WO2000039356A1 - Silane coatings for bonding rubber to metals - Google Patents
Silane coatings for bonding rubber to metals Download PDFInfo
- Publication number
- WO2000039356A1 WO2000039356A1 PCT/US1999/031209 US9931209W WO0039356A1 WO 2000039356 A1 WO2000039356 A1 WO 2000039356A1 US 9931209 W US9931209 W US 9931209W WO 0039356 A1 WO0039356 A1 WO 0039356A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- silane
- bis
- group
- substituted
- silyl
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
- C08J5/124—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives using adhesives based on a macromolecular component
-
- 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
- B05D7/16—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 using synthetic lacquers or varnishes
-
- 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
-
- 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
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2321/00—Characterised by the use of unspecified rubbers
-
- 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 for metals. More particularly, the present invention provides silane coatings which not only provide improved adhesion to rubber and other polymers, but also provide corrosion protection (with or without a polymer layer).
- 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.
- Solvent-based adhesive systems are used in other applications for bonding metals to sulfur-cured rubbers. Although the performance of the various methods currently employed is adequate, they still suffer from several drawbacks. 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 metal 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.
- a method of treating a metal substrate comprising:
- silane composition comprising at least one substantially unhydrolyzed aminosilane which has one or more secondary or tertiary amino groups.
- Suitable aminosilanes include:
- -n is either 1 or 2;
- each R 1 is individually chosen from the group consisting of: C, - C 24 alkyl and C 2
- 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:
- 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
- -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: £>/ ' s-(trimethoxysilylpropyl)amine, bis-
- 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.
- 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.
- -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);
- 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 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.
- 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).
- the -OR 1 groups in the bis-silyl aminosilane(s) and the bis-silyl polysulfur silane(s) are replaced by hydroxyl groups.
- 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) may be used, if needed, to raise the pH of the silane solution.
- 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, however, are stable for at least up to 30 days, and therefore need not be used immediately after mixing.
- 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 0% silanes by volume.
- 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.
- 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. While heated drying (or curing) promotes crosslinking, too much crosslinking in the silane coating may prevent sufficient adhesion between a rubber and the metal substrate. Of course the amount of crosslinking can be tailored to suit one's particular needs (such as the desired bond strength between the metal substrate and rubber), and 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 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.
- these bis-silyl aminosilanes have the general structure:
- each R 1 is chosen from the group consisting of: C, - C 24 alkyl (preferably d - 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, in the hydrolyzed silane solutions of the present invention, at least a portion (and preferably all or substantially all) of the R 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 1 - 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, - 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:
- each Q is individually chosen from the group consisting of: C-, - C 6 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, - 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").
- 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.
- 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, 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 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.
- R 1 is as defined previously
- each R 2 is as described previously
- 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, - C 10 alkenylene substituted with one or more amino groups, arylene, and alkylarylene.
- R 3 and R 5 should not all be hydrogen (else the aminosilane will have no secondary or tertiary aminosilane groups).
- 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
- unhydrolyzed secondary or tertiary aminosilane(s) will provide a durable, corrosion-preventing film
- organofunctional silanes such as bis- silyl polysulfur silanes
- organofunctional silane simply means a silane having one or more trisubstituted silyl groups, and one or more organofunctional groups.
- 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 (such as about 10 to about 60 minutes). It should be noted, however, that 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.).
- 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 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.
- A-1170 bis-(trimethoxysilylpropyl) amine
- the unhydrolyzed A1170/A1289 mixture provided excellent adhesion to all three rubber formulations (with or without the cobalt adhesion promoter).
- 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).
- silane mixture had aged for one week
- 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.
- 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.
- the silane coated panels were then placed into a 3% NaCI 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.
- Example 14 In order to examine the corrosion protection provided by the silane compositions of the present invention on magnesium alloys, a 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).
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Metallurgy (AREA)
- Medicinal Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Electrochemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19983867T DE19983867T1 (en) | 1998-12-30 | 1999-12-30 | Silane coatings for binding rubber to metals |
EP99968980A EP1157146B1 (en) | 1998-12-30 | 1999-12-30 | Silane coatings for bonding rubber to metals |
AU27168/00A AU2716800A (en) | 1998-12-30 | 1999-12-30 | Silane coatings for bonding rubber to metals |
DE69912322T DE69912322T2 (en) | 1998-12-30 | 1999-12-30 | SILANE COATINGS FOR BINDING RUBBER TO METALS |
AT99968980T ATE252653T1 (en) | 1998-12-30 | 1999-12-30 | SILANE COATINGS FOR BONDING RUBBER TO METALS |
PCT/EP2000/003709 WO2000063462A1 (en) | 1999-04-14 | 2000-04-11 | Silane coatings for adhesion promotion |
AU45562/00A AU4556200A (en) | 1999-04-14 | 2000-04-11 | Silane coatings for adhesion promotion |
Applications Claiming Priority (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US22321098A | 1998-12-30 | 1998-12-30 | |
US09/223,210 | 1998-12-30 | ||
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 | |
US09/356,927 | 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 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2000039356A1 true WO2000039356A1 (en) | 2000-07-06 |
WO2000039356A9 WO2000039356A9 (en) | 2001-08-16 |
Family
ID=27451893
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1999/031209 WO2000039356A1 (en) | 1998-12-30 | 1999-12-30 | Silane coatings for bonding rubber to metals |
PCT/US1999/031324 WO2000039177A2 (en) | 1998-12-30 | 1999-12-30 | Silane treatment for electrocoated metals |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1999/031324 WO2000039177A2 (en) | 1998-12-30 | 1999-12-30 | Silane treatment for electrocoated metals |
Country Status (6)
Country | Link |
---|---|
EP (2) | EP1333107B1 (en) |
AT (2) | ATE506465T1 (en) |
AU (1) | AU2402200A (en) |
DE (3) | DE69912322T2 (en) |
ES (1) | ES2211228T3 (en) |
WO (2) | WO2000039356A1 (en) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6416869B1 (en) * | 1999-07-19 | 2002-07-09 | University Of Cincinnati | Silane coatings for bonding rubber to metals |
FR2847913A1 (en) * | 2002-11-28 | 2004-06-04 | Electro Rech | Surface treatment of metal workpieces coated with a passivated zinc layer before coating with rubber comprises using finishing bath containing an organosilicon corrosion inhibitor and an organic adhesive compound |
US7063735B2 (en) | 2003-01-10 | 2006-06-20 | Henkel Kommanditgesellschaft Auf Aktien | Coating composition |
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 |
WO2007030532A3 (en) * | 2005-09-09 | 2007-04-26 | Univ Cincinnati | Method of applying silane coating to metal composition |
JP2007511622A (en) * | 2003-10-08 | 2007-05-10 | ユニバーシティー オブ シンシナティ | Silane composition and method for bonding rubber to metal |
US7887938B2 (en) | 2003-01-10 | 2011-02-15 | Henkel Ag & Co. Kgaa | Coating composition |
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 |
US7994249B2 (en) | 2005-09-09 | 2011-08-09 | The University Of Cincinnati | Silane coating compositions and methods of use thereof |
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 |
EP2926951A1 (en) | 2014-04-01 | 2015-10-07 | Technische Universität Kaiserslautern | Methods for simultaneously cleaning and activating component surfaces by means of a combination of carbon dioxide snow jets and the application of adhesive substances |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102008007261A1 (en) | 2007-08-28 | 2009-03-05 | Evonik Degussa Gmbh | Aqueous silane systems based on bis (trialkoxysilylalkyl) amines |
DE102007040802A1 (en) * | 2007-08-28 | 2009-03-05 | Evonik Degussa Gmbh | Composition containing low VOC aminoalkyl-functional silicon compounds for coating paper or film |
DE102009017822A1 (en) | 2009-04-20 | 2010-10-21 | Evonik Degussa Gmbh | Aqueous silane systems based on tris (alkoxysilylalkyl) amines and their use |
EP2284234B1 (en) * | 2009-07-23 | 2012-08-29 | Henkel AG & Co. KGaA | Condensable composition containing water for treating metal surfaces |
CN102482514B (en) | 2009-08-31 | 2015-09-23 | 比克化学股份有限公司 | Coating tackifier on different substrate materials surface |
DE102011084183A1 (en) | 2011-03-25 | 2012-09-27 | Evonik Degussa Gmbh | Aqueous silane-based anti-corrosive formulation |
US9273215B2 (en) | 2012-10-30 | 2016-03-01 | Rohm And Haas Electronic Materials Llc | Adhesion promoter |
JP6375304B2 (en) * | 2012-11-09 | 2018-08-15 | ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツングBASF Coatings GmbH | Method for improving paint curability of articles coated with phosphate-contaminated electrodeposition paint composition and electrodeposition paint composition |
US9153357B1 (en) * | 2014-03-27 | 2015-10-06 | Rohm And Haas Electronic Materials Llc | Adhesion promoter |
TWI688609B (en) * | 2014-11-13 | 2020-03-21 | 美商道康寧公司 | Sulfur-containing polyorganosiloxane compositions and related aspects |
EP3398998A1 (en) | 2017-05-03 | 2018-11-07 | Evonik Degussa GmbH | Aqueous brine-gel compound as storage-stable precursor for zinc-rich primers |
US11939490B2 (en) * | 2017-07-31 | 2024-03-26 | Momentive Performance Materials Inc. | Curable surface-protective coating composition, processes for its preparation and application to a metallic substrate and resulting coated metallic substrate |
WO2020160531A1 (en) * | 2019-02-01 | 2020-08-06 | Lumishield Technologies Incorporated | Methods and compositions for improved adherence of organic coatings to materials |
KR20210124994A (en) * | 2019-02-13 | 2021-10-15 | 케메탈 게엠베하 | Improved process for applying silane-based coatings on solid surfaces, particularly on metal surfaces |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
EP0435781A2 (en) * | 1989-11-21 | 1991-07-03 | Pechiney Rhenalu | Process for adhering rubber on aluminium |
EP0738748A1 (en) * | 1995-03-29 | 1996-10-23 | Compagnie Generale Des Etablissements Michelin-Michelin & Cie | Process for treating a stainless steel article to improve its adhesion to a rubber composition |
US5622782A (en) * | 1993-04-27 | 1997-04-22 | Gould Inc. | Foil with adhesion promoting layer derived from silane mixture |
WO1999020705A1 (en) * | 1997-10-23 | 1999-04-29 | Aar Cornelis P J V D | Rubber to metal bonding by silane coupling agents |
WO1999067444A1 (en) * | 1998-06-24 | 1999-12-29 | University Of Cincinnati | Corrosion prevention of metals using bis-functional polysulfur silanes |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE787691A (en) * | 1971-08-17 | 1973-02-19 | Degussa | ORGANOSILICIC COMPOUNDS CONTAINING SULFUR |
-
1999
- 1999-12-30 EP EP03006851A patent/EP1333107B1/en not_active Expired - Lifetime
- 1999-12-30 ES ES99968980T patent/ES2211228T3/en not_active Expired - Lifetime
- 1999-12-30 AU AU24022/00A patent/AU2402200A/en not_active Abandoned
- 1999-12-30 AT AT03006851T patent/ATE506465T1/en not_active IP Right Cessation
- 1999-12-30 AT AT99968980T patent/ATE252653T1/en active
- 1999-12-30 WO PCT/US1999/031209 patent/WO2000039356A1/en active IP Right Grant
- 1999-12-30 DE DE69912322T patent/DE69912322T2/en not_active Expired - Lifetime
- 1999-12-30 WO PCT/US1999/031324 patent/WO2000039177A2/en active Application Filing
- 1999-12-30 EP EP99968980A patent/EP1157146B1/en not_active Expired - Lifetime
- 1999-12-30 DE DE19983867T patent/DE19983867T1/en not_active Withdrawn
- 1999-12-30 DE DE69943383T patent/DE69943383D1/en not_active Expired - Lifetime
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
EP0435781A2 (en) * | 1989-11-21 | 1991-07-03 | Pechiney Rhenalu | Process for adhering rubber on aluminium |
US5622782A (en) * | 1993-04-27 | 1997-04-22 | Gould Inc. | Foil with adhesion promoting layer derived from silane mixture |
EP0738748A1 (en) * | 1995-03-29 | 1996-10-23 | Compagnie Generale Des Etablissements Michelin-Michelin & Cie | Process for treating a stainless steel article to improve its adhesion to a rubber composition |
WO1999020705A1 (en) * | 1997-10-23 | 1999-04-29 | Aar Cornelis P J V D | Rubber to metal bonding by silane coupling agents |
WO1999067444A1 (en) * | 1998-06-24 | 1999-12-29 | University Of Cincinnati | Corrosion prevention of metals using bis-functional polysulfur silanes |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6416869B1 (en) * | 1999-07-19 | 2002-07-09 | University Of Cincinnati | Silane coatings for bonding rubber to metals |
FR2847913A1 (en) * | 2002-11-28 | 2004-06-04 | Electro Rech | Surface treatment of metal workpieces coated with a passivated zinc layer before coating with rubber comprises using finishing bath containing an organosilicon corrosion inhibitor and an organic adhesive compound |
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 |
US7332021B2 (en) | 2003-01-10 | 2008-02-19 | Henkel Kommanditgesellschaft Auf Aktien | Coating composition |
US7063735B2 (en) | 2003-01-10 | 2006-06-20 | Henkel Kommanditgesellschaft Auf Aktien | Coating composition |
US7887938B2 (en) | 2003-01-10 | 2011-02-15 | Henkel Ag & Co. Kgaa | Coating composition |
JP2007511622A (en) * | 2003-10-08 | 2007-05-10 | ユニバーシティー オブ シンシナティ | Silane composition and method for bonding rubber to metal |
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 |
WO2007030532A3 (en) * | 2005-09-09 | 2007-04-26 | Univ Cincinnati | Method of applying silane coating to metal composition |
US7704563B2 (en) | 2005-09-09 | 2010-04-27 | The University Of Cincinnati | Method of applying silane coating to metal composition |
US7964286B2 (en) | 2005-09-09 | 2011-06-21 | University of Cinicnnati | Coating composition of oil and organofunctional silane, and tire cord coated therewith |
US7994249B2 (en) | 2005-09-09 | 2011-08-09 | The University Of Cincinnati | Silane coating compositions and methods of use thereof |
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 |
EP2926951A1 (en) | 2014-04-01 | 2015-10-07 | Technische Universität Kaiserslautern | Methods for simultaneously cleaning and activating component surfaces by means of a combination of carbon dioxide snow jets and the application of adhesive substances |
Also Published As
Publication number | Publication date |
---|---|
EP1333107B1 (en) | 2011-04-20 |
WO2000039177A2 (en) | 2000-07-06 |
AU2402200A (en) | 2000-07-31 |
EP1333107A3 (en) | 2004-01-02 |
DE69912322D1 (en) | 2003-11-27 |
WO2000039177A3 (en) | 2000-11-23 |
EP1157146B1 (en) | 2003-10-22 |
DE69943383D1 (en) | 2011-06-01 |
EP1157146A1 (en) | 2001-11-28 |
ATE252653T1 (en) | 2003-11-15 |
ATE506465T1 (en) | 2011-05-15 |
EP1333107A2 (en) | 2003-08-06 |
DE19983867T1 (en) | 2002-02-28 |
ES2211228T3 (en) | 2004-07-01 |
WO2000039356A9 (en) | 2001-08-16 |
DE69912322T2 (en) | 2004-05-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6756079B2 (en) | Silane coatings for bonding rubber to metals | |
EP1157146B1 (en) | Silane coatings for bonding rubber to metals | |
US6827981B2 (en) | Silane coatings for metal | |
AU726765B2 (en) | Method of preventing corrosion of metals using silanes | |
US6596835B1 (en) | Method of treating metals using amino silanes and multi-silyl-functional silanes in admixture | |
EP1017880B1 (en) | Method and compositions for preventing corrosion of metal substrates | |
JP3993244B2 (en) | Prevention of corrosion of metal sheet using vinylsilane | |
US6106901A (en) | Method of treating metals using ureido silanes and multi-silyl-functional silanes in admixture | |
EP1097259A1 (en) | Corrosion prevention of metals using bis-functional polysulfur silanes | |
WO2000063462A1 (en) | Silane coatings for adhesion promotion | |
WO2000063303A1 (en) | Silane treatments for corrosion resistance and adhesion promotion | |
WO2001006036A1 (en) | Acyloxy silane treatments for metals | |
MXPA99004235A (en) | Method of preventing corrosion of metal sheet using vinyl silanes |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AL AM AT AU AZ BA BB BG BR BY CA CH CN CR CU CZ DE DK DM EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GH GM KE LS MW SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
AK | Designated states |
Kind code of ref document: C2 Designated state(s): AE AL AM AT AU AZ BA BB BG BR BY CA CH CN CR CU CZ DE DK DM EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: C2 Designated state(s): GH GM KE LS MW SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG |
|
COP | Corrected version of pamphlet |
Free format text: PAGES 5, 21, 46 AND 55, DESCRIPTION, REPLACED BY NEW PAGES 5, 21, 46 AND 55; PAGE 58, CLAIMS, REPLACED BY A NEW PAGE 58; DUE TO LATE TRANSMITTAL BY THE RECEIVING OFFICE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1999968980 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 1999968980 Country of ref document: EP |
|
RET | De translation (de og part 6b) |
Ref document number: 19983867 Country of ref document: DE Date of ref document: 20020228 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 19983867 Country of ref document: DE |
|
WWG | Wipo information: grant in national office |
Ref document number: 1999968980 Country of ref document: EP |