WO2000063303A1 - Traitements au silane pour ameliorer l'adhesion et la resistance a la corrosion - Google Patents

Traitements au silane pour ameliorer l'adhesion et la resistance a la corrosion Download PDF

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Publication number
WO2000063303A1
WO2000063303A1 PCT/EP2000/003711 EP0003711W WO0063303A1 WO 2000063303 A1 WO2000063303 A1 WO 2000063303A1 EP 0003711 W EP0003711 W EP 0003711W WO 0063303 A1 WO0063303 A1 WO 0063303A1
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WO
WIPO (PCT)
Prior art keywords
bis
silane
silyl
coating
group
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PCT/EP2000/003711
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English (en)
Inventor
Wim J. Van Ooij
Guru P. Sundararajan
Original Assignee
University Of Cincinnati
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Filing date
Publication date
Priority claimed from GBGB9908515.1A external-priority patent/GB9908515D0/en
Priority claimed from US09/356,912 external-priority patent/US6416869B1/en
Priority claimed from PCT/US1999/031324 external-priority patent/WO2000039177A2/fr
Application filed by University Of Cincinnati filed Critical University Of Cincinnati
Priority to AU39672/00A priority Critical patent/AU3967200A/en
Priority to DE10084461T priority patent/DE10084461T1/de
Publication of WO2000063303A1 publication Critical patent/WO2000063303A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/20—Pretreatment
    • 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/14—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • 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
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/02—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using non-aqueous solutions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/54—No clear coat specified
    • 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
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/20—Use of solutions containing silanes

Definitions

  • the present invention relates to silane coatings. More particularly, the invention relates to silane coatings for increasing corrosion resistance in metals and/or improving bonding of metals to polymers, ceramics to polymers and glass to polymers. Description of Related Art
  • metal surfaces are electrocoated in order to not only protect the metal surface, but also to provide an aesthetically-pleasing appearance.
  • Electrocoating is an electrochemical process by which an organic coating is applied to a metal using electrical current.
  • the metal article (or substrate) to be coated is immersed in a bath containing the electrocoat material, and a D.C. current is applied to the bath.
  • the workpiece i.e., the metal article to be coated
  • acts as one electrode usually the cathode
  • a second electrode is provided in the bath (typically the electrodialysis cell itself) acts as the second electrode.
  • the electrically charged particles of the coating material will migrate to the oppositely-charged electrode (i.e., the workpiece), and are deposited thereon.
  • the organic coatings used in electrocoating processes are typically paints or primers.
  • Metal used in the automobile industry are typically electrocoated with a primer prior to painting.
  • automotive metals include cold rolled steel (“CRS”), electrogalvanized steel (“EGS”), hot dipped galvanized steel (“HDG”), galvanneal (annealed hot-dipped galvanized steel), aluminum and aluminum alloys, and other zinc-alloy coated metals.
  • CRS cold rolled steel
  • EVS electrogalvanized steel
  • HDG hot dipped galvanized steel
  • galvanneal annealed hot-dipped galvanized steel
  • aluminum and aluminum alloys and other zinc-alloy coated metals.
  • Zinc phosphate conversion coatings typically require a chromate rinse which is environmentally undesirable, and must be modified with fluorides when used on aluminum surfaces.
  • chromate rinse which is environmentally undesirable, and must be modified with fluorides when used on aluminum surfaces.
  • silane coatings have been developed for preventing corrosion of metal substrates.
  • U.S. Patent No. 5,108,793 describes a technique of coating certain metal substrates with an inorganic silicate followed by treating the silicate coating with an organofunctional silane (U.S. Patent No.5, 108,793).
  • U.S. Patent No.5,292,549 teaches the rinsing of metallic coated steel sheet with a solution containing an organic silane and a crossiinking agent.
  • Other silane coatings are described in U.S. Patent Nos. 5,750,197 and 5,759,629, both of which are incorporated herein by way of reference.
  • the corrosion protection provided by a particular silane coating will depend upon the identity of the metal substrate itself.
  • the silane coating must also be compatible with any polymer layer to be applied over the silane coating (such as paints, adhesives or rubbers).
  • any polymer layer to be applied over the silane coating such as paints, adhesives or rubbers.
  • a particular silane coating may provide excellent paint adhesion and corrosion protection, that same silane coating may provide little or no adhesion to certain rubbers. Thus, it is often necessary to tailor the silane coating to the specific application.
  • any treatment used prior to electrocoating must provide an electrically conductive coating which is also resistant to the harsh conditions of the electrocoat bath. For example, when cathodic electrocoating is used, any pretreatment coating must be resistant to a pH of about 10-12. While zinc phosphate conversion coatings are electrically conductive and can withstand the alkaline bath conditions, most silane films are insulators and may not withstand a high alkaline environment.
  • silane solution which may be applied to a substrate in order to improve adhesion between glass and polymer coatings.
  • silane solution which may be applied to a substrate in order to improve adhesion between ceramics and polymer coatings.
  • One aspect of the present invention provides a method of treating a metal substrate, comprising:
  • silane solution comprising at least one silane which has been at least partially hydrolyzed, the silane chosen from the group consisting of bis-silyl aminosilanes and bis-silyl polysulfur silanes.
  • the silane coated metal substrate has improved corrosion resistance, even without subsequent painting or application of an other type of polymer coating (such as a paint, adhesive, plastic or rubber).
  • the silane coating also provides improved adhesion to polymer coatings, such as rubbers, adhesives and paints, particularly electrocoat paints.
  • Suitable bis-silyl aminosilanes for use in the present invention include:
  • each R 1 is individually chosen from the group consisting of: hydrogen, C - C 24 alkyl and C 2 - C 24 acyl; each R 2 is individually chosen from the group consisting of: substituted aliphatic groups, unsubstituted aliphatic groups, substituted aromatic groups, and unsubstituted aromatic groups; and X is either:
  • each R 3 is individually chosen from the group consisting of: hydrogen, substituted and unsubstituted aliphatic groups, and substituted and unsubstituted aromatic groups; and R 4 is chosen from the group consisting of: substituted and unsubstituted aliphatic groups, and substituted and unsubstituted aromatic groups.
  • Suitable bis-silyl polysulfur silanes include:
  • each R 1 is an alkyl or an acetyl group
  • Z is — Q — Sx — Q —
  • each Q is an aliphatic or aromatic group
  • x is an integer of from 2 to 10.
  • the above methods may be used on a variety of metal substrates, including: -a metal substrate having a zinc-containing coating;
  • -steel e.g., cold rolled steel, hot rolled steel, coated steel and stainless steel
  • the present invention also provides a silane solution comprising at least one substantially hydrolyzed bis-silyl aminosilane; and at least one substantially hydrolyzed bis-silyl polysulfur silane.
  • the silane treatment solution may be utilised in additional treatment methods to electrocoating.
  • the treatment solution finds utility in methods of adhesion promotion between glass and polymers, and ceramics and polymers.
  • Suitable polymer coatings include rubbers, adhesives plastics and paints.
  • plastic coatings include acrylic, polyester, polyurethane, polyethylene, polyimide, polyphenylene oxide, polycarbonate, polyamide, epoxy, phenolic, acrylonitrile-butadiene-styrene, and acetal plastics.
  • Particular preferable rubber coatings include sulfur cured rubbers, nitrile rubbers, chloroprene rubbers, polyisoprenes, polybutadienes, siliicone rubbers (including fluorosilicone rubbers), acrylic rubbers and isoprene-acrylonitrile rubbers.
  • ceramics generally include (but are not limited to) silica, alumina, silicon nitride, boron carbide and boron nitride.
  • glass generally includes (but is not limited to) soda glass, barium glass, strontium glass, borosilicate glass and glass-ceramics containing lanthanum.
  • Silane coated substrates as well as metal substrates, including electrocoated metal substrates, are also provided by the present invention.
  • an electrochemically applied coating i.e., electrocoating
  • the silane coating is applied from a silane solution which includes at least one bis-silyl aminosilane, at least one bis-silyl polysulfur silane, or a mixture of at least one bis-silyl aminosilane and at least bis-silyl polysulfur silane.
  • the silane coating is applied from a solution wherein the silanes have been at least partially hydrolyzed.
  • the silane undercoating provides corrosion protection which is at least equivalent to that provided by phosphate conversion coatings, and also provides excellent adhesion between the metal and the electrocoat.
  • the electrocoat films are of the same thickness as those formed on phosphate conversion coatings, and are free of craters and other defects.
  • the method of applying the silane coating is much simpler than phosphate conversion coating methods, and avoids the environmentally undesirable by-products of phosphate conversion coatings (such as chromium).
  • the silane coatings of the present invention also provide improved corrosion protection, even without subsequent electrocoating, and provide adhesion to other polymer layers (such as non-electrocoat paints, rubbers and adhesives). Therefore, the present application is not limited to silane coatings for improving electrocoat adhesion.
  • the use of certain silane coatings for promoting adhesion and/or preventing corrosion of metal surfaces is known in the art.
  • Applicants have previously found that the corrosion of metal can be prevented by applying a treatment solution containing one or more hydrolyzed vinyl silanes to the metal, and that paint may be applied directly over the resulting silane coating (see U.S. Patent No. 5,759,629). While the corrosion protection and paint adhesion provided by the resulting vinyl silane coating was surprisingly superior to conventional chromate-based treatments, Applicants have found that vinyl silane coatings of the type described in their U.S. Patent No. 5,759,629 do not provide adhesion between the metal surface and an electrocoat equivalent to that provided by phosphate conversion coatings.
  • BTSE 1,2-bis-(triethoxysilyl)ethane
  • ⁇ -UPS ⁇ -ureidopropyltrialkoxysilane
  • SAAPS N-[2-(vinylbenzylamino)- ethyl]-3-aminopropyltrimethoxysilane
  • a silane coating applied from a silane solution which includes at least one bis-silyl aminosilane, at least one bis-silyl polysulfur silane, or a mixture of at least one bis-silyl aminosilane and at least bis-silyl polysulfur silane provides excellent adhesion between a metal substrate and an electrocoating.
  • the solutions and methods of the present invention may be used on a variety of substrates.
  • the substrates include metals, including zinc, zinc alloys, metal substrates having a zinc-containing coating, steel (e.g., cold rolled steel, hot rolled steel and stainless steel), aluminum, aluminum alloys, and magnesium alloys.
  • the metal substrate can even be sandblasted prior to using the solutions and methods of the present invention.
  • a steel substrate such as hot rolled steel
  • Sandblasting typically leaves a high surface roughness as well as surface contaminants, both of which create difficulties when one attempts to apply a coating to sandblasted substrates.
  • the solutions and methods of the present invention allow for the formation of silane coatings on sandblasted substrates.
  • the solutions and methods of the present invention are particularly useful on sheet metals used in the automotive industry, since such metals are often electrocoated. These automotive metals include: steel (particularly cold rolled steel ("CRS”)); steel having a zinc-containing coating, such as galvanized steel (especially hot dipped galvanized steel (“HDG”) and electrogalvanized steel
  • GAS galvanneal
  • galvanized steel galvanneal (annealed hot dipped galvanized steel) and similar types of coated steel; zinc and zinc alloys, zinc-nickel alloy (typically about 5% to about 13% nickel content), and zinc-cobalt alloy (typically about 1 % cobalt); aluminum; and aluminum alloys.
  • the solutions of the present invention may also be used on a variety of other metals, such as GALVALUME® (a 55%-AI/43.4%-
  • the solutions of the present invention may be applied to the metal prior to shipment to the end-user, and even provide corrosion protection during shipment and storage (including the prevention of wet-storage stain such as white rust).
  • the end user merely applies an electrocoating in the usual manner directly on top of the silane coating provided by the present invention.
  • the silane coatings of the present invention not only provide excellent corrosion protection, but also provide superior adhesion between the metal substrate and the electrocoat. Thus, unlike many of the currently-employed treatment techniques, the silane coatings of the present invention need not be removed prior to electrocoating.
  • the solutions of the present invention comprise one or more bis-silyl aminosilanes, one or more bis-silyl polysulfur silanes, or a mixture of one or more bis-silyl aminosilanes and one or more bis-silyl polysulfur silanes.
  • the solutions do not require the use or addition of silicates or aluminates, and eliminate the need for phosphate conversion coatings.
  • the silanes in the treatment solution should be at least partially hydrolyzed, and are preferably substantially fully hydrolyzed.
  • the silane solutions of the present invention preferably include water, and may include one or more compatible solvents (such as ethanol, methanol, propanol or isopropanol), as needed.
  • a solvent will generally be needed only if the solution includes a bis-silyl polysulfur silane (in order to solubilize the polysulfur silane).
  • the amount of solvent needed will vary depending upon the amount (if any) of bis-silyl polysulfur silane(s) in the solution.
  • the ratio of water to solvent may be between about 1:99 and about 99:1 , more preferably between about 1:1 and about 1 :20.
  • the silanes may be prepared as an emulsion without a solvent.
  • the silane(s) is simply mixed with water and a suitable surfactant known to those skilled in the art.
  • a emulsified, hydrolyzed solution of a bis-silyl polysulfur silane can be prepared, for example, by mixing a 5% solution of the silane in water along with 0.2% of a surfactant (by volume).
  • Suitable surfactants include, for example, sorbitan fatty acid esters (such as Span 20, available from ICI Surfactants).
  • the application pH of the silane solution is preferably between about 3.5 and about 10.
  • the term "application pH” refers to the pH of the silane solution when it is applied to the metal surface, and may be the same as or different from the pH during solution preparation.
  • the pH may be adjusted by the addition of one or more acids, preferably organic acids such as acetic, formic, propionic or iso-propionic.
  • Sodium hydroxide (or other compatible base) may be used, if needed, to raise the pH of the treatment solution.
  • the preferred pH is between about 4 and about 9, most preferably between about 6 and about 9.
  • the preferred pH is between about 3.5 and about 10, most preferably between about 6 and about 9.
  • the silane solution of the present invention includes both a bis- silyl aminosilane and bis-silyl polysulfur silane
  • the preferred application pH is between about 4 and about 9, most preferably between about 8 and about 9 (particularly when used to improve electrocoat adhesion). It should be pointed out that pH adjustment is not always necessary, since many of the silanes used in the present invention have a natural pH in an aqueous solution which falls within the preferred ranges mentioned above.
  • the preferred bis-silyl aminosilanes which may be employed in the present invention have two trisubstituted silyl groups, wherein the substituents are individually chosen from the group consisting of hydroxy, alkoxy, aryloxyand acyloxy.
  • these bis-silyl aminosilanes have the general structure:
  • each R 1 is chosen from the group consisting of: hydrogen, C, - C 24 alkyl (preferably C, - C 6 alkyl), and C 2 - C 24 acyl (preferably C 2 -C 4 acyl).
  • Each R 1 may be the same or different, however the bis-silyl aminosilane(s) is hydrolyzed in the solution such that at least a portion (and preferably all or substantially all) of the non-hydrogen R 1 groups are replaced by a hydrogen atom.
  • each R is individually chosen from the group consisting of: hydrogen, ethyl, methyl, propyl, iso-propyl, butyl, iso-butyl, sec-butyl, ter-butyl and acetyl.
  • Each R 2 in the aminosilane(s) may be a substituted or unsubstituted aliphatic group, or a substituted or unsubstituted aromatic group, and each R 2 may be the same or different.
  • each R 2 is chosen from the group consisting of: C, - C 10 alkylene, C, - C 10 alkenylene, arylene, and alkylarylene. More preferably, each R 2 is a C, - C 10 alkylene (particularly propylene).
  • X may be:
  • each R 3 may be a hydrogen, a substituted or unsubstituted aliphatic group, or a substituted or unsubstituted aromatic group, and each R 3 may be the same or different.
  • each R 3 is chosen from the group consisting of hydrogen, C - C 6 alkyl and C, - C 6 alkenyl. More preferably, each R 3 is a hydrogen atom.
  • R 4 in the aminosilane(s) may be a substituted or unsubstituted aliphatic group, or a substituted or unsubstituted aromatic group.
  • R 4 in the aminosilane(s) may be a substituted or unsubstituted aliphatic group, or a substituted or unsubstituted aromatic group.
  • R 4 is chosen from the group consisting of: C, - C 10 alkylene, C, - C 10 alkenylene, arylene, and alkylarylene. More preferably, R 4 is a C, - C 10 alkylene (particularly ethylene).
  • Particularly preferred bis-silyl aminosilanes which may be used in the present invention include:
  • the preferred bis-silyl polysulfur silanes which may be employed in the present invention include:
  • each R 1 is as described before.
  • the polysulfur silane(s) is hydrolyzed in the treatment solution such that at least a portion (and preferably all or substantially all) of the non-hydrogen R 1 groups are replaced by a hydrogen atom.
  • Z is — Q — S x — Q — , wherein each Q is an aliphatic (saturated or unsaturated) or aromatic group, and x is an integer of from 2 to 10.
  • Q within the bis-functional polysulfur silane can be the same or different.
  • each Q is individually chosen from the group consisting of: C, - C ⁇ alkyl (linear or branched), C, - C 6 alkenyl (linear or branched), C, - C 6 alkyl substituted with one or more amino groups, C, - C 6 alkenyl substituted with one or more amino groups, benzyl, and benzyl substituted with C 1 - C 6 alkyl.
  • bis-silyl polysulfur silanes include bis- (triethoxysilylpropyl) sulfides having 2 to 10 sulfur atoms. Such compounds have the following formula:
  • x is an integer of from 2 to 10.
  • One particularly preferred compound is bis-(triethoxysilylpropyl) tetrasulfide (also referred to as bis-(triethoxysilylpropyl) sulfane, or'TESPT).
  • Commercially-available forms ofTESPT (suchas A-1289, available from Witco) , however, are actually mixtures of bis-(triethoxysilylpropyl) sulfides having 2 to 10 sulfur atoms. In other words, these commercially- available forms of TESPT have a distribution of sulfide chain lengths, with the S 3 and S 4 sulfides predominating.
  • the scope of the present invention includes silane solutions containing mixtures of bis-silyl polysulfur silanes, either alone or in combination with one or more bis-silyl aminosilanes.
  • the aminosilane(s) and the polysulfur silanes in the solutions of the present invention are at least partially, and preferably are substantially fully hydrolyzed in order to facilitate the bonding of the silanes to the metal surface and to each other.
  • the non-hydrogen R 1 groups are replaced by a hydrogen atom.
  • Hydrolysis of the silanes may be accomplished, for example, by merely mixing the silanes in water, and optionally including a solvent (such as an alcohol) in order to improve silane solubility and solution stability.
  • the silanes may first be dissolved in a solvent, and water then added to accomplish hydrolysis.
  • the pH may be maintained below about 10, more preferably in the preferred application pH ranges described previously.
  • the pH may be adjusted, for example, by the addition of a compatible organic acid, as described previously.
  • the various silane concentrations discussed and claimed herein are all defined in terms of the ratio between the amount (by volume) of unhydrolyzed silane(s) employed to prepare the treatment solution (i.e., prior to hydrolyzation), and the total volume of treatment solution components (i.e., bis-silyl aminosilanes, bis-silyl polysulfur silanes, water, optional solvents and optional pH adjusting agents).
  • concentrations herein refer to the total amount of unhydrolyzed aminosilanes employed, since multiple aminosilanes may optionally be present.
  • the polysulfur silane(s) concentrations herein are defined in the same manner.
  • the concentration of hydrolyzed silanes in the silane solution beneficial results will be obtained over a wide range of silane concentrations and ratios. It is preferred, however, that the solution have at least about 0.1% silanes by volume, wherein this concentration refers to the total concentration of bis-silyl aminosilane(s) and/or bis-silyl polysulfur silane(s) in the silane solution.
  • the optimum silane concentration will vary depending upon the intended use. For example, higher concentrations of silanes may be effectively employed when the silane coating is to be used for corrosion protection only.
  • the solution has between about 0.1% and about 10% silanes by volume.
  • the most preferred concentration of bis-silyl aminosilane is between about 0.5% and about 3% by volume.
  • the most preferred concentration of bis-silyl polysulfur silane is between about 3% and about 7% by volume.
  • the total silane concentration is most preferably between about 1% and about 3%.
  • the present invention is not limited to any particular range of silane ratios. It is preferred, however, that the ratio of bis-silyl aminosilane(s) to bis-silyl polysulfur silane(s) in the silane solution is between about 1:99 and about 99:1. More preferably, particularly when the silane solution is to be applied to cold rolled steel, this ratio is between about 3:1 and about 99:1. Even more preferably, this ratio is between about 3:1 and about 9:1. As reported in Application Serial No.
  • the silane solutions of the present invention having both a bis-silyl aminosilane and a bis- silyl polysulfur silane also provide excellent adhesion to rubbers (particularly sulfur-cured rubbers).
  • silane solutions for improving rubber bonding preferably have a ratio of bis-silyl aminosilane(s) to bis-silyl polysulfur silane(s) of between about 1:10 and about 10:1 , most preferably between about 1 :3 and about 1:1.
  • the particularly preferred application pH for silane coatings used to improve rubber adhesion is between about 4 and about 7.
  • the treatment solution may optionally include one or more solvents (such as an alcohol) in order to improve silane solubility.
  • solvents such as an alcohol
  • Particularly preferred solvents include: methanol, ethanol, propanol and isopropanol.
  • the ratio of water to solvent may be between about 1:99 and about 99:1, more preferably between about 1:1 and about 1:20. The method of preparing the silane solution is very simple.
  • the unhydrolyzed silanes, water, solvent (if needed), and a small amount of acid (if pH adjustment is needed) are combined with one another.
  • the solution is then stirred at room temperature in order to hydrolyze the silanes.
  • the hydrolysis may take up to several hours to complete, and its completion will be evidenced by the solution becoming clear.
  • hydrolysis may be allowed to proceed for several days (such as 3 or 4 days) for optimal performance.
  • the aminosilanes and polysulfur silanes are separately hydrolyzed in the same manner (including aging of the hydrolyzed polysulfur silane for 3-4 days or longer).
  • the polysulfur silane may be prepared as an emulsion, with no solvent (other than water). The two solutions are then mixed together prior to coating of the metal substrate, and it is preferred that the two silane solutions are mixed with one another immediately prior to the coating of the metal substrate.
  • ceramic or glass substrates may be treated, with any of the silane treatment compositions of any aspect of the present invention, in an analogous way to the treatment of a metal substrate.
  • the metal surface to be coated with the solution of the present invention may be solvent and/or alkaline cleaned by techniques well-known to those skilled in the art prior to application of the silane solution of the present invention.
  • the silane solution (prepared in the manner described above) is then applied to the metal surface (i.e., the sheet is coated with the silane solution) by, for example, dipping the metal into the solution (also referred to as "rinsing"), spraying the solution onto the surface of the metal, or even brushing or wiping the solution onto the metal surface.
  • dipping the metal into the solution also referred to as "rinsing”
  • spraying spraying the solution onto the surface of the metal
  • even brushing or wiping the solution onto the metal surface Various other application techniques well- known to those skilled in the art may also be used.
  • the duration of dipping is not critical, as it generally does not significantly affect the resulting film thickness. It is merely preferred that whatever application method is used, the contact time should be sufficient to ensure complete coating of the metal. For most methods
  • the metal substrate may be air-dried at room temperature, or, more preferably, placed into an oven for heat drying.
  • Preferable heated drying conditions include temperatures between about 20°C and about 200°C with drying times of between about 30 seconds and about 60 minutes (higher temperatures allow for shorter drying times). Temperatures above about 200°C should be avoided, except in the case of aluminum substrates. More preferably, heated drying is performed at a temperature of at least about 100°C, for a time sufficient to allow the silane coating to dry. While heated drying is not necessary to achieve satisfactory results (particularly in the case of silane solutions containing only a polysulfur silane), it will reduce the drying time thereby lessening the likelihood of the formation of white rust during drying.
  • the treated metal may be shipped to an end-user, or stored for later use.
  • the coatings of the present invention provide significant corrosion protection, even without being electrocoated.
  • the coatings of the present invention provide corrosion resistance during both shipping and storage prior to electrocoating. More importantly, this silane coating need not be removed prior to electrocoating.
  • the end-user such as an automotive manufacturer
  • may electrocoat a second coating such as a primer, a paint, or other protective or decorative coating directly on top of the silane coating without additional treatment (such as the application of a phosphate conversion coating).
  • the silane coatings of the present invention not only provide a surprisingly high degree of adhesion to the electrocoating, but also prevent delamination and underpaint corrosion even if a portion of the base metal is exposed to the atmosphere.
  • the silane coatings of the present invention may be used beneath either cathodic or anodic electrocoat materials, particularly cathodic electrocoats used in the automotive industry.
  • Cathodic (or cationic) electrocoat materials are deposited as a coating on the cathode during an electrocoating process. Therefore, when a cathodic coating is applied by electrocoating, the workpiece (i.e., the metal substrate previously coated with the silane solution) becomes the cathode in the electrocoat cell.
  • the pH of the cathode i.e., the metal substrate
  • silane coatings of the present invention are not only electrically conductive (as is required for proper electrocoating to take place), but also are resistant to alkali. Therefore, the silane coatings of the present invention allow for the formation of an excellent, high-build electrocoat film (i.e., coating).
  • the electrocoating process may be accomplished using apparatus and methods well-known to those skilled in the art.
  • silane coated metal substrates prepared in accordance with the present invention may be electrocoated in the same manner as metal substrates which have been treated with phosphate conversion coatings.
  • Suitable electrocoat materials include cathodic epoxy-urethane electrocoats such as ED-5000 (available from PPG
  • the electrocoat may be applied by standard electrocoating techniques known to those skilled in the art.
  • the various silane solutions described in the following examples were prepared by mixing the indicated silane(s) with water, solvent (ethanol), and acetic acid (if needed to provide the indicated pH during solution preparation).
  • the silanes were first hydrolyzed separately in a solution of water and solvent, and the hydrolyzed silane solutions were then mixed to form the final silane solution composition in indicated.
  • the silane solutions were hydrolyzed for at least 24 hours prior to application.
  • the indicated metal substrates were solvent-cleaned, alkaline-cleaned, water rinsed, then dipped into the silane solution for approximately 1 minute, and then (unless otherwise indicated) dried at 100°C for about 5-10 minutes.
  • the samples were then cathodically electrocoated with ED- 5000 using standard electrocoating conditions (250-300 volts, at room temperature, for about 5 minutes). After electrocoating, each sample was baked at 350°F for about 20 minutes.
  • the silane coatings of the present invention also provide improved corrosion protection, even without subsequent electrocoating, and provide adhesion to other polymer layers (such as non-electrocoat paints, rubbers and adhesives).
  • Applicants' testing has shown that the silane coatings of the present invention provide improved corrosion protection and improved adhesion to a variety of paints and paint systems, including polyester, polyurethane, epoxy and acrylic paints (or combinations thereof). These paints can be water-borne, solvent-based or even powder paints.
  • the present application is not limited to silane coatings for improving electrocoat adhesion.
  • Example 1 As shown in the table which follows, corrosion performance of electrocoated metal substrates having a silane undercoating in accordance with the present invention were compared to untreated metals and metals treated with a conventional phosphate conversion coating. Electrochemical impedance spectroscopy (EIS) was used to evaluate corrosion protection. In EIS testing, the polarization resistance, R P , provides a measure of the corrosion resistance, with larger values of R p , indicating better corrosion resistance.
  • the A-1170 silane solutions comprised 2 parts silane (by volume), 48 parts water, and 50 parts ethanol. Unless otherwise noted, the pH of the silane solutions was also adjusted to about 8 during solution preparation. For solutions containing 5% A-1289, the solution further comprised 5% water and 90% ethanol. In addition, panels coated with solutions containing A1289 (with no A1170) were dried at room temperature, rather than baked.
  • A-1170 bis-(trimethoxysilylpropyl) amine
  • A-1289 bis-(triethoxysilylpropyl) tetrasulfide
  • Example 1 Additional samples were prepared in the manner described above in Example 1.
  • the solutions included equal parts silane(s) and water (by volume), with the remainder being ethanol (e.g., 2% UPS, 2% water, 96% ethanol).
  • ethanol e.g., 2% UPS, 2% water, 96% ethanol.
  • panels coated with solutions containing only A1289 were dried at room temperature, while panels coated with the other silane solutions were dried at 100°C for about 5-10 minutes prior to electrocoating.
  • the pH of the silane solutions was 8, unless otherwise noted.
  • UPS ⁇ -ureidopropyltrialkoxysilane
  • SAAPS N-[2-(vinylbenzylamino)-ethyl]-3-aminopropyltrimethoxysilane
  • A-1170 bis-(trimethoxysilylpropyl) amine
  • A-1289 bis-(triethoxysilylpropyl) tetrasulfide
  • both A-1289 and A-1170 provided negligible delamination on metals other than CRS.
  • the A-1289 and A-1170 solutions performed marginally better than the blank sample (i.e., alkaline-cleaned only), but significantly worse than the phosphated sample.
  • the silane solution containing a mixture of A-1289 and A-1170 performed remarkably better than either silane alone, and nearly as well as the phosphated sample.
  • Electrocoated samples prepared in the manner described in Example 2 were also tested by scribing the sample, and then immersing the scribed panels in 3% NaCl for 5 days at 60°C. Creep was then measured in the manner described above in Example 2.
  • silane coatings were applied to pure aluminum panels in the manner described in Example 2. The panels were not electrocoated. After drying, the silane coated panels were then placed into a 3% NaCl solution for 192 hours. Corrosion was evaluated qualitatively, and the results are shown below.
  • the mixture of hydrolyzed A1170 and A1289 provided excellent corrosion protection (superior to hydrolyzed A1170 alone, and at least equivalent to hydrolyzed A1289 alone).
  • the silane solutions and methods of the present invention not only provide superior adhesion to electrocoats, but also provide corrosion protection (with or without a polymer layer over the silane coating).
  • silane solutions of the present invention also provide adhesion to other types of paint systems (in addition to electrocoats).
  • Example 8
  • silane coating was applied to a panel of magnesium alloy AZ31-B in the manner described previously. It should be noted that both the silane coated panel, as well as the uncoated control, were first cleaned in a chromic acid solution in order to remove the graphite layer present on the panels.
  • the silane solution comprised a hydrolyzed mixture of 2% A-1170 and 5% A-1289. The resulting silane film was cured at 160°C for 40 minutes. The panels were not electrocoated.
  • the silane coated magnesium panel, as well as an uncoated magnesium panel were then subjected to EIS in order to evaluate corrosion protection.
  • the corrosion rate for the untreated panel was 7500 mpy, while the silane treated panel exhibited a corrosion rate of only 5 mpy.
  • the silane solutions and methods of the present invention provide corrosion protection on magnesium alloys (with or without a polymer layer over the silane coating).

Abstract

La présente invention concerne un procédé de traitement d'un substrat par application d'un revêtement à base d'une solution de silane comprenant au moins un bis-silyle aminosilane ayant été au moins partiellement hydrolysé, et au moins un bis-silyle polysulfure silane ayant été au moins partiellement hydrolysé. Le revêtement de silane confère une résistance à la corrosion ainsi qu'une meilleure adhésion sur les revêtements par électrodéposition et sur les autres polymères. L'invention concerne également des substrats revêtus de silane, ainsi qu'une solution de silane.
PCT/EP2000/003711 1999-04-14 2000-04-11 Traitements au silane pour ameliorer l'adhesion et la resistance a la corrosion WO2000063303A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU39672/00A AU3967200A (en) 1999-04-14 2000-04-11 Silane treatments for corrosion resistance and adhesion promotion
DE10084461T DE10084461T1 (de) 1999-04-14 2000-04-11 Silanbehandlungen für Korrosionsbeständigkeit und Haftvermittlung

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
GBGB9908515.1A GB9908515D0 (en) 1999-04-14 1999-04-14 Bonding rubber to metals by silanes
GB9908515.1 1999-04-14
US35692799A 1999-07-19 1999-07-19
US09/356,912 US6416869B1 (en) 1999-07-19 1999-07-19 Silane coatings for bonding rubber to metals
US09/356,927 1999-07-19
US09/356,912 1999-07-19
PCT/US1999/031324 WO2000039177A2 (fr) 1998-12-30 1999-12-30 Traitement aux silanes de metaux revetus par electrodeposition
USPCT/US99/31324 1999-12-30

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Publication Number Publication Date
WO2000063303A1 true WO2000063303A1 (fr) 2000-10-26

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WO2002080295A2 (fr) * 2001-01-19 2002-10-10 World Properties Inc. Appareil et procede destines a des composants de cellules electrochimiques
EP1415019A2 (fr) * 2001-06-28 2004-05-06 Algat Sherutey Gimur Teufati Traitement permettant de renforcer la resistance a la corrosion d'une surface a base de magnesium
US6811917B2 (en) 2000-08-14 2004-11-02 World Properties, Inc. Thermosetting composition for electrochemical cell components and methods of making thereof
WO2005035634A2 (fr) * 2003-10-08 2005-04-21 University Of Cincinnati Composition de silane et procede de liaison de caoutchouc a des metaux
US7138203B2 (en) 2001-01-19 2006-11-21 World Properties, Inc. Apparatus and method of manufacture of electrochemical cell components
US7482421B2 (en) * 2002-07-24 2009-01-27 The University Of Cincinnati Superprimer
US7972659B2 (en) 2008-03-14 2011-07-05 Ecosil Technologies Llc Method of applying silanes to metal in an oil bath containing a controlled amount of water
US8609755B2 (en) 2005-04-07 2013-12-17 Momentive Perfomance Materials Inc. Storage stable composition of partial and/or complete condensate of hydrolyzable organofunctional silane
CN107109067A (zh) * 2014-11-13 2017-08-29 美国道康宁公司 含硫聚有机硅氧烷组合物及相关方面

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WO1999067444A1 (fr) * 1998-06-24 1999-12-29 University Of Cincinnati Prevention de la corrosion de metaux au moyen de silanes de polysulfure bis-fonctionnels

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US4151157A (en) * 1977-06-28 1979-04-24 Union Carbide Corporation Polymer composite articles containing polysulfide silicon coupling agents
US4210459A (en) * 1977-06-28 1980-07-01 Union Carbide Corporation Polymer composite articles containing polysulfide silicon coupling agents
US5622782A (en) * 1993-04-27 1997-04-22 Gould Inc. Foil with adhesion promoting layer derived from silane mixture
WO1999020705A1 (fr) * 1997-10-23 1999-04-29 Aar Cornelis P J V D Collage caoutchouc sur metal par des agents de couplage renfermant un silane
WO1999067444A1 (fr) * 1998-06-24 1999-12-29 University Of Cincinnati Prevention de la corrosion de metaux au moyen de silanes de polysulfure bis-fonctionnels

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Publication number Priority date Publication date Assignee Title
US6811917B2 (en) 2000-08-14 2004-11-02 World Properties, Inc. Thermosetting composition for electrochemical cell components and methods of making thereof
WO2002080295A2 (fr) * 2001-01-19 2002-10-10 World Properties Inc. Appareil et procede destines a des composants de cellules electrochimiques
WO2002080295A3 (fr) * 2001-01-19 2004-08-05 World Properties Inc Appareil et procede destines a des composants de cellules electrochimiques
US7138203B2 (en) 2001-01-19 2006-11-21 World Properties, Inc. Apparatus and method of manufacture of electrochemical cell components
EP1415019A2 (fr) * 2001-06-28 2004-05-06 Algat Sherutey Gimur Teufati Traitement permettant de renforcer la resistance a la corrosion d'une surface a base de magnesium
EP1415019A4 (fr) * 2001-06-28 2006-12-20 Alonim Holding Agricultural Co Traitement permettant de renforcer la resistance a la corrosion d'une surface a base de magnesium
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US7482421B2 (en) * 2002-07-24 2009-01-27 The University Of Cincinnati Superprimer
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WO2005035634A3 (fr) * 2003-10-08 2005-12-29 Univ Cincinnati Composition de silane et procede de liaison de caoutchouc a des metaux
WO2005035634A2 (fr) * 2003-10-08 2005-04-21 University Of Cincinnati Composition de silane et procede de liaison de caoutchouc a des metaux
US8609755B2 (en) 2005-04-07 2013-12-17 Momentive Perfomance Materials Inc. Storage stable composition of partial and/or complete condensate of hydrolyzable organofunctional silane
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US7972659B2 (en) 2008-03-14 2011-07-05 Ecosil Technologies Llc Method of applying silanes to metal in an oil bath containing a controlled amount of water
CN107109067A (zh) * 2014-11-13 2017-08-29 美国道康宁公司 含硫聚有机硅氧烷组合物及相关方面
EP3218424A4 (fr) * 2014-11-13 2018-12-19 Dow Silicones Corporation Compositions de polyorganosiloxane contenant du soufre et aspects connexes
CN107109067B (zh) * 2014-11-13 2021-04-13 美国陶氏有机硅公司 含硫聚有机硅氧烷组合物及相关方面

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