Classifications

• • 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
  • C09D5/08—Anti-corrosive paints
• • 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
  • C09D5/08—Anti-corrosive paints
  • C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
  • C09D5/084—Inorganic compounds
• • 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
  • C09D5/08—Anti-corrosive paints
  • C09D5/10—Anti-corrosive paints containing metal dust
• • 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
  • C23C18/122—Inorganic polymers, e.g. silanes, polysilazanes, polysiloxanes
• • 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
  • C23C18/1254—Sol or sol-gel processing
• • 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
  • C23C18/1262—Process of deposition of the inorganic material involving particles, e.g. carbon nanotubes [CNT], flakes
  • C23C18/127—Preformed particles
• • 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
  • C23C22/05—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 aqueous solutions
  • C23C22/06—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 aqueous solutions using aqueous acidic solutions with pH less than 6
  • C23C22/48—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 aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
• • 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
  • C23C22/05—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 aqueous solutions
  • C23C22/06—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 aqueous solutions using aqueous acidic solutions with pH less than 6
  • C23C22/48—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 aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
  • C23C22/50—Treatment of iron or alloys based thereon
• • 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
  • C23C22/05—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 aqueous solutions
  • C23C22/68—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 aqueous solutions using aqueous solutions with pH between 6 and 8
• • 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
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31652—Of asbestos
  • Y10T428/31663—As siloxane, silicone or silane

Definitions

• the present invention relates to a new anti-corrosion formulation based on an aqueous silane system as binder, to a process for preparing it and to the use thereof for coatings, more particularly for protecting metals from corrosion.
• aqueous silane systems are not preparable simply by mixing silanes with water, since many silanes are insoluble in the aqueous phase and undergo hydrolysis and condensation on contact with water. In corrosion control, therefore, it is customary to use silane systems with organic solvents and defined amounts of water. In order to modify the properties of the silane systems and to enhance the corrosion control, they can be formulated with additives, pigments and fillers.
• U.S. Pat. No. 5,051,129 claims the composition of an aqueous solution which consists of a water-soluble aminosilane and an alkyltrialkoxysilane. It is prepared by adding a defined amount of water to the silane mixture, followed by heat treatment at 60° C. The silane mixture prepared in this way is dissolved in water, in a specific proportion, and is used to impart water repellency to surfaces.
• EP 0 716 128 claims water-based, organopolysiloxane-containing compositions, processes for preparing them and use thereof.
• Mixing water-soluble aminoalkylalkoxysilanes with alkyltrialkoxysilanes and/or dialkyldialkoxysilanes and adding water at a defined pH produces compositions containing organopolysiloxane.
• the hydrolysis alcohol formed is removed by distillation. Consequently, VOC-free, aqueous, polysiloxane-containing compositions are obtained, which can be used to impart water repellency to surfaces and mineral building materials, and for other applications.
• WO 2000/39177 describes the use of bis-silylaminosilanes and/or bis-silylpolysulphanes in aqueous solutions.
• the silanes are mixed with water, an alcohol and optionally acetic acid and hydrolysed for at least 24 hours. This is followed by application to metals.
• U.S. Pat. No. 6,955,728 describes the use of acetoxysilanes in combination with other silanes in aqueous solutions and the application to metals.
• the systems used include bis(trialkoxysilylpropyl)amines in combination with acetoxysilanes.
• the aqueous solutions always include at least the hydrolysis alcohol.
• WO 2004/076717 uses bis-silylaminosilanes in combination with other silanes and with a metal chelate in aqueous solutions.
• the silanes are subjected to partial hydrolysis by ageing for at least 2 weeks in aqueous concentrates. Then a metal chelate is added and the system is diluted further with water. Moreover, all aqueous formulations still contain the alcohol from the hydrolysis.
• the aqueous systems are used for pretreating metal surfaces.
• WO 2004/076718 relates to a method for the coating of a metallic surface using an aqueous solution which comprises a partially hydrolysed silane such as bis-silylaminosilane, for example, and a partially hydrolysed, fluorine-containing silane.
• a partially hydrolysed silane such as bis-silylaminosilane, for example
• fluorine-containing silane enhances the water repellency and the corrosion resistance of the coating system.
• the hydrolysis alcohol is not removed from the systems.
• U.S. Pat. No. 5,206,285 describes the preparation and use of water-based adducts of an epoxysilane and an aminosilane.
• the aqueous silane systems are not solvent-free. They are used for metal coating and are said to enhance the corrosion resistance.
• EP 1 760 128 claims an aqueous two-component adhesion promoter composition and also the use thereof for adhesive bonding or sealing.
• One component present in the adhesion promoter may be a bis-silylaminosilane.
• DE 10 2004 037 045 relates to aqueous silane nanocomposites prepared from glycidyloxypropylalkoxysilanes and aqueous silica sols in the presence of a catalyst.
• the aqueous systems are virtually solvent-free and are suitable for metal coatings.
• a disadvantage are the high crosslinking temperatures of 200° C.
• U.S. Pat. No. 6,468,336 describes the formulation and use of an anti-corrosion coating for steel.
• the water-based formulation comprises waterglass as binder and as pigments zinc, iron phyllosilicates, and also further fillers.
• the formulations described are said to provide excellent corrosion control in film thicknesses of 15 to 25 ⁇ m.
• EP 1 191 075 teaches a water-based two-component system for anti-corrosion coatings on steel.
• the first component comprises water, an aminoalkyltrialkoxysilane, an acid, an epoxysilane and conductive pigments.
• the second component consists of zinc powder.
• the completed mixture is said to allow a processing life of 16 hours.
• the alcohol from the hydrolysis of the silane was not removed, and the aqueous system was applied to give a dry film thickness of 25 ⁇ m.
• the coated metal sheets showed no corrosion after 7 months of outdoor weathering.
• WO 2000/46311 describes the treatment of metal substrates with a formulation comprising a ureidosilane, a multisilylsilane and a solvent.
• the silanes are first partly hydrolysed and then formulated.
• the hydrolysis alcohol is not removed, and the formulation is used without pigments.
• WO 2002/22745 claims a solvent-free anti-corrosion primer.
• the primer is composed of a stabilized silica sol, a phyllosilicate, a calcined aluminium phyllosilicate and zinc dust.
• the dry film thickness of the coating is approximately 15 to 25 ⁇ m. The abrasion resistance and the processing life were ascertained.
• WO 2003/022940 describes an anti-corrosion system consisting of an aqueous silica sol, optionally an organic resin, zinc dust and further additives.
• the systems are characterized by the abrasion resistance and the pencil hardness.
• WO 2006/079516 relates to an aqueous binder and coating material based on an aminoalkylsilane and a formylaminopropyltrialkoxysilane, respectively, and also on an epoxysilane.
• the binder is based on an aminoalkylalkoxysilane and an epoxy-functional alkoxysilane, and on a well-defined mode of preparation.
• the coating material disclosed therein was formulated on the basis of the binder with addition of pigments, including conductive pigments, and additives.
• WO 99/14277 describes an aqueous primer composition which consists of a reactive resin (dispersion), an organofunctional silane (amino- or epoxysilane; no bis-silylsilanes) and a curing reagent. Adhesive bonds on metal substrates treated with this primer exhibit very good strengths in a shearing test in combination with an epoxy resin.
• WO 2008/133916 describes a method of treating metal surfaces.
• the method involves treatment with an aqueous formulation consisting of hydrolysed/condensed silanes.
• the silanes used may be aminosilanes containing hydroxyl groups.
• the coating systems produced in this way are not solvent-free.
• the treated metal substrates were coated, and exhibit reduced scribe creep as compared with the standard treatment.
• U.S. Pat. No. 6,929,826 claims a method of surface-treating metals. The method involves treating them with a formulation comprising an epoxysilane and a tetraalkoxysilane.
• WO 2006/137663 describes a composition consisting of an aminosilane and an epoxysilane.
• the formulation further comprises a magnesium and vanadium compound and an acid. Preparation takes place in a water/alcohol mixture.
• the metal substrates treated with this formulation exhibit high corrosion resistance and effective adhesion to organic coatings.
• the systems are not solvent-free.
• WO 2009/059798 discloses a formulation and coating of a metal.
• the formulation consists of tetraethoxysilane, vinyltrimethoxysilane, phenyltriethoxysilane, and propyltrimethoxysilane. Furthermore, other components such as alcohols, catalysts, silica sols and additives are claimed.
• the coatings of the invention must be heated for curing. The formulation is said to protect metal substrates from corrosion.
• EP 0 274 428 teaches a composition which consists of an alkyltrialkoxysilane, a vinyltrialkoxysilane and/or further silanes such as an epoxysilane, of an organic solvent and of an aluminium sol.
• WO 2009/030538 teaches aqueous compositions based on bisalkoxyalkylsilylamines that are substantially free from organic solvents and that release no alcohol even on crosslinking. Furthermore, such systems may be based on other organosilanes, such as 3-glycidyloxypropyltrialkoxysilanes, and also alkylalkoxysilanes. The systems may also include fillers, such as silica, titanium dioxide and aluminium oxide, and also colour pigments. Additionally disclosed are the preparation process and the use—including use as an anti-corrosion coating.
• silanes and aqueous silane systems are able to develop a coating on numerous substrates. These coatings are unable to develop active corrosion control, instead being able only to develop a passive corrosion coat, and may also act as binder and/or crosslinker in coating compositions. Accordingly, binders may also be seen as crosslinkers. Active corrosion control can be achieved by means of corrosion inhibitors. In order to allow such formulations, more particularly eco-friendly aqueous formulations, to be produced, the binder and the anti-corrosion additions must be compatible, in order to provide an extremely stable and effective formulation which can be processed in a reasonable time frame on the industrial scale.
• An object of the present invention accordingly, was to provide a further aqueous and largely VOC-free anti-corrosion composition based on so-called bis-aminosilane cocondensates as binders, this composition being substantially compatible with particulate additions and also, optionally, further additives, and being storage-stable as such at least for several hours to weeks before application.
• a particular concern furthermore, was that such formulations can be cured at room temperature and achieve effective adhesion and corrosion control on metal substrates.
• Another desideratum is that anti-corrosion coatings obtainable on this basis can be applied in different film thicknesses and are readily repaintable after curing, in other words exhibiting effective adhesion to coatings, more particularly to organic (paint) coatings.
• compositions preferably at room temperature, more preferably at 16 to 26° C., more particularly at 20° C., and, with additions from the group consisting of particulate metals, metal alloys and/or metal compounds, including metal oxides or metal salts, and also, optionally, further additives, are advantageously compatible, storage-stable and suitable for application.
• present compositions it is possible, furthermore, to produce advantageously thin films on metal, to which further paint coats can be applied and with which at the same time it is possible to obtain effective adhesion to the primer and/or to the metal.
• Binders are, generally speaking, liquids, which bond solids with a fine degree of division, additionally may have a crosslinking effect in a preparation, and allow adhesion to the substrate.
• the binder In order that a formulation comprising a binder and a particulate adjuvant can be produced, the binder must be compatible with the adjuvant—that is, it must wet the adjuvant. In this way the adjuvant can be dispersed in the binder, and the positive qualities of the system are obtained.
• Formulations comprising a binder and adjuvant may find broad application, for example, in corrosion control. Aqueous systems are particularly advantageous in this context, since they contain substantially no organic solvents or other environmentally hazardous substances.
• Aqueous sol-gel systems not only are eco-friendly but are also very variable and can be put to very diverse uses.
• New present binders based on aqueous sol-gel systems not only are able to cure at low temperatures, but also improve the adhesion of further coatings to these systems—that is, they have good repaintability.
• aqueous binders are very diverse. They can be employed as a basis for a variety of formulations, especially as binders in combination with particulate metals and/or with particulate metal compounds and also, optionally, with further additives. If the system is to have hydrophobic properties, then an alkyltrialkoxysilane may be used as a further component alongside the epoxy-functional alkoxysilane and the bis-amino-functional alkoxysilanes.
• organofunctional silanes or else tetraalkoxysilanes may also be used in addition to the epoxy-functional alkoxysilanes and the bis-amino-functional alkoxysilanes.
• the proportions of the silane components may advantageously be adjusted in such a way that the completely hydrolysed and condensed product is stable in the aqueous solution and nevertheless cures at low temperature on the substrate or as binder in the formulation. Not only the proportion, however, but also the sequence of the metered addition has a key influence on the product properties.
• the hydrolysis alcohol is advantageously removed from the reaction system during the preparation of the binder, allowing the provision of a largely VOC-free aqueous product.
• the active substance of the binder consists generally of completely hydrolysed and at least partially condensed or cocondensed silanes.
• the solids content of the pure epoxy-functional alkoxysilane in the aqueous sol-gel system must advantageously be up to 70% by weight, while the solids content of the pure bis-amino-functional alkoxysilane ought only to be not more than approximately 10% by weight, without becoming solid.
• the dry residue (also designated here as solids content) of the condensates or cocondensates in the binder is situated preferably in the range from 1% to 50% by weight, more preferably between 3% and 45% by weight and very preferably between 5% and 35% by weight.
• the present invention accordingly provides a composition
• a composition comprising
• R 1 and R 2 independently of one another are each a linear or branched alkyl group having 1 to 4 C atoms, and x is 0 or 1, and on at least one bis(alkoxysilylalkyl)amine of the general formula II
• the binder for the composition of the invention can be prepared advantageously by a procedure in which first of all water is introduced in a molar excess, based on the silanes of the formulae I and II and also, optionally, on the aforementioned silicon compounds used, and is adjusted to an acidic pH with addition of an organic or inorganic acid, a silica sol being added optionally,
• an ⁇ -glycidyloxyalkylalkoxysilane of the formula I is metered in and the mixture is heated, optionally further acid is metered in, and at least one bis(alkoxysilylalkyl)amine of the general formula II and also optionally at least one further silicon compound from the group consisting of tetraalkoxysilane, alkylalkoxysilane, aminoalkylalkoxysilane, ureidoalkylalkoxysilane, carboxyalkylalkoxysilane and thiocyanatoalkylalkoxysilane is metered in and the system is caused to react, subsequently the resultant hydrolysis alcohol is removed at least proportionately from the reaction mixture under reduced pressure, the binder thus obtained is optionally diluted with water and/or an aqueous acid and is subsequently filtered, the dry residue of the binder being 1% to 50% by weight, preferably 5% to 40% by weight, more preferably 8% to 35% by weight, more particularly
• composition of the invention may be present advantageously as a one-component system and used as such.
• binder and at least one of the stated additions in the form of a two-component system, the components being mixed prior to the application to give such a composition. In this case it is also possible to add further additives.
• a composition of the invention advantageously has a dry residue (solids content) of 1% to 50% by weight, preferably 3% to 45% by weight, more preferably 3% to 35% by weight, based on the composition.
• a composition of the invention is characterized by an amount of particulate metals and/or metal compounds in the composition of 1% to 95% by weight, preferably 3% to 90% by weight, more preferably 5% to 85% by weight, very preferably 10% to 80% by weight.
• Additions in present compositions are preferably particulate metals, metal alloys and/or metal compounds, more particularly metal oxides, selected from the group consisting of conductive and non-conductive fillers, zinc powders, zinc flakes, zinc dust, powders and flakes of zinc alloys, such as zinc-bismuth alloys, magnesium and magnesium alloys, aluminium powders, aluminium flakes, powders and flakes of aluminium alloys, titanium dioxide, red iron oxide, yellow iron oxide, calcium carbonate, talc, aluminium silicates, barium sulphate, kaolin, magnesium silicates, crystalline quartz, amorphous quartz, calcium magnesium carbonate, calcium silicates, aluminium oxide, zeolites, wollastonites, zinc oxide, zinc phosphate, bismuth vanadate, lead chromate, silicon carbide and inorganic colour pigments.
• metal oxides selected from the group consisting of conductive and non-conductive fillers, zinc powders, zinc flakes, zinc dust, powders and flakes of zinc alloys,
• the particulate additions here advantageously have a particle size of 5 nm to 50 ⁇ m, preferably of 10 nm to 40 ⁇ m, more preferably of 15 nm to 30 ⁇ m.
• the particle size may be determined by means, for example, of a Camsizer, Horiba LA-30, LB-550, and also LA-950 from Retsch Technology.
• the particle size may be determined accordingly from 1 nm wet and from 100 nm dry.
• the conductive additions more particularly provide protection from corrosion when they are used in sufficient concentration and are in contact with the metal substrate. Hence metal substrates protected against corrosion with a coating comprising particulate metals can advantageously be welded.
• compositions of the invention may additionally comprise additives advantageously selected from the group consisting of defoamers, thickeners, rheological assistants, dispersion assistants, anti-settling agents, rust inhibitors, wetting agents, organic pigments, polymers and polymer dispersions, and catalysts for the condensation and curing.
• additives advantageously selected from the group consisting of defoamers, thickeners, rheological assistants, dispersion assistants, anti-settling agents, rust inhibitors, wetting agents, organic pigments, polymers and polymer dispersions, and catalysts for the condensation and curing.
• additives advantageously selected from the group consisting of defoamers, thickeners, rheological assistants, dispersion assistants, anti-settling agents, rust inhibitors, wetting agents, organic pigments, polymers and polymer dispersions, and catalysts for the condensation and curing.
• polymers accordingly, it is possible for example, but not exclusively, to use acrylate dispersions, PU dispers
• additives or polymers or cobinders it is possible, furthermore, to use organic film-formers and also adhesion promoters based on acrylic esters, acrylic-polyester-polyurethane copolymers, ethylene-acrylic copolymers, and polyester resins having free carboxyl groups.
• compositions of the invention may be characterized by an amount of additives of in each case 0% to 5% by weight, more particularly of thickener of 0% to 5% by weight and/or of anti-settling agent of 0% to 5% by weight and/or of wetting agent of 0% to 3% by weight and/or of corrosion inhibitor of 0% to 1% by weight, based in each case on the composition, the sum of all the constituents present in the composition making 100% by weight.
• Typical thickeners are, for example, polyacrylic acid polymers, cellulose ethers, polyurethanes, acrylate polymers, hydroxyethylcellulose, which are used at concentrations of 0.005% to 4.0% by weight, preferably of 0.008% to 3.0% by weight and very preferably of 0.01% to 2.0% by weight.
• thickeners and rheology modifiers include Coapur 6050 and Coapur XS 71 from Coatex.
• anti-settling agents examples include laponites, bentonites, glycerol stearates, polyamides, xanthan, polyethylene waxes, modified and non-modified fumed silica, as for example Aerosil® R 812 S or Aerosil® R 805, which are used likewise at concentrations of up to 4% by weight, preferably 0.01% to 3% by weight, more particularly from 0.1% to 2% by weight.
• Typical wetting agents are, for example, BYK 348 and also ethoxylated alcohols, which are used at concentrations of up to 3% by weight, preferably from 0.01% to 2.5% by weight or very preferably from 0.1% to 1.5% by weight.
• Typical corrosion inhibitors are molybdates, phosphates, chromates, borates and also, in particular, organic corrosion inhibitors. These organic corrosion inhibitors are used at lower concentrations, suitably up to 1.0% by weight, preferably 0.8% by weight, more preferably 0.5% by weight, more particularly from 0.00001% to 0.1% by weight, based in each case on the composition, with the sum of all the constituents present in the composition making 100% by weight.
• Possible catalysts for the condensation and curing are, for example, Tyzor LA (DuPont), titanium acetylacetonate and tetrakis(triethanolamine)zirconate.
• the present invention further provides a process for preparing a composition of the invention, which is characterized in that first of all a binder is prepared, comprising at least one cocondensate based on an w-glycidyloxyalkylalkoxysilane of the formula I
• R 1 is methyl and/or ethyl, and also, optionally, on at least one further silicon compound from the group consisting of tetraalkoxysilane, alkylalkoxysilane, mercaptoalkylalkoxysilane, carboxyalkylalkoxysilane, aminoalkylalkoxysilane, ureidoalkylalkoxysilane, thiocyanatoalkylalkoxysilane and silica sols, said binder being prepared by a procedure in which water is introduced in a molar excess, based on the silanes of the formulae I and
• the w-glycidyloxyalkylalkoxysilane of the formula I in a molar ratio to the bis(alkoxysilylalkyl)amine of the general formula II of 0.1:99.9 to 99:1, preferably of 1:99 to 95:5, more preferably up to 80:20, very preferably up to 70:30, more particularly the w-glycidyloxyalkylalkoxysilane is used in the binder at 0.001 to 42 mol %, preferably from 0.01 to 30 mol %, more preferably from 0.1 to 15 mol %, very preferably from 0.2 to 1.5 mol %.
• the procedure more particularly in the process of the invention is that water is introduced in a molar excess, based on the silanes of the formulae I and II and also, optionally, the aforementioned silicon compounds that are used, of suitably 2 to 1000 mol of water, preferably 5 to 500 mol, more particularly 10 to 100 mol of water per mole of the Si-bonded alkoxy groups present in the silanes used, under inert gas.
• the inert gas used in the reaction is generally nitrogen or argon.
• an organic or inorganic acid this acid being advantageously selected from the group consisting of formic acid, acetic acid, propionic acid, hydrochloric acid, nitric acid, sulphuric acid and phosphoric acid.
• Said acids may be used in aqueous form or else in concentrated form.
• Using one of said acids, preferably with formic acid it is possible more particularly to adjust the pH of the reaction mixtures and/or product mixtures, particularly of the binder, during and/or after the reaction, to 1 to 6.5, preferably 2 to 6, more particularly to 2.5; 3; 3.5; 4; 4.5; 5 and also 5.5, advantageously.
• binders used in accordance with the invention can also be stabilized in the neutral and alkaline ranges.
• an aqueous alkali or a suitable base it is possible to set the pH advantageously to a neutral or alkaline value, more particular to 7; 7.5, 8; 8.5; 9; 9.5; 10; 10.5; 11; 11.5; 12; 12.5; 13 and also 14—cf. the examples.
• Further bases besides alkalis, such as aqueous NaOH or KOH, which can be used advantageously are preferably N,N-dimethylethanolamine or else Tyzor TEAZ [tetrakis(triethanolamine)zirconate].
• 3-glycidyloxypropyltrimethoxysilane and/or 3-glycidyloxypropyltriethoxysilane as ⁇ -glycidyloxyalkylalkoxysilane of the formula I and to meter it into the acidic aqueous mixture obtained before, and to heat the mixture over 0.1 to 3 hours, preferably 0.5 to 1.5 or 2 hours, with stirring and/or mixing, to a temperature of 50 to 90° C., preferably 55 to 70° C., more particularly 60 to 65° C.
• the heated, acidic and ⁇ -glycidyloxyalkylalkoxysilane-containing mixture is admixed preferably with bis(trimethoxysilylpropyl)amine and/or bis(triethoxysilylpropyl)amine.
• a tetraalkoxysilane preferably tetramethoxysilane, tetraethoxysilane, an alkylalkoxysilane, preferably C1-C16-alkylalkoxysilanes, more particularly methyltrimethoxysilane, methyltriethoxysilane, n-propyltrimethoxysilane (PTMO), n-propyltriethoxysilane (PTEO), isobutyltrimethoxysilane (IBTMO), isobutyltriethoxysilane (IBTEO), octyltrimethoxysilane (OCTMO), octyltriethoxysilane (OCTEO), mercaptoalkylalkoxysilane, preferably 3-mercaptopropyltrimethoxysilane
• the metered addition of the aforementioned silanes here takes place advantageously at a pH of 2 to 6, preferably 3 to 5, and with stirring at 50 to 90° C., preferably 60 to 65° C. Subsequently the mixture is advantageously caused to react over 0.3 to 6 hours, preferably 2 to 4 hours, possibly accompanied by further stirring; that is, the alkoxysilanes used hydrolyse substantially completely hydrolysed and condensed or cocondensed.
• the binder thus present may optionally be diluted with water and/or an aqueous acid or aqueous base in order, for example, to adjust the pH, the amount of dry residue and/or the viscosity.
• the binder subsequently, is suitably filtered, preference being given to the use of a fine-pored filter plate, in order to remove relatively coarse aggregates that may have formed during the reaction.
• a binder obtainable in this way possesses at room temperature a generally oil-like consistency, is slightly cloudy to clear, and ranges from yellowish to colourless.
• an organic or inorganic acid selected from the group consisting of formic acid, acetic acid, propionic acid, hydrochloric acid, nitric acid, sulphuric acid and phosphoric acid and also an aqueous base selected from the group consisting of sodium hydroxide, potassium hydroxide or else Tyzor TEAZ [tetrakis(triethanolamine)zirconate] or N,N-dimethylethanolamine or other bases are preferably used, with the pH being adjusted during and/or after the reaction in the binder and/or after formulation in the composition to 1 to 14, preferably 2 to 12, more preferably 2.5 to 9, very preferably 3 to 8, more particularly to 3.5; 4; 4.5; 5; 5.5; 6; 6.5; 7; 7.5; 8 and also 8.5, in which context the addition of at least one of the aforementioned particulate metals, metal alloys and/or metal compounds to the binder may also result in a change in the pH, more particularly the addition of zinc, zinc oxide
• a composition of the invention can be produced in corresponding mixers or mixing assemblies which are known per se to the skilled person.
• composition of the invention or composition obtainable in accordance with the invention for coatings which cure in the air at a temperature of 16 to 26° C., with more particular advantage for coatings on metals and metal alloys for protection from corrosion.
• compositions of the invention are notable with particular advantage for a comparatively excellent processing stability and outstanding user properties and also eco-friendly properties for corrosion control applications on metal substrates.
• the pH of the reaction mixtures was determined using pH paper (special-purpose indicator pH 2.5-4.5, Merck; pH-Fix 0.0-6.0, Machery-Nagel).
• the pH values in the binders and the compositions formulated from them were determined alternatively using a Metrohm 826 pH mobile pH meter.
• the formulations were diluted 1:1 with water prior to measurement.
• the solids content (also referred to as dry residue) of the aqueous silane systems was determined as follows:
• the filter was dried in a platinum crucible, ashed and calcined at 800° C. for 1 hour in a muffle furnace. After having been weighed, the residue was smoked off with hydrofluoric acid, the crucible was calcined by means of a fan burner and optionally calcined again at 800° C., and, after it had cooled, was weighed. The difference between the two weighings gave the amount of SiO 2 .
• the alcohol determination was carried out by means of GC.
• a clear, yellowish liquid having a pH of 4.3 was obtained.
• the product is stable on storage for at least 6 months.
• SiO 2 content 5.9% by weight
• a clear, yellowish liquid having a pH of 5.0 was obtained.
• the product is stable on storage for at least 6 months.
• SiO 2 content 5.7% by weight
• a clear, yellowish liquid having a pH of 4.4 was obtained.
• the product is stable on storage for at least 6 months.
• SiO 2 content 6.1% by weight
• the batch was admixed with 95.71 g of water, in order to achieve the theoretical solids content of 15%. However, the viscosity was so high that dilution was carried out additionally with 272.2 g of water to a solids content of approximately 10%.
• a clear, yellowish liquid having a pH of 4.4 was obtained.
• the product is stable on storage for at least 6 months.
• SiO 2 content 4.3% by weight
• a clear, yellowish liquid having a pH of 4.2 was obtained.
• the product is stable on storage for at least 6 months.
• SiO 2 content 5.8% by weight
• a clear, yellowish liquid having a pH of 5.2 was obtained.
• the product is stable on storage for at least 6 months.
• SiO 2 content 5.6% by weight
• a clear, yellowish liquid having a pH of 4.8 was obtained.
• the product is stable on storage for at least 6 months.
• SiO 2 content 5.3% by weight
• SiO 2 content 6.3% by weight
• a clear, yellowish liquid having a pH of 4.5 was obtained.
• the product is stable on storage for at least 6 months.
• SiO 2 content 6.0% by weight
• a milkily cloudy, slightly orange liquid having a pH of 4.0 was obtained.
• the product is stable on storage for at least 6 months.
• SiO 2 content 9.7% by weight
• a milkily cloudy liquid having a pH of 3.9 was obtained.
• the product is stable on storage for at least 6 months.
• SiO 2 content 13.9% by weight
• a slightly yellow, milkily cloudy liquid having a pH of 4.2 was obtained.
• the product is stable on storage for at least 6 months.
• SiO 2 content 15.6% by weight
• a milkily cloudy liquid having a pH of 4.0 was obtained.
• the product is stable on storage for at least 6 months.
• SiO 2 content 15.5% by weight
• a milkily cloudy liquid having a pH of 4.3 was obtained.
• the product is stable on storage for at least 6 months.
• SiO 2 content 10.7% by weight
• a milkily cloudy liquid having a pH of 4.2 was obtained.
• the product is stable on storage for at least 6 months.
• SiO 2 content 20.5% by weight
• a milkily cloudy liquid having a pH of 4.3 was obtained.
• the product is stable on storage for at least 6 months.
• SiO 2 content 20.7% by weight
• a milkily cloudy liquid having a pH of 4.2 was obtained.
• the product is stable on storage for at least 6 months.
• SiO 2 content 15.7% by weight
• a cloudy, pale beige liquid having a pH of 5.0 was obtained.
• the product is stable on storage for at least 6 months.
• SiO 2 content 10.7% by weight
• a clear, yellowish liquid having a pH of 4.5 was obtained.
• the product is stable on storage for at least 6 months.
• SiO 2 content 6.1% by weight
• a clear, yellowish liquid having a pH of 4.5 was obtained.
• the product is stable on storage for at least 6 months.
• SiO 2 content 5.8% by weight
• a clear, yellowish liquid having a pH of 4.5 was obtained.
• the product is stable on storage for at least 6 months.
• SiO 2 content 5.1% by weight
• a yellowish liquid having a pH of 4.5 was obtained.
• the product is stable on storage for at least 6 months.
• SiO 2 content 5.1% by weight
• a clear, colourless liquid having a pH of 4.5 was obtained.
• the product is stable on storage for at least 6 months.
• SiO 2 content 5.1% by weight
• a clear, colourless liquid having a pH of 4.5 was obtained.
• the product is stable on storage for at least 6 months.
• SiO 2 content 5.1% by weight
• the batch was again distilled at approximately 180 mbar to remove 36.19 g of alcohol/water mixture, and was admixed with 51.22 g of DI water.
• the cooled residue was filtered on a Seitz T-950 filter plate.
• a milky white liquid having a pH of approximately 4.3 was obtained.
• the product is stable on storage for at least 6 months.
• SiO 2 content 10.8% by weight
• the cooled residue was filtered on a Seitz T-950 filter plate.
• a milky white liquid having a pH of approximately 4.0 was obtained.
• the product is stable on storage for at least 6 months.
• SiO 2 content 15.8% by weight
• SiO 2 content 13.6% by weight
• SiO 2 content 11.0% by weight
• a liquid having a pH of 4.0 was obtained.
• the product is stable on storage for at least 6 months.
• SiO 2 content 10.5% by weight
• a clear, yellowish liquid having a pH of 4.0 was obtained.
• the product is stable on storage for at least 6 months.
• SiO 2 content 6.7% by weight
• a clear, yellowish liquid having a pH of 3.9 was obtained.
• the product is stable on storage for at least 6 months.
• SiO 2 content 6.9% by weight
• a clear, yellowish liquid having a pH of 3.9 was obtained.
• the product is stable on storage for at least 6 months.
• SiO 2 content 6.0% by weight
• a milkily cloudy liquid having a pH of 3.9 was obtained.
• the product is stable on storage for at least 6 months.
• SiO 2 content 11.0% by weight
• the batch was stirred at 65° C. for 3 hours. Finally, at approximately 130 mbar, 340.64 g of alcohol/water mixture were removed by distillation. The residue, cooled to RT, was filtered on a Seitz K-900 filter plate. The final mass of the residue was 1259.89 g.
• a clear, yellowish liquid having a pH of 3.9 was obtained.
• the product is stable on storage for at least 6 months.
• Dry residue 17.4% by weight (for the application tests, the product was diluted with DI water to a solids content of 15% by weight)
• SiO 2 content 6.2% by weight
• Solids content (% by pH adjusted Assessment of weight) after addition with aqueous stability of Binder from of aqueous KOH KOH to alkalified binder
• Example 8 10 12 stable
• Example 7 10 12 stable
• Example 6 10 12 stable
• Example 3 10 12 stable
• Example 2 10 12 stable
• the pH of samples of the acidic aqueous binders from Examples 2, 3, 6, 7 and 8 was adjusted to pH 12 using a 10% strength aqueous KOH solution. For this, alkali solution was added rapidly.
• the examples marked in the table as “stable” were stable at the stated pH for at least 1 week.
• the steel test panels were cleaned with an organic solvent (ethyl acetate) and then placed into an alkaline cleaning bath (composition: 10.0 g/l S 5610 (Chemetal), pH 11.5, 60° C., 35 seconds). Following alkaline cleaning, the metal substrates were rinsed with DI water. The excess water was blown from the surface using a compressed-air gun.
• organic solvent ethyl acetate
• alkaline cleaning bath composition: 10.0 g/l S 5610 (Chemetal), pH 11.5, 60° C., 35 seconds.
• the corrosion tests (also referred to for short as NSS) were carried out in a salt spray mist (testing according to DIN 50021-SS).
• Binders used for the application examples were as follows:
• Binder 1 reproduced according to Example 3 from WO2006/079516 (comparative composition) dry residue 16.2% by weight Binder 2 Dynasylan ® AR (comparative composition, solvent-containing) dry residue 27.3% by weight Binder 3 from Example 6 (70% GLYMO) dry residue 15.6% by weight Binder 4 from Example 2 (50% GLYMO) dry residue 14.9% by weight Binder 5 from Example 9 (60% GLYMO) dry residue 16.8% by weight Binder 6 from Example 30 dry residue 20.9% by weight Binder 7 from Example 31 dry residue 15.0% by weight Binder 8 from Example 35 dry residue 17.4% by weight
• Additions B and C were prepared in a universal mixing machine (type AM 501 T from Hauschild). Addition mixtures B and C were each mixed in the universal mixing machine at 3000 rpm for 3 ⁇ 30 seconds.
• compositions prepared for comparative examples (the pH of the compositions was measured in each case 30 minutes following preparation): Com- Mass of Mass of Binder:addi- parative binder addition tion weight examples
• the plates were dried at 20° C. for 24 hours and scribed.
• the adhesion of the coated substrates was tested by means of a cross-cut test.
• Comparative Example 1 1 Comparative Example 2: 1 Application Example 1: 1 Comparative Example 3: 0 Comparative Example 4: 1 Application Example 2: 1 Comparative Example 5: 2 Application Example 3: 0 Application Example 4: 1
• coated and scribed substrates were tested for corrosion resistance in a salt spray mist (DIN 50021-SS) and assessed.
• Comparative Example 1 corrosion at the scribe and partially over the surface Comparative Example 2: largely corrosion-free
• Application Example 1 largely corrosion-free
• Comparative Example 3 corrosion at the scribe and over the surface Comparative Example 4: delaminations of the coating with corrosion
• Application Example 2 largely corrosion-free
• Comparative Example 5 corrosion at the scribe and partially over the surface
• Application Example 3 no corrosion at the scribe or over the surface
• Application Example 4 corrosion at the scribe and partially over the surface
• the sample from Application Example 3 was coated with a 2-component epoxy resin: Standox, EP primer-surfacer and Standox EP hardener. Mixing ratio 2:1 (according to specification).
• the coating system was applied using a bar applicator (80 ⁇ m wet film thickness, ⁇ 30 ⁇ m dry film thickness) and cured at 20° C. for 24 hours.
• a comparative sample (steel panel cleaned only) was likewise coated.
• Comparative Example 1 shows corrosion at the scribe and partially over the surface after just 26 hours. In contrast, Application Comparative Example 2 and Application Example 1 are without scribe corrosion.
• Comparative Example 3 shows corrosion at the scribe and over the surface after 26 hours in the salt spray mist, whereas Application Comparative Example 4 exhibits only some corrosion at the scribe, although some instances of delamination can be observed. The best results are shown by Application Example 2. There is no determinable corrosion at the scribe.
• Comparative Example 5 and Application Example 4 show corrosion at the scribe after 150 hours in the salt spray mist, whereas Application Example 3 is entirely corrosion-free at the scribe after 150 hours.
• Application Example 5 shows no scribe corrosion after 28, 90 or 150 hours. Over the surface, however, a slight discolouration can be observed.
• Application Example 6 shows no scribe corrosion after 17 hours, partial scribe corrosion after 150 hours and almost full-depth scribe corrosion after 250 hours. The surface, however, is corrosion-free.
• Application Example 7 shows no scribe corrosion after 19 hours in the salt spray mist. After 135 hours, however, full-depth corrosion at the scribe can be determined.

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