11*** glass silver 30 min. @ 25 C/30 min. @ 100 C None A - 10.0 12 glass aluminum 5 min. @ 25 C/30 min. @ 100 C Good A - 2.0 *A=acetone
I=IPA
N=MeOH **no acid, no water ***used alone-not within scope of this invention.
TABLE ill Appearance
% Retention ofRemaining
Sample Pass/Fail of Silver Silver
B failed* 0
C passed 65 smooth/brilliant
D passed 65 smooth/brilliant *loss of adhesion occurred at the silver/basecoat interface.
Claims (9)
1. A method of forming an adherent metal surface on a substrate comprising the steps of:
(i) treating a solid substrate with at least one organofunctionalsilane, or a partial hydrolysates
thereof, having the general formula (I):
or a mixture of such an organofunctional silane or the partial hydrolysate(s) thereof with a second silane, or a partial hydrolysates thereof, which has general formula (II)::
(RO)bSiR4-b" (II), in which formulae R is an alkyl radical of 1-4 carbon atoms, R' is a difunctional hydrocarbon radical having from 1-12 carbon atoms or a -CH2CH2CH2NHCH2CH2- radical,
X is an -NH2,
-SH, OH or Cl radical, R" is a phenyl radical, or an alkyl radical of 1 1M carbon atoms, and a and b each have a value of 2 or 3, c has a value of O or 1 and a+c=3; (ii) drying the silane treated surface until the majority of volatile materials have been removed;
and, thereafter, (iii) depositing a metal on the silane treated surface to form a thin continuous film or coating
thereon.
2. A method of forming an adherent metal surface on a substrate comprising the steps of: (i) treating a solid substrate with a curable organic or silicone basecoat and curing said basecoat; (ii) treating said cured basecoat with at least one organofunctional silane, or a partial
hydrolysate(s) thereof, having the general formula (I):
or a mixture of such an organofunctional silane, or the partial hydrolysate(s) thereof, with a second silane, or a partial hydrolysate(s) thereof, which has the general formula (II)::
(RO)bSiR4-b" (II), in which formulae R is an alkyl radical of 1-4 carbon atoms, R' is a difunctional hydrocarbon radical having from 1-12 carbon atoms or a -CH2CH2CH2NHC H2CH2- radical,
X is an -NH2,
-SH, OH or CI radical, R" is a phenyl radical, or an alkyl radical of 1--4 carbon atoms, and
a and b each have a value of 2 or 3, c has a value of O or 1 and a+c=3; (iii) drying the silane treated surface until the majority of volatile materials have been removed
and, thereafter, (iv) depositing a metal on the silane treated surface to form a thin continuous film or coating
thereon.
3. A method of forming an adherent metal surface on a substrate comprising the steps of: (i) treating a solid substrate with a curable organic or silicone basecoat which contains at least
one organofunctional silane, or a partial hydrolysate(s) thereof, having the general formula
(I):
or a mixture of such an organofunctional silane, or the partial hydrolysate(s) thereof, with a second silane, or a partial hydrolysate(s) thereof, which has the general formula (all):: (RO)bSlR114b (it), in which formulae R is an alkyl radical or 1-4 carbon atoms, R' is a difunctional hydrocarbon radical having from 1-12 carbon atoms or a -CH2CH2CH2NHCH2CH2- radical, Xis an-NH2,
-SH, OH or Cl radical, R" is a phenyl radical, or an alkyl radical of 1 4 carbon atoms and a
and b each have a value of 2 or 3, c has a value or O or I and a+c=3;
(ii) drying the basecoat until the majority of volatiles have been removed; and, thereafter;
(iii) depositing a metal on the basecoat to form a thin continuous film or coating thereon.
4. A method as claimed in claim 1,2 or 3 wherein the metal deposited is selected from a group consisting of copper, nickel, tin, silver, silver solder, gold, aluminum, platinum, titanium, zinc and chrome.
5. A method as claimed in claim 1,2 or 3 wherein the substrate is selected from a group consisting of plastics, wood, cardboard, glass, metals, silicone rubbers and silicone resins.
6. A method as claimed in claim 1,2 or 3 wherein the substrate is in the form of a lens.
7. The method of claim 1,2 or 3 wherein there is also present a clear topcoat on the deposited metal surface.
8. A method as claimed in any one of claims 1 to 3, substantially as herein described with reference to any one of the specific examples.
9. An article prepared by the method of any one of claims 1 to 8.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US12019780A | 1980-02-11 | 1980-02-11 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2070070A true GB2070070A (en) | 1981-09-03 |
| GB2070070B GB2070070B (en) | 1983-07-27 |
Family
ID=22388818
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8012664A Expired GB2070070B (en) | 1980-02-11 | 1980-04-17 | Adhesion of metal coatings to solid substrates |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JPS5857508B2 (en) |
| KR (1) | KR850001683B1 (en) |
| AU (1) | AU536293B2 (en) |
| BE (1) | BE883736A (en) |
| CA (1) | CA1159729A (en) |
| DE (1) | DE3016560C2 (en) |
| FR (1) | FR2475566A1 (en) |
| GB (1) | GB2070070B (en) |
| IT (1) | IT1140987B (en) |
| NL (1) | NL179301C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2123442A (en) * | 1982-06-18 | 1984-02-01 | Western Electric Co | Chemical surface modification of metals coating with metals |
| US4521444A (en) * | 1982-12-10 | 1985-06-04 | U.S. Philips Corporation | Method of providing a metal layer on a substrate |
| US4618506A (en) * | 1983-12-27 | 1986-10-21 | U.S. Philips Corporation | Method of providing a metal mirror |
| WO2005056868A1 (en) * | 2003-11-17 | 2005-06-23 | Dow Corning Corporation | Method of metallizing a silicone rubber substrate |
| US20130149445A1 (en) * | 2010-10-20 | 2013-06-13 | Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung E.V. | Method for producing a strong bond between a polymer substrate and an inorganic layer |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3316693A1 (en) * | 1983-05-06 | 1984-11-08 | Leybold-Heraeus GmbH, 5000 Köln | METHOD FOR PRODUCING AMORPHOUS CARBON LAYERS ON SUBSTRATES AND SUBSTRATES COATED BY THE METHOD |
| EP0176062A3 (en) * | 1984-09-27 | 1987-07-15 | Dow Corning Corporation | Silane bonding agents for high temperature applications and method therefor |
| DE3726372C2 (en) * | 1986-08-27 | 1988-10-13 | Toyoda Gosei Kk | Molded article made of plastic |
| US5147518A (en) * | 1991-03-07 | 1992-09-15 | E. I. Du Pont De Nemours And Company | Process for adhering metal to polyimide film |
| DE19859695A1 (en) * | 1998-12-23 | 2000-06-29 | Leybold Systems Gmbh | Coating plastic substrates with light reflective layer, e.g. in headlight reflector manufacture by precoating with low carbon content thin crosslinked hydrocarbon, silicon oxide, silicon nitride or silicon oxynitride barrier layer |
| JP6613677B2 (en) * | 2015-07-17 | 2019-12-04 | 三星ダイヤモンド工業株式会社 | Method and apparatus for dividing brittle substrate |
| CN107265887B (en) * | 2017-06-14 | 2020-06-09 | 卜庆革 | Conductive metalized nickel or silver plated glass material, glass cloth and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51126931A (en) * | 1975-04-29 | 1976-11-05 | Matsushita Electric Works Ltd | Method of surface metallizing |
| JPS52128968A (en) * | 1976-04-22 | 1977-10-28 | Sumitomo Chemical Co | Method of vacuum evaporation |
| US4173553A (en) * | 1977-12-23 | 1979-11-06 | Dow Corning Corporation | Non-coloring, abrasion resistant, adherent coating for gold and silver surfaces |
-
1980
- 1980-04-15 CA CA000349898A patent/CA1159729A/en not_active Expired
- 1980-04-17 GB GB8012664A patent/GB2070070B/en not_active Expired
- 1980-04-23 AU AU57724/80A patent/AU536293B2/en not_active Ceased
- 1980-04-25 NL NLAANVRAGE8002423,A patent/NL179301C/en not_active IP Right Cessation
- 1980-04-29 DE DE3016560A patent/DE3016560C2/en not_active Expired
- 1980-05-08 JP JP55061210A patent/JPS5857508B2/en not_active Expired
- 1980-05-30 IT IT8022481A patent/IT1140987B/en active
- 1980-06-06 FR FR8012615A patent/FR2475566A1/en active Granted
- 1980-06-10 BE BE0/200970A patent/BE883736A/en not_active IP Right Cessation
- 1980-10-06 KR KR1019800003842A patent/KR850001683B1/en active
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2123442A (en) * | 1982-06-18 | 1984-02-01 | Western Electric Co | Chemical surface modification of metals coating with metals |
| US4521444A (en) * | 1982-12-10 | 1985-06-04 | U.S. Philips Corporation | Method of providing a metal layer on a substrate |
| US4618506A (en) * | 1983-12-27 | 1986-10-21 | U.S. Philips Corporation | Method of providing a metal mirror |
| WO2005056868A1 (en) * | 2003-11-17 | 2005-06-23 | Dow Corning Corporation | Method of metallizing a silicone rubber substrate |
| US20130149445A1 (en) * | 2010-10-20 | 2013-06-13 | Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung E.V. | Method for producing a strong bond between a polymer substrate and an inorganic layer |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS56112453A (en) | 1981-09-04 |
| CA1159729A (en) | 1984-01-03 |
| AU536293B2 (en) | 1984-05-03 |
| FR2475566A1 (en) | 1981-08-14 |
| NL179301C (en) | 1986-08-18 |
| DE3016560A1 (en) | 1981-08-20 |
| GB2070070B (en) | 1983-07-27 |
| IT1140987B (en) | 1986-10-10 |
| IT8022481A0 (en) | 1980-05-30 |
| BE883736A (en) | 1980-12-10 |
| KR830004586A (en) | 1983-07-16 |
| NL8002423A (en) | 1981-09-01 |
| AU5772480A (en) | 1981-08-20 |
| KR850001683B1 (en) | 1985-11-22 |
| FR2475566B1 (en) | 1984-06-08 |
| DE3016560C2 (en) | 1984-01-12 |
| NL179301B (en) | 1986-03-17 |
| JPS5857508B2 (en) | 1983-12-20 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |