WO2000063462A1 - Revetements de silane facilitant l'adhesion - Google Patents

Revetements de silane facilitant l'adhesion Download PDF

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Publication number
WO2000063462A1
WO2000063462A1 PCT/EP2000/003709 EP0003709W WO0063462A1 WO 2000063462 A1 WO2000063462 A1 WO 2000063462A1 EP 0003709 W EP0003709 W EP 0003709W WO 0063462 A1 WO0063462 A1 WO 0063462A1
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WIPO (PCT)
Prior art keywords
silane
bis
silyl
group
substituted
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PCT/EP2000/003709
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English (en)
Inventor
Wim J. Van Ooij
Senthil K. Jayaseelan
Eric A. Mee
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University Of Cincinnati
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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/US1999/031209 external-priority patent/WO2000039356A1/fr
Application filed by University Of Cincinnati filed Critical University Of Cincinnati
Priority to AU45562/00A priority Critical patent/AU4556200A/en
Publication of WO2000063462A1 publication Critical patent/WO2000063462A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule 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
    • 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
    • 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
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1295—Process of deposition of the inorganic material with after-treatment of the deposited inorganic material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/544—Silicon-containing compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/548—Silicon-containing compounds containing sulfur

Definitions

  • the present invention relates to silane coatings for metals, ceramics and polymers. More particularly, the present invention provides silane coatings which not only provide improved adhesion to rubber and other polymers, but also provide corrosion protection for metal substrates (with or without a polymer layer).
  • metallic coated steel sheet such as galvanized steel is used in many industries, including the automotive, construction and appliance industries.
  • the galvanized steel is painted or otherwise coated with a polymer layer to achieve a durable and aesthetically-pleasing product.
  • Galvanized steel particularly hot-dipped galvanized steel, however, often develops "white rust" during storage and shipment.
  • White rust also called “wet-storage stain” is typically caused by moisture condensation on the surface of galvanized steel which reacts with the zinc coating.
  • the wet-storage stain is black in color (“black rust”).
  • White rust (as well as black rust) is aesthetically unappealing and impairs the ability of the galvanized steel to be painted or otherwise coated with a polymer.
  • the surface of the galvanized steel must be pretreated in order to remove the white rust and prevent its reformation beneath the polymer layer.
  • Various methods are currently employed to not only prevent the formation of white rust during shipment and storage, but also to prevent the formation of white rust beneath a polymer coating (e.g., paint).
  • the surface of the steel is often passivated by forming a thin chromate film on the surface of the steel. While such chromate coatings do provide resistance to the formation of white rust, chromium is highly toxic and environmentally undesirable. It is also known to employ a phosphate conversion coating in conjunction with a chromate rinse in order to improve paint adherence and provide corrosion protection. It is believed that the chromate rinse covers the pores in the phosphate coating, thereby improving the corrosion resistance and adhesion performance. Once again, however, it is highly desirable to eliminate the use of chromate altogether. Unfortunately, however, the phosphate conversion coating is generally not very effective without the chromate rinse.
  • 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 crosslinking 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 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/or corrosion protection, that same silane coating may provide little or no adhesion to certain rubbers.
  • the silane coatings (or films) known heretofore are typically applied from an aqueous solution wherein the silane(s) are at least partially hydrolyzed.
  • the resulting silane films often contain residual water that can only be driven out by a high temperature heat treatment.
  • adhesive bonding between metal, glass and ceramic substrates and polymers, particularly rubber is also of interest.
  • many automobile components such as tire cords and vibration dampers
  • Steel tire cords for example, are typically coated with a thin layer of brass in order to promote adhesion between the underlying steel and the sulfur-cured rubber.
  • adhesion promoters such as cobalt salt additives, and HRH systems (hexamethylenetetramine, resorcinol and hydrated silica) are also used to further enhance rubber adhesion for tire cords.
  • Solvent- based adhesive systems are used in other applications for bonding metals to sulfur-cured rubbers.
  • Cobalt salts for example, are expensive and pose availability problems, while brass stimulates galvanic corrosion in conjunction with steel.
  • Solvent-based adhesives are flammable and hence hazardous.
  • silanes Although certain silanes have been found to promote adhesion between a metal substrate and a polymer layer, the results are typically system dependent. In other words, the amount of adhesion provided by a particular silane coating typically depends on the substrate as well as the polymer layer to be adhered thereto. For example, while certain silane solutions may provide improved adhesion between a metal substrate and a peroxide-cured rubber, these same silane solutions will often not provide the same results for sulfur- cured rubber. Thus, there is also a need for methods of improving the adhesion between a metal substrate and a polymer layer, particularly sulfur-cured rubber.
  • silane coatings on a metal substrates for improving corrosion resistance and/or polymer adhesion.
  • silane coatings which provide improved adhesion to rubber, including sulfur-cured and peroxide-cured rubber.
  • silane coatings which provide improved adhesion of polymers to glass and ceramics.
  • One aspect of the present invention provides a method of treating a substrate, comprising: (a) providing a substrate; and
  • Suitable aminosilanes include:
  • each R 2 is individually chosen from the group consisting of: substituted aliphatic groups, unsubstituted aliphatic groups, substituted aromatic groups, and unsubstituted aromatic groups;
  • R 5 is chosen from the group consisting of: hydrogen, C-, - C 10 alkylene, C, - C 10 alkylene substituted with one or more amino groups, C 1 - C 10 alkenylene, C 1 - C 10 alkenylene substituted with one or more amino groups, arylene, and alkylarylene;
  • 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;
  • Particularly preferred aminosilanes include bis-silyl aminosilanes having two trisubstituted silyl groups, wherein the substituents are individually chosen from the group consisting of alkoxy, aryloxy and acyloxy.
  • Suitable bis-silyl aminosilanes include:
  • each R 1 is individually chosen from the group consisting of: 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;
  • R 4 is chosen from the group consisting of: substituted and unsubstituted aliphatic groups, and substituted and unsubstituted aromatic groups.
  • exemplary bis-silyl aminosilanes include: Jb s-(trimethoxysilylpropyl)amine,
  • the composition may further include at least one "other" substantially unhydrolyzed silane (i.e., an unhydrolyzed silane other than an aminosilane having at least one secondary or tertiary amino group).
  • organofunctional silanes such as at least one substantially unhydrolyzed bis-silyl polysulfur silane, may be included in order to provide improved adhesion to a polymer (such as a paint, an adhesive, a plastic or a rubber, including sulfur- cured rubber).
  • Suitable "other" silanes include bis-silyl polysulfur silanes comprising:
  • each R 1 is an alkyl or an acetyl group
  • Z is — Q — S x — Q —
  • each Q is an aliphatic or aromatic group
  • x is an integer of from 2 to 10.
  • An exemplary bis-silyl polysulfur silane is bis-(triethoxysilylpropyl) tetrasulfide.
  • one or more substantially unhydrolyzed bis- silyl aminosilanes are combined with one or more substantially unhydrolyzed bis-silyl polysulfur silanes to provide a silane composition which may be applied to a metal substrate.
  • the resultant silane coating not only provides corrosion protection (even without a polymer coating thereover), but also provides surprisingly improved adhesion to polymers such as paints, adhesives, plastics and rubbers.
  • the silane coating provides improved adhesion to sulfur-cured rubbers, as well as peroxide-cured rubbers. Uncured (or even cured) rubber compounds are simply applied directly on the silane coating, and then cured in the usual fashion (or, if already cured, the rubber is simply heated while applying pressure). Sulfur-cured and peroxide-cured rubber compounds known to those skilled in the art may be adhered to metal substrates in this manner, using standard rubber curing methods also known to those skilled in the art.
  • the above mixture of one or more bis-silyl aminosilanes and one ore more bis-silyl polysulfur silanes may also be provided as a partially or substantially hydrolyzed silane solution.
  • This hydrolyzed silane solution also provides surprising adhesion to polymers, particularly sulfur-cured and peroxide- cured rubbers.
  • silane (t methoxysilylpropyl) amine) provides corrosion protection.
  • mixtures of at least one aminosilane and at least one bis-silyl polysulfur silane provide further improvements in both corrosion protection and polymer adhesion (particularly to sulfur-cured rubber).
  • the silanes do not have to be hydrolyzed, as previously believed, since these silane mixtures provide corrosion protection and enhanced polymer adhesion whether hydrolyzed or unhydrolyzed.
  • one or more unhydrolyzed aminosilanes may even be applied to a metal substrate alone (with or without the addition of other silanes), since applicants have found that silane coatings applied in this manner will form a dry film which provides corrosion protection.
  • the solutions and methods of the present invention may be used on a variety of substrates including ceramics, glass and metals.
  • metals include (but are not limited to): zinc and zinc alloys, such as titanium-zinc (zinc which has a very small amount of titanium added thereto), zinc-nickel alloy (typically about 5% to about 13% nickel content), and zinc-cobalt alloy (typically about 1 % cobalt); metal substrates having a zinc-containing coating, such as galvanized steel (especially hot dipped galvanized steel (“HDG”) and electrogalvanized steel
  • GES GALVALUME
  • GALFAN® a 5%-AI/95%-Zn alloy coated sheet steel manufactured and sold by Weirton Steel Corp., of Weirton, WV
  • galvanneal annealed hot dipped galvanized steel
  • -steel such as cold rolled steel, carbon steel, hot rolled steel and stainless steel, including steel which has been sandblasted; -aluminum and aluminum alloys; -copper and copper alloys, such as brass; -magnesium alloys; and
  • Suitable polymer coatings include rubbers, adhesives plastics and paints.
  • 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.
  • 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
  • the silane solutions and mixtures of the present invention may be applied to the metal prior to shipment to the end-user, and provide corrosion protection during shipment and storage.
  • the coated metal may be used as is, or, more preferably the end user may apply a polymer layer (such as paint, rubber, or adhesive) directly on top of the silane coating in the usual manner.
  • the silane coatings of the present invention not only provide excellent corrosion protection, but also provide superior adhesion between the metal substrate and the polymer layer. These silane coatings (or films) are also very durable and highly deformable, and therefore provide significant corrosion protection even after deep drawing of the coated metal.
  • the methods and compositions of the present invention are particularly useful for bonding metals to rubber, including sulfur-cured rubber.
  • the present invention provides improved adhesion between metals and sulfur-cured rubber without the need for cobalt adhesion promoters in the rubber composition.
  • the metal substrate can even be sandblasted prior to applying the silane solutions and mixtures 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 silane compositions of the present invention comprise one or more 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 may be substantially unhydrolyzed, partially hydrolyzed, or substantially fully hydrolyzed.
  • the term “substantially unhydrolyzed” simply means that the silane(s) are applied either in a pure state (no added solvents) or from a solution which does not include water. However, it is recognized that such silane(s) may absorb some water from the atmosphere, hence the term “substantially unhydrolyzed” (water is not purposefully added to the silane(s)).
  • the silane solutions of the present invention may also comprise one or more substantially unhydrolyzed aminosilanes having at least one secondary or tertiary amino group, with or without additional silanes or non-aqueous solvents.
  • Applicants have found that these unhydrolyzed aminosilanes will dry to a hard film at room temperature (typically in 30 minutes or less.
  • the silane coating applied from one or more unhydrolyzed aminosilanes will readily crosslink, and will even crosslink other silanes which are included in the coating. This finding is quite surprising, since conventional wisdom suggests that silanes should only be applied to metals in a hydrolyzed state (i.e., from a solution which includes water).
  • the hydrolyzed silane solutions of the present invention preferably comprise one or more bis-silyl aminosilanes and one or more bis-silyl polysulfur silanes.
  • These hydrolyzed silane solutions also preferably include water (for hydrolysis), and one or more compatible solvents (such as ethanol, methanol, propanol or isopropanol) in order to solubilize the polysulfur silane.
  • compatible solvents such as ethanol, methanol, propanol or isopropanol
  • the amount of solvent employed will depend upon the concentration of polysulfur silane(s) in the solution, and the solution should therefore include sufficient solvent to solubilize the polysulfur silane(s).
  • the ratio of water to solvent in the silane solution may be between about
  • the two silanes bis-silyl aminosilane and bis-silyl polysulfur silane are hydrolyzed separately before being mixed with one another to form the silane solution which is applied to the metal substrate.
  • one or more bis-silyl aminosilanes may be hydrolyzed by mixing the silane(s) with water at the desired concentration.
  • a compatible solvent such as an alcohol
  • hydrolysis of the bis-silyl aminosilane will generally proceed to completion without an added solvent (and the resulting hydrolyzed silane solution will remain stable).
  • One or more bis-silyl polysulfur silanes may be hydrolyzed in a similar fashion, however a compatible solvent should be included since these silanes are generally not water-soluble.
  • hydrolysis of the bis-silyl polysulfur silane(s) may take place in a solution having a water to solvent ratio (by volume) of between about 1:99 and about 99:1 , more preferably between about 1 :1 and about 1 :20.
  • the hydrolyzed 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.
  • An 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 Once the emulsion of polysulfur silane has been prepared, it may simply be mixed with one or more hydrolyzed bis-silyl aminosilanes as described below and then applied to the metal substrate.
  • the pH may be maintained below about 10, more preferably between about 4 and about 9 (particularly for hydrolysis of the bis-silyl aminosilane).
  • the pH ranges preferred during solution preparation should not be confused with the application pH (i.e., the pH of the silane solution applied to the metal substrate).
  • the pH may be adjusted, for example, by the addition of one or more compatible acids, preferably organic acids such as acetic, formic, propionic or iso-propionic.
  • Sodium hydroxide or other compatible base
  • Some silanes provide an acidic pH when mixed with water alone, and for these silanes pH adjustment may not be needed to accelerate silane hydrolysis.
  • the individual silane solutions are preferably stirred for at least 24 hours to ensure complete hydrolysis. In the case of the solution of bis-silyl polysulfur silane(s), hydrolysis may be allowed to proceed for several days (such as 3-4 days, or more) for optimal performance.
  • Once the individual silane solutions have been separately hydrolyzed they are mixed with one another prior to application on the metal substrate.
  • the hydrolyzed silane mixtures are stable for at least up to 30 days, and therefore need not be used immediately after mixing.
  • 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., aminosilanes, 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 silane concentration in each may vary significantly from the desired total silane concentration in the mixed silane solution (i.e., the solution which is applied to the metal substrate). It is preferred, however, that the silane concentration in the individual hydrolyzed solutions is approximately the same as the desired total silane concentration in the mixed silane solution in order to simplify the final mixing step. In this manner, the final mixed silane solution may be prepared simply by mixing the appropriate ratio of the individual silane solutions.
  • the concentration of hydrolyzed silanes in the final, mixed silane solution beneficial results will be obtained over a wide range of silane concentrations and ratios. It is preferred, however, that the hydrolyzed solution have at least about 0.1 % silanes by volume, wherein this concentration refers to the total concentration of bis-silyl aminosilane(s) and bis-silyl polysulfur silane(s) in the solution. More preferably, the solution has between about 0.1 % and about 10% silanes by volume.
  • the ratio of bis-silyl aminosilane(s) to bis-silyl polysulfur silane(s) in the hydrolyzed silane solution a wide range of silane ratios provide beneficial results.
  • the ratio of bis-silyl aminosilane(s) to bis-silyl polysulfur silane(s) is between about 1:99 and about 99:1. More preferably, particularly when the hydrolyzed silane solution is to be used for rubber bonding, this ratio is between about 1:10 and about 10:1. Even more preferably, this ratio is between about 1 :3 and about 3:1.
  • 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 application pH is preferably between about 4 and about 7, most preferably between about 4 and about 5.
  • the pH of the mixed silane solution may be adjusted in the manner described previously.
  • 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 mixed hydrolyzed silane 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.
  • the hydrolyzed silane solution (prepared in the manner described above) is 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 the solution onto the surface of the metal or 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
  • the metal substrate may simply be air-dried at room temperature. Heated drying is not preferred if the hydrolyzed silane coating is to be used for improving rubber adhesion, since it is preferred that the coating remain only partially crosslinked.
  • the present invention is therefore not limited to silane coatings dried only at room temperature. Once dried, the treated metal may be shipped to an end-user, or even stored for later use.
  • the coatings applied from hydrolyzed silane solutions of the present invention provide significant corrosion resistance during both shipping and storage. More importantly, this silane coating need not be removed prior to application of a polymer layer on top of the silane coating. Thus, the end-user, such as an automotive manufacturer, may apply a polymer (such as a paint, an adhesive or rubber) directly on top of the silane coating without additional treatment (such as the application of chromates or the use of solvent-based adhesives).
  • the hydrolyzed silane coatings of the present invention not only provide a surprisingly high degree of adhesion to the polymer layer, but also prevent delamination and underpaint corrosion even if a portion of the base metal is exposed to the atmosphere. As reported in Application Serial No.
  • the hydrolyzed silane solutions of the present invention having both a bis-silyl aminosilane and a bis- silyl polysulfur silane also provide excellent adhesion to paints (particularly electrocoats) and other polymeric adhesives.
  • the hydrolyzed silane solutions of the present application also provide improved corrosion protection, as well as adhesion to other non-rubber polymers (such as paints and adhesives).
  • the hydrolyzed silane coatings of the present invention are particularly useful for bonding rubber to various metal substrates, particularly sulfur-cured rubbers such as natural rubber ("NR"), NBR, SBR and EPDM compounds.
  • NR natural rubber
  • the uncured rubber compound is merely applied directly on top of the silane coating, and is then cured in the typical fashion (i.e., using the cure conditions required for the particular rubber compound employed).
  • Even previously cured rubber may be adhered to the metals using the silane coatings of the present invention simply by applying the cured rubber compound directly on top of the silane coating and thereafter applying sufficient heat and pressure to adhere the rubber to silane coating (and hence to the metal substrate).
  • the silane coatings provided by the hydrolyzed silane solutions of the present invention provide improved rubber adhesion, as well as significant corrosion protection.
  • An added benefit of the improved adhesion provided by the hydrolyzed silane coatings of the present invention is that the sulfur-cured rubbers may be formulated without cobalt adhesion promoters, since the silane coatings of the present invention improve rubber adhesion without such promoters.
  • the hydrolyzed silane coatings of the present invention also provide corrosion protection and bonding to polymers other than rubber (such as paint), the present invention has the added benefit of providing silane solutions and methods which may be used in a myriad of applications. Thus, manufacturers need not use one silane solution for corrosion protection, another for paint adhesion, yet another for adhesion to peroxide-cured rubber, and still another for adhesion to sulfur-cured rubber.
  • the hydrolyzed silane solutions of the present invention are suitable for all of these applications on a variety of metals.
  • 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 alkoxy, aryloxy and acyloxy.
  • each R 1 is chosen from the group consisting of: C 1 - C 24 alkyl (preferably C, - C 6 alkyl), and C 2 - C 24 acyl (preferably C 2 -C 4 acyl).
  • Each R may be the same or different, however, in the hydrolyzed silane solutions of the present invention, at least a portion (and preferably all or substantially all) of the R 1 groups are replaced by a hydrogen atom.
  • each R 1 is individually chosen from the group consisting of: 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 is chosen from the group consisting of: C, - C 10 alkylene, C 1 - C 10 alkenylene, arylene, and alkylarylene. More preferably, R 4 is a C, - C 10 alkylene (particularly ethylene).
  • Exemplary preferred bis-silyl aminosilanes which may be used in the present invention include: Jb/s-(trimethoxysilylpropyl)amine (which is sold under the tradename A-
  • the preferred bis-silyl polysulfur silanes which may be employed in the present invention include:
  • each R 1 is as described before.
  • at least a portion (and preferably all or substantially all) of the 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 6 alkyl (linear or branched), C, - C 6 alkenyl
  • Particularly preferred bis-silyl polysulfur silanes include bis-
  • 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").
  • TESPT bis-(triethoxysilylpropyl) tetrasulfide
  • Commercially-available forms of TESPT such as A-1289, available from Witco
  • 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 hydrolyzed silane solutions containing mixtures of bis-silyl polysulfur silanes in combination with one or more bis-silyl aminosilanes. Coatings Applied from Unhydrolyzed Silanes
  • unhydrolyzed silanes may be applied directly onto the metal substrate in order to not only provide corrosion protection, but also to provide improved adhesion to polymer layers (such as paints, adhesives, plastics or rubbers).
  • at least one aminosilane having at least one secondary or tertiary amino group is applied to the metal substrate in a substantially unhydrolyzed state (i.e., the R 1 groups are not replaced by a hydrogen atom).
  • One or more additional silanes organofunctional or non- organofunctional may also be mixed with the aminosilane, however even an unhydrolyzed aminosilane by itself provides corrosion protection.
  • aminosilanes which may be applied to a metal substrate in an unhydrolyzed state include aminosilanes having at least one secondary or tertiary amino group.
  • Suitable unhydrolyzed aminosilanes include:
  • n is either 1 or 2.
  • n is either 1 or 2.
  • R 2 is as described previously, and X is as described previously.
  • R 5 may be hydrogen, C, - C 10 alkylene, C - C 10 alkylene substituted with one or more amino groups, C, - C 10 alkenylene, C 1 - C 10 alkenylene substituted with one or more amino groups, arylene, and alkylarylene.
  • Suitable diaminosilanes include those silanes having at least one trialkoxysilyl or triacetoxysilyl group, as well as two amino groups, at least one of which is a secondary amino group.
  • Suitable diamino silanes include
  • SAAPS 2-(vinylbenzylamino)ethyl]-3-aminopropyltrimethoxy
  • AEPS aminoethyl-aminopropyltrimethoxy silane
  • bis- (triethoxysilylpropyl)ethylene diamine a bis-silyl, diamino silane
  • the unhydrolyzed secondary or tertiary aminosilane(s) may also be combined with one or more additional unhydrolyzed silanes, particularly organofunctional silanes, prior to application to the metal substrate. In this fashion, one can tailor the silane coating to the particular application. While one or more unhydrolyzed secondary or tertiary aminosilane(s) will provide a durable, corrosion-preventing film, applicants have found that the addition of one or more other unhydrolyzed silanes (particularly organofunctional silanes, such as bis-silyl polysulfur silanes), will not only provide corrosion resistance but also polymer adhesion. "Organofunctional silane” simply means a silane having one or more trisubstituted silyl groups, and one or more organofunctional groups.
  • One preferred embodiment of the present invention comprises a mixture of one or more aminosilanes having at least one secondary or tertiary amino group (especially the bis-silyl aminosilanes described previously) and one or more bis-silyl polysulfur silanes (as described above), with the silanes in a substantially unhydrolyzed state.
  • the silane(s) may be applied to the metal substrate as a pure silane mixture (i.e., no solvents or water), or may be diluted with a compatible solvent (other than water).
  • Suitable solvents for example, include, ethanol, methanol, propanol and isopropanol. Diluting the unhydrolyzed silane(s) with a compatible solvent allows the thickness of the silane to be controlled.
  • the unhydrolyzed silane(s) are simply coated onto the metal substrate, such as by wiping, dipping or spraying the silane (or silane mixture) onto the metal. Thereafter, the silane coating is dried. If the unhydrolyzed silane mixture applied to the metal substrate contains only aminosilanes, the coating is preferably dried at room temperature. Alternatively, the aminosilane coating may be dried by heating to a temperature of between about 100° and about 250° for a period of time sufficient to form a dry film (i.e., silane coating).
  • the silane coating is preferably dried by heating the coated metal to a temperature of between about 100°C and about 250°C (more preferably to a temperature of between about 100°C and about 160°C, for a period of time sufficient to form a dry film
  • the amount of drying time will obviously vary with the drying temperature, as well as the nature of the silane coating (e.g., silane concentrations, amount of organic solvent, etc.). Thus, longer periods of time than that specified may be used.
  • the unhydrolyzed silanes will become partially crosslinked, thereby forming a semi-crosslinked silane coating which not only provides significant corrosion protection, but also improved adhesion to polymers such as paints, adhesives and rubbers (particularly sulfur-cured rubbers).
  • the silane coated metal should merely be dried for a period of time sufficient to form a dry film (i.e., so that the silane film is semi-crosslinked).
  • the silane film may be fully crosslinked (or cured) simply by heating the silane coated metal substrate for a longer period of time and/or at a higher temperature. While a fully crosslinked silane film is not desired for polymer adhesion, it will provide significant corrosion protection.
  • the unhydrolyzed silane mixtures of the present invention are prepared simply by mixing the silanes with one another in their pure, unhydrolyzed state in the desired ratio.
  • the resulting silane mixture may be diluted with a compatible solvent, if desired. If a solvent is used, the total silane concentration should be at least about 10% (by volume), more preferably at least about 25%.
  • a wide range of silane ratios provide beneficial results.
  • the ratio of aminosilane(s) to other silanes is between about 1 :10 and about 10:1. More preferably, particularly when the unhydrolyzed silane mixture is to be used for rubber bonding, this ratio is between about 1 :3 and about 1 :1.
  • unhydrolyzed silane compositions having at least one secondary or tertiary aminosilane provide a silane coating which is highly resistant to corrosion.
  • the silane compositions include one or more organofunctional silanes (particularly at least one bis-silyl polysulfur silane), the resultant silane coating provides superior adhesion to polymers (such as paints, adhesives and rubbers). In fact, the adhesion to sulfur-cured rubbers is even greater than that provided by the hydrolyzed silane solutions of the present invention.
  • the unhydrolyzed silane compositions of the present invention provide unexpectedly high levels of adhesion to a variety of rubber compositions, including sulfur-cured rubber such as high-sulfur rubber systems, low-sulfur rubber systems, EV rubber systems, and semi-EV rubber systems.
  • the unhydrolyzed silane compositions of the present invention also provide superior adhesion to other polymer layers, such as various types of paints.
  • 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 corrosion protection or rubber adhesion.
  • the coatings provided by the unhydrolyzed silane compositions of the present invention are also highly stable. Therefore, a polymer layer may be applied long after the silane coating is established on the metal substrate, and the silane coated metal (without a polymer layer) may be exposed to the environment without significant deleterious effect.
  • silane coatings provided by the unhydrolyzed silane compositions of the present invention provide a high level of corrosion protection even without a polymer layer thereon, and will still provide improved polymer adhesion even after a lengthy exposure to the environment.
  • 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 hydrolyzed separately in a solution of water and solvent, and the hydrolyzed silane solutions were then mixed to form the final silane solution composition indicated.
  • the individual silane solutions were hydrolyzed for at least 24 hours prior to application.
  • the metal substrates were solvent-cleaned, alkaline-cleaned, water rinsed, dried, dipped into the silane solution for approximately 1 minute, and then dried at room temperature.
  • a 5% A1170 solution was prepared by mixing 5% A1170, 5% water and 90% ethanol (by volume). The pH was adjusted to the indicated amount by adding acetic acid as needed. The silane solution was stirred for at least 24 hours in order to complete hydrolysis.
  • the silanes were separately hydrolyzed in the same manner (5% silane, 5% water and 90% alcohol). After at least 24 hours of hydrolysis, the two silane solutions were mixed together to provide the indicated ratio of A1170:A1289, with the total silane concentration in the mixed silane solutions being 5% in all cases.
  • CRS panels were ultrasonically cleaned in acetone, hexane and methanol. The panels were then alkaline cleaned in the usual manner, rinsed in deionized water, and blow-dried with hot air. The panels were then dipped into the silane solution for 30-45 seconds, and thereafter dried.
  • a layer of the specified uncured rubber composition was sandwiched between two silane coated panels. One half of each metal panel was shielded from the rubber by a Mylar film in order to prevent bonding in that region.
  • the composite article was then cured in a hydraulic press at 160°C (8 minutes for Rubber Compound 1 , 11 minutes for Rubber Compound 2, and 5 minutes for
  • A-1170 bis-(trimethoxysilylpropyl) amine
  • A-1289 bis-(triethoxysilylpropyl) tetrasulfide
  • mixtures of hydrolyzed A1170 and A1289 provided adhesion which was surprisingly superior to that provided by either silane alone.
  • a hydrolyzed solution of A1170 provided no adhesion at all, yet even a small addition of A1170 to a hydrolyzed solution of A1289 improves adhesion.
  • Other hydrolyzed silane solutions provided no adhesion to the sulfur-cured rubber, including the two-step BTSE / VS treatment which has previously been shown to provide excellent adhesion to peroxide- cured rubbers.
  • silane coatings were applied from pure silanes (either pure A1170, or a mixture consisting only of A1170 and A1289 in the indicated ratio). After the silanes were mixed with one another, the resultant silane mixture was wiped onto the metal (which had been cleaned in the manner described previously) using a paper towel. Unless otherwise noted, the silane coating applied in this manner was then dried for one hour at 150°C. Thereafter, the rubber composition was bonded to the silane coated metal in the manner described previously.
  • the silane mixtures of the present invention allows for the elimination of the cobalt adhesion promoter, while also providing improved corrosion protection.
  • the unhydrolyzed silane mixtures of the present invention provide excellent rubber adhesion on a variety of brass alloys, including Alloy 360 brass (which will not adhere to sulfur-cured rubber).
  • Example 7 (such as paint), it also provides excellent corrosion protection (even without a polymer layer on top of the silane coating).
  • silane mixture had aged for 2 days * silane mixture had aged for one week Example 8
  • NedZinc a zinc-titanium alloy
  • the cured rubber compositions were applied to silane coated panels, and then cured by standard curing conditions. Rubber adhesion was tested according to ISO 813 (equivalent to ASTM D429B), and was reported qualitatively. The panels were tested immediately after curing, and after the specified exposure time in water at 100°C.
  • EPDM 3 and NBR 2 were standard peroxide-cured EPDM and NBR rubbers, respectively.
  • the unhydrolyzed silane mixtures of the present invention may be applied as pure silanes (i.e., no solvents), or with significant quantities of non-aqueous solvents (such as ethanol or methanol).
  • silane coatings were applied to pure aluminum panels.
  • the hydrolyzed silane solutions were prepared and applied in the manner described in Example 1
  • the unhydrolyzed silanes were prepared and applied as described in Example 4.
  • 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 unhydrolyzed silanes also provided excellent corrosion prevention.
  • the silane solutions and methods of the present invention not only provide superior polymer adhesion, but also provide corrosion protection (with or without a polymer layer over the silane coating).
  • the corrosion protection provided by the methods of the present invention on CRS and EGS was also measured quantitatively by conducting standard electrochemical polarization tests. The results of these tests are shown below, wherein the rate of corrosion is reported in millimeters per year.
  • 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 an unhydrolyzed 1 :1 mixture of A-1170 and A-1289. The resulting silane film was dried at room temperature for 24 hours.
  • the silane coated magnesium panel, as well as an uncoated magnesium panel were then subjected to two hours of neutral salt spray testing in order to evaluate corrosion protection.
  • the untreated panel showed an enormous amount of pitting, as well as uniform and galvanic corrosion.
  • the silane treated panel exhibited no galvanic corrosion, nad much less pitting and uniform corrosion than the untreated panel.
  • 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

L'invention concerne un procédé de traitement d'un substrat consistant à appliquer un revêtement d'une composition de silane présentant au moins une aminosilane sensiblement non hydrolysée comportant un ou plusieurs groupes aminés secondaires ou tertiaires. L'invention a aussi pour objet des procédés favorisant l'adhésion d'un polymère (comme du caoutchouc) à un substrat.
PCT/EP2000/003709 1999-04-14 2000-04-11 Revetements de silane facilitant l'adhesion WO2000063462A1 (fr)

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GB9908515.1 1999-04-14
GBGB9908515.1A GB9908515D0 (en) 1999-04-14 1999-04-14 Bonding rubber to metals by silanes
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
US09/356,912 1999-07-19
US09/356,927 1999-07-19
USPCT/US99/31209 1999-12-30
PCT/US1999/031209 WO2000039356A1 (fr) 1998-12-30 1999-12-30 Revetements de silane pour lier le caoutchouc aux metaux

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WO2004012874A1 (fr) 2002-08-02 2004-02-12 The Government Of The United States Of America, Represented By The Secretary, Dept. Of Health And Human Services Substrats reticules enduits de polyamine a liberation d'oxyde nitrique, compositions contenant ces substance s et methode de production associee
EP1263889B1 (fr) * 2000-03-03 2005-05-04 Dow Corning Corporation Revetements isolants comprenant des bis-silanes
US7201944B2 (en) 2002-12-18 2007-04-10 Bridgestone Firestone North American Tire, Llc Rubber compositions and articles thereof having improved metal adhesion and metal adhesion retention with bright steel
US7928079B2 (en) 2005-10-31 2011-04-19 The United States Of America, As Represented By The Secretary, Department Of Health And Human Services Polysaccharide-derived nitric oxide-releasing carbon-bound diazeniumdiolates
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
US8029906B2 (en) * 2003-10-08 2011-10-04 University Of Cincinnati Silane compositions and methods for bonding rubber to metals
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
US20140134321A1 (en) * 2009-10-13 2014-05-15 The University Of North Carolina At Chapel Hill Nitric oxide-releasing coatings
US9540471B2 (en) 2012-07-17 2017-01-10 The United States Of America, As Represented By The Secretary, Department Of Health And Human Services Nitric oxide-releasing diazeniumdiolated polyvinylpyrrolidone-based polymers, and compositions, medical devices, and uses thereof
US9713652B2 (en) 2011-02-28 2017-07-25 The University Of North Carolina At Chapel Hill Nitric oxide-releasing S-nitrosothiol-modified silica particles and methods of making the same
CN114032486A (zh) * 2021-11-11 2022-02-11 北京星航机电装备有限公司 一种复合结构热防护涂层及其制备方法

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1263889B1 (fr) * 2000-03-03 2005-05-04 Dow Corning Corporation Revetements isolants comprenant des bis-silanes
WO2004012874A1 (fr) 2002-08-02 2004-02-12 The Government Of The United States Of America, Represented By The Secretary, Dept. Of Health And Human Services Substrats reticules enduits de polyamine a liberation d'oxyde nitrique, compositions contenant ces substance s et methode de production associee
US7201944B2 (en) 2002-12-18 2007-04-10 Bridgestone Firestone North American Tire, Llc Rubber compositions and articles thereof having improved metal adhesion and metal adhesion retention with bright steel
US8029906B2 (en) * 2003-10-08 2011-10-04 University Of Cincinnati Silane compositions and methods for bonding rubber to metals
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
US10041176B2 (en) 2005-04-07 2018-08-07 Momentive Performance Materials Inc. No-rinse pretreatment methods and compositions
US7928079B2 (en) 2005-10-31 2011-04-19 The United States Of America, As Represented By The Secretary, Department Of Health And Human Services Polysaccharide-derived nitric oxide-releasing carbon-bound diazeniumdiolates
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
US20140134321A1 (en) * 2009-10-13 2014-05-15 The University Of North Carolina At Chapel Hill Nitric oxide-releasing coatings
US9713652B2 (en) 2011-02-28 2017-07-25 The University Of North Carolina At Chapel Hill Nitric oxide-releasing S-nitrosothiol-modified silica particles and methods of making the same
US9540471B2 (en) 2012-07-17 2017-01-10 The United States Of America, As Represented By The Secretary, Department Of Health And Human Services Nitric oxide-releasing diazeniumdiolated polyvinylpyrrolidone-based polymers, and compositions, medical devices, and uses thereof
CN114032486A (zh) * 2021-11-11 2022-02-11 北京星航机电装备有限公司 一种复合结构热防护涂层及其制备方法

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