WO2021043985A1 - Composition de revêtement à base de solvant organique pour le revêtement d'une surface d'un substrat métallique pour l'augmentation du coefficient de frottement de la surface du substrat métallique - Google Patents

Composition de revêtement à base de solvant organique pour le revêtement d'une surface d'un substrat métallique pour l'augmentation du coefficient de frottement de la surface du substrat métallique Download PDF

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Publication number
WO2021043985A1
WO2021043985A1 PCT/EP2020/074773 EP2020074773W WO2021043985A1 WO 2021043985 A1 WO2021043985 A1 WO 2021043985A1 EP 2020074773 W EP2020074773 W EP 2020074773W WO 2021043985 A1 WO2021043985 A1 WO 2021043985A1
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Prior art keywords
metal
coating composition
organic
particulate
metal substrate
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PCT/EP2020/074773
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English (en)
Inventor
Lars PLATE
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Atotech Deutschland Gmbh
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Application filed by Atotech Deutschland Gmbh filed Critical Atotech Deutschland Gmbh
Priority to JP2022514566A priority Critical patent/JP2022546769A/ja
Priority to CN202080067127.9A priority patent/CN114514291A/zh
Publication of WO2021043985A1 publication Critical patent/WO2021043985A1/fr

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    • 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
    • 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
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/10—Metal compounds
    • C08K3/14—Carbides

Definitions

  • Organic-solvent based coating composition for coating a surface of a metal substrate for increasing the coefficient of friction of the surface of the metal substrate
  • the present invention relates to an organic-solvent based coating composition for coating a surface of a metal substrate for increasing the coefficient of friction of the surface of the metal substrate; and a method for preparing such a composition.
  • the present invention is further directed to a method for coating a surface of a metal substrate; and a metal substrate with a surface comprising such coating.
  • anti-corrosive coatings are applied to the surfaces of metallic substrates to protect the metallic surfaces from corrosion.
  • Such typical anti-corrosive coatings may comprise chromium coatings.
  • Such chromium coat ings provide an additional barrier layer at the metallic surface, since such chromium coatings are quickly passivated due to contact with ambient air. However, the resulting products of such passivated chromium coatings may impair the decorative and/or functional properties of the surface of the metal substrate.
  • Alternative anti-corrosive coatings may comprise aqueous and solvent-based anti-corrosion compositions including particulate metals, such as zinc and/or aluminum.
  • Such zinc and/or aluminum coatings are typically electrochemically less noble than the surface of the metal substrate to be coated, thereby providing a cathodic protection of the surface of the metal substrate.
  • Such zinc and/or aluminum coatings can be applied directly to the surface of the metal substrate to provide corrosion protection.
  • the resulting products of such coatings may also impair the decorative and/or functional properties of the surface of the metal substrate.
  • the surfaces of many metal substrates such as metal screws, metal nuts, metal clamps and/or metal springs have to withstand such mechanical forces. Consequently, such metallic surfaces typically comprise an increased coefficient of friction, so that manufacturing tools effectively can exert mechanical forces on the metallic surfaces without slipping off said surfaces.
  • a zinc-filled coating composition to be applied to a metal surface is dis closed, wherein the composition comprises silanes and titanium compounds as binding agents.
  • GB 1 499 556 a method of hydrolyzing ethyl silicate is disclosed to provide a gellable hydrolysate.
  • a coating for ferrous metals as cathodic protection is disclosed, wherein the coating is composed of water, zinc dust, aluminum powder, sodium aluminum silicate, iron oxide, titanium dioxide ore, and a thixotrope, such as clay.
  • cross-linked polymeric compositions for ca thodic protection of metal surfaces are disclosed. These cross-linked polymeric composi tions are formed by reaction of a tetra-alkyl titanate ester and polymers resulting from the partial hydrolysis of tetraethyl orthosilicate in an aqueous acidic medium.
  • a water-reducible, chromium-free coating composition for providing cor rosion protection to a metal substrate.
  • the coating composition comprises a high-boiling organic liquid, a particulate metal, such as particulate zinc or aluminum, a thick ener, such as hydroxyethylcellulose, and a silane-based binding agent.
  • a chromium-free coating composition comprising aluminum particles and zinc particles as corrosion inhibitor, and a binder such as silicate and an or ganic titanate.
  • compositions for providing corrosion protection of metal sub strates comprising metal particles and a film-forming binder, the binder comprising a titanate and a polyfunctional polymer.
  • a chromium-free anti-corrosion coating for metal parts wherein the composition comprises a particulate metal and at least one element selected from yttrium, zirconium, lanthanum, cerium, praseodymium and neodymium as a reinforcing agent for the anticorrosion properties of the composition.
  • an object of the present invention to provide an organic-solvent based coating composition for coating a surface of a metal substrate for increasing the coefficient of friction of the surface of the metal substrate, which shall not exhibit the aforementioned shortcomings of the known prior art coating compositions.
  • an object of the present invention to provide an organic-solvent based coating composition, which shall be also suitable to be used for coating surfaces of metal substrates.
  • an object of the present invention to provide an organic-solvent based coating composition comprising a simple as possible general coating composition, prefera bly with chemicals as cheap as possible.
  • an organic-solvent based coating composition for coating a surface of a metal substrate for increasing the coefficient of friction of the surface of the metal substrate having all features of claim 1 according to a first aspect of the present invention.
  • Appropriate modifications of the inventive organic-solvent based coating composition are covered in de pendent claims 2 to 12.
  • claim 13 comprises a method for preparing an organic-solvent based coating composition for coating a surface of a metal substrate for increasing the coefficient of friction of the surface of the metal substrate according to a second aspect of the present invention.
  • claim 14 comprises a method for coating a surface of a metal substrate.
  • claim 15 comprises a metal substrate with a surface, wherein the surface of the metal substrate comprises a coating obtained by a method of coating according to the third aspect.
  • the invention is in particular suitable for depositing coatings on a surface of a metal substrate for example in the field of coatings for electronics and/or mechanical engineering equipment, where there is a need for protective coatings, e.g. for corrosion protection and in particular additionally with an increased coefficient of friction/(correspondingly an in creased K-value).
  • Typical metal substrates to be coated by the coating composition accord ing to the present invention comprise metal screws, metal nuts, metal clamps and/or metal springs.
  • the basic material of the metal substrate can comprise known ferrous metals, such as iron, steel, i.e. carbon steel, and also mixtures thereof.
  • the present invention according to the first aspect of the present invention provides an organic-solvent based coating composition for coating a surface of a metal substrate for increasing the coefficient of friction of the surface of the metal substrate, the composition comprising
  • the organic-solvent based coating composition according to the present inven tion is suitable for depositing a coating on a surface of a metal substrate for increasing the coefficient of friction (correspondingly K-value) of the surface of the metal substrate and to provide an effective anti-corrosion protection of the surface of the metal substrate.
  • the organic-solvent based coating composition is suitable for depositing a coat ing on a plurality of different kind of metal substrates, such as iron or steel.
  • the present invention provides a chromium-free organic-solvent based coating composition that at least approaches the coating characteristics of a chromium-based coating composi tion.
  • the achieved coatings possess good or even excellent anti-corrosive properties and pos sess good or even excellent mechanical properties such as a high coefficient of friction (cor respondingly a high K-value).
  • the present invention provides an organic-solvent based coating composition that provides good stability over the life of the composition.
  • inventive amended organic-solvent based coating composition comprises a very simple general composition with mostly cheap chemicals.
  • the present invention according to the first aspect provides an organic-solvent based coat ing composition for coating a surface of a metal substrate for increasing the coefficient of friction of the surface of the metal substrate, the composition comprising
  • the addition of the at least one metal carbide at a total concentration ranging from 0.1 wt- % to 5 wt.-% along with the other above defined features provides a coating composition which enables depositing a coating on the surface of the metal substrate with advantageous properties, such as a good or even excellent (i.e. desired) coefficient of friction (correspond ingly K-value) of the coated surfaces and a good or even excellent corrosion protection.
  • the terms “for increasing the coefficient of friction” and “increased coefficient of friction” denote that the present invention must be suitable in order to achieve this effect. This is preferably the case compared to an identical organic-solvent based coating composition with the difference that (iii) is not present or present below or above, respectively, the concentration ranging from 0.1 wt.-% to 5 wt.-%, and/or (ii) is not at least one particulate metal provided as metal flakes and having a diameter ranging from 1 pm to 100 pm.
  • an increased coefficient of friction is obtained if (ii) and (iii) are set as defined throughout the present text, preferably as defined as being preferred.
  • Metal carbides possess a high melting point and are extremely hard and abrasion-resistant, thereby allowing for a coating composition to be applied to the metal surface with advanta geous mechanical properties such as an increased coefficient of friction (correspondingly K- value).
  • metal carbide includes metal carbides, semi-metal carbides, and transition-metal carbides. Most preferred metal carbides are tran sition-metal carbides.
  • the at least one binding agent in the composition allows to provide a coating of the surface of the metal substrate, which does not flake off the surface of the metal substrate.
  • the at least one binding agent fixes the coating on the metal surface to be coated and the at least one binding agent connects the pigments (i.e. the sum of the at least one particulate metal as well as the at least one metal carbide and optional further filler particles) present in the coating composition, thereby ensuring the formation of a permanent and stable coating.
  • the at least one binding agent is adapted to provide a stable dispersion of the at least one particulate metal and the at least one metal carbide in the at least one organic solvent.
  • the at least one particulate metal is provided as metal flakes.
  • the at least one metal carbide is selected from the group consisting of transition metal carbides and semi-metal carbides, preferably the at least one metal carbide comprises a metal of subgroups IV (“titan group”) to VII (“manganese group”) of the periodic table of elements, preferably titan carbide, tantalum carbide and/or tungsten carbide, and/or a metal of main group III knowledgeableboron group”) and/or main group IV (“carbon group”) of the periodic table of elements, preferably boron carbide and/or silicon carbide, most preferably the at least one metal carbide is selected as tungsten carbide and/or silicon carbide.
  • a most preferred carbide in the organic-solvent based coating composition is tungsten car bide.
  • Preferred is an organic-solvent based coating composition of the present invention, wherein the at least one metal carbide is not chemically modified. This means that preferably the surface of the at least one metal carbide is not chemically modified. This furthermore pref erably means that the surface of the at least one metal carbide is not chemically modified by an amine moiety and/or a carboxylic moiety.
  • an organic-solvent based coating composition of the present invention wherein more than 60 wt.-% of the at least one metal carbide has a diameter of less than 1 pm, based on the total weight of said metal carbide, preferably of 900 nm or less, more preferably of 800 nm or less, even more preferably of 700 nm or less, yet even more prefer ably of 600 nm or less, most preferably of 500 nm or less.
  • the coating composition comprises the at least one metal carbide at a total con centration ranging from 0.25 wt.-% to 3.5 wt.-%, preferably from 0.4 wt.-% to 2.4 wt.-%.
  • the coating of the surface of the metal sub strate comprises an excellent coefficient of friction (correspondingly K-value) and corrosion protection.
  • the at least one particulate metal comprises particulate aluminum and/or (pref erably and) particulate zinc, and/or the at least one particulate metal comprises a metal-zinc-alloy, wherein the metal comprises aluminum, magnesium, tin, nickel, cobalt and/or manganese, preferably the at least one particulate metal is selected as particulate aluminum and/or (preferably and) particulate zinc.
  • the at least one particulate metal comprises at least particulate zinc.
  • the at least one par ticulate metal comprises particulate zinc and particulate aluminum (preferably as distinct particulate metals), wherein the organic-solvent based coating composition preferably com prises more particulate zinc than particulate aluminum, based on wt.-% and the total weight of the organic-solvent based coating composition. Particularly zinc is needed in order to achieve an acceptable corrosion resistance.
  • the at least one particulate metal provided as metal flakes have a diameter ranging from 1 pm to 100 pm, preferably from 5 pm to 30 pm.
  • the at least one particulate metal is not a powder.
  • most preferably particu late zinc and particulate aluminum is not present in the organic-solvent based coating com position as a powder.
  • “powder” typically refers to a diameter of significantly below 1 pm.
  • particulate metals in particular zinc
  • a variety of particulate metals, in particular zinc, in the coating composition results in an increased cathodic protection of the coating composition.
  • combining aluminum and zinc as particulate metal preferably aluminum flakes and zinc flakes, ensures excellent properties of the coating.
  • an ad vantageously high coefficient of friction (correspondingly K-value) is obtained.
  • the at least one particulate metal comprises particulate zinc at a concentration ranging from 31.5 wt.-% to 49.5 wt.-%, based on the total weight of the coating composition.
  • the at least one particulate metal comprises particulate aluminum at a concen tration ranging from 2.6 wt.-% to 9.8 wt.-%, based on the total weight of the coating compo sition.
  • the at least one particulate metal comprises particulate aluminum and particulate zinc preferably at a total concentration ranging from 20 wt.-% to 50 wt.-% based on the total weight of the coating composition, preferably from 30 wt.-% to 50 wt.-%.
  • the coating of the surface of the metal substrate ob tained ensures an excellent cathodic corrosion protection, while in combination with the metal carbide an excellent coefficient of friction (correspondingly K-value) is provided.
  • the particulate aluminum and the particulate zinc are provided as aluminum flakes and zinc flakes, respectively.
  • the aluminum flakes and the zinc flakes preferably have a diameter ranging from 1 pm to 100 pm, more preferably from 5 pm to 30 pm.
  • Providing aluminum flakes and/or zinc flakes allows for an efficient preparation of the coating composition according to the present invention and excellently contributes to an increased coefficient of friction (correspondingly K-value).
  • the coating composition comprises at least one organic solvent, preferably selected from the group consisting of alcohols, preferably comprising ethanol, iso-propanol, butanol, bu- tan-1-ol, and/or iso-octanol; alkyl ethers of glycol, preferably comprising 1-methoxy-2-pro- panol; mono-alkyl ethers of ethylene glycol; diethylene glycol; propylene glycol; ketones, preferably comprising methyl ethyl ketone and/or methyl isobutyl ketone; iso-phorone; es ters; ethers, preferably comprising 2-ethoxyethyl acetate and/or 2-ethoxyethanol; aromatic hydrocarbons, preferably comprising benzene, toluene and/or xylene; aromatic solvent blends derived from petroleum, preferably comprising hydrogen-treated heavy naphta oil and/or a mixture of aliphatic and naphtenic hydrocarbon
  • the coating composition comprises the at least one organic solvent at a total concentration ranging from 3 wt.-% to 25 wt.-% based on the total weight of the coating composition, preferably from 4 wt.-% to 15 wt.-%.
  • the preferred organic solvents and/or the preferred concentration ranges of the organic sol vents allow for an efficient dispersion of all components of the coating composition of the present invention.
  • the coating composition comprises at least one thickening agent, preferably se lected from the group consisting of ethers of hydroxyethylcellulose, methylcellulose, methylhydroxypropylcellulose, ethyl-hydroxyethylcellulose, methylethylcellulose, xanthan gum, urethane-based thickening agents, organically modified clays, preferably organically modified hectorite and/or organically modified smectite clays; fumed silica, hydrophilic fumed silica, modified urea and mixtures thereof.
  • an organic-solvent based coating composition is preferred not com prising silica.
  • the coating composition comprises at least one wetting agent, wherein preferably the wetting agent is selected as a non-ionic agent, more preferably as non-ionic alkylphenol polyethoxy adducts and/or alkoxylated polyalkylenes, and/or preferably as an anionic wet ting agent, more preferably as organic phosphate esters, and/or a diester sulfosuccinate, even more preferably as sodium bistridecyl sulfosuccinate, and/or more preferably as a low molecular polymethylalkylsiloxane, most preferably polydimethylsiloxane, and modifications thereof, even more preferably as methylalkylpolysiloxane, polyethersiloxane and/or polyes- tersiloxane.
  • the wetting agent is selected as a non-ionic agent, more preferably as non-ionic alkylphenol polyethoxy adducts and/or alkoxylated
  • the coating composition comprises the at least one thickening agent and/or (pref erably and) the at least one wetting agent at a total concentration ranging from 0.1 wt.-% to 5 wt.-% based on the total weight of the coating composition, preferably from 0.5 wt.-% to 4.0 wt.-%.
  • the viscosity of the coating composition can be efficiently adjusted.
  • the wetting agent pref erably at the preferred concentrations, the surface of the particulate metal and/or the metal carbide can be efficiently wetted.
  • the at least one binding agent comprises at least one
  • - silane agent preferably selected from the group consisting of 3-aminopropyltriethox- ysilane, 3-aminopropyltrimethoxy-silane, N-(3-(trimethoxysilyl)propyl)ethylenediamine, N- (3-(triethoxysilyl)propyl)-ethylenediamine, vinyltrimethoxysilane, vinyltriethoxysilane, (3- glycidyloxypropyl)trimethoxysilane, (3-glycidyloxy-propyl)-triethoxysilane, and mixtures, oli gomers and/or hydrolysates thereof, and/or
  • - monomers and/or oligomers of silica acid ester preferably selected from the group con sisting of tetramethylorthosilicate, tetraethylorthosilicate, tetrapropylorthosilicate, tetrabu- tylorthosilicate and mixtures, oligomers and/or hydrolysates thereof.
  • the at least one silane agent has a total concentration ranging from 1 wt.-% to 50 wt.-%, based on the total weight of the coating composition, preferably from 2 wt.-% to 35 wt.-%.
  • the at least one binding agent has a total concentration ranging from 1 wt.-% to 50 wt.-%, based on the total weight of the coating composition, preferably from 2 wt.-% to 35 wt.-%.
  • the at least one binding agent comprises (preferably further comprises) at least one titanate compound, preferably comprising a titanium alkoxide, and/or titanium chelate, and/or titanate oligomer formed by partial hydrolysis of titanate monomer, wherein preferably the titanium alkoxide comprises tetra-n-propyl titanate, tetra-iso-propyl titanate, tetra-n-butyl titanate, tetra-tert-butyl titanate and/or tetra-2-ethyl hexyl titanate, wherein preferably the titanium chelate comprises complexes of titanium with at least one dicarbonyl compound, more preferably titanium di-iso-propoxide-bis-(acetylacetonate), tita nium oxy-acetylacetonate, titanium di-iso-propoxide-bis-(2,2,6,6-tetramethyl-3,5-heptanedi- onate), titanium bis-(
  • the at least one titanate compound has a total concentration from 1 wt.-% to 50 wt.-%, based on the total weight of the coating composition, more preferably from 10 wt.-% to 45 wt.-%.
  • the at least one binding agent is selected as at least one silane agent and at least one titanate compound (i.e. a mixture of both), wherein preferably the total concentra tion of the at least one silane agent and the at least one titanate compound ranges from 1 wt.-% to 50 wt.-%, based on the total weight of the coating composition, preferably from 20 wt.-% to 45 wt.-%.
  • the silane binding agent and/or (preferably and) the titanate binding agent allows to provide a coating of the surface of the metal sub strate, which does not flake off the surface of the metal substrate.
  • an organic-solvent based coating composition according to the present invention wherein the at least one binding agent comprises at least one titanate binding agent.
  • a titanate binding agent is of great benefit in order to achieve an excellent corrosion resistance.
  • the organic solvent is free of water or the amount of water in the organic solvent is 1 wt.-% or less, preferably 0.1 wt.-% or less.
  • the organic-solvent based coating composition of the present invention is free of water or the amount of water in the organic solvent is 1 wt.-% or less, preferably 0.1 wt.-% or less.
  • an organic-solvent based coating composition according to the present inven tion, wherein said composition is substantially free of, preferably does not comprise, a lubri cant. This ensures an increased coefficient of friction (correspondingly K-value). More pre ferred is an organic-solvent based coating composition according to the present invention, wherein said composition is substantially free of, preferably does not comprise, a polypro pylene wax, preferably is substantially free of, preferably does not comprise, a polyalkylene wax, most preferably is substantially free of, preferably does not comprise, any wax. Typi cally, lubricants and waxes decrease the coefficient of friction, which is not desired in the context of the present invention.
  • the present invention is directed to a method for preparing an organic-solvent based coating composition for coating a surface of a metal substrate for increasing the coefficient of friction of the surface of the metal substrate, the method com prising the steps
  • step (c) providing at least one particulate metal provided as metal flakes and having a di ameter ranging from 1 pm to 100 pm; wherein the compounds according to steps (a), (b), and/or (preferably and) (c) are provided together and/or (preferably or) separately, and wherein the compounds according to the steps (a), (b) and/or (preferably and) (c) are preferably provided in a varying order;
  • a homogenous organic-solvent based coating composition can be obtained (i.e. with preferably a homogeneous distribution).
  • the liquid compounds are provided, before the solid compounds are dispersed within the liquid compounds.
  • some of the compounds according to steps (a) to (c) may be provided separately.
  • the order in which said compounds are provided may be varied in respect to the specific compounds used.
  • a first step (a) the at least one organic solvent together with the at least one binding agent and optional additional liquid components, such as liquid additives, is pro vided, wherein as a second step (b) the at least one metal carbide together with optional additional solid additives is provided, wherein as a third step (c) the at least one particulate metal is provided, wherein as a fourth step (d) the compounds provided during steps (a) to (c) are mixed to obtain the organic-solvent based coating composition.
  • first step (a) the at least one organic solvent together with the at least one binding agent and optional additional liquid components, such as liquid additives, is pro vided, wherein as a second step (b) the at least one metal carbide together with optional additional solid additives is provided, wherein as a third step (c) the at least one particulate metal is provided, wherein as a fourth step (d) the compounds provided during steps (a) to (c) are mixed to obtain the organic-solvent based coating composition.
  • the mixture is stirred between steps (a), (b) and/or (c) for a defined period of time wherein preferably the defined period of time is longer as for liquid components as for solid compounds.
  • the period of time preferably ranges from 1 min to 60 min.
  • the organic-solvent based coating composition is filtered, preferably through a sieve.
  • organic-solvent based coating composition according to the present invention preferably described as being preferred
  • the following preferred features preferably apply likewise to the organic-solvent based coating composition according to the present invention.
  • the at least one metal carbide is selected from the group of tran sition metal carbides and/or semimetal carbides, wherein more preferably the least one metal carbide comprises metal ions of subgroups IV (“titan group”) to VII (“manganese group”) of the periodic table of elements, even more preferably titan carbide, tantalum car bide and/or tungsten carbide, and/or metal ions of main group 111 tiltboron group”) and/or main group IV (“carbon group”) of the periodic table of elements, even more preferably boron carbide and/or silicon carbide, and wherein most preferably the least one metal carbide is selected as tungsten carbide and/or silicon carbide.
  • the coating composition comprises the least one metal carbide at a total concentration ranging from 0.25 wt.-% to 3.5 wt.-%, preferably from 0.4 wt.-% to 2.4 wt.-%.
  • the at least one particulate metal is selected as particulate alumi num and particulate zinc, and/or wherein the at least one particulate metal is selected as a metal-zinc-alloy, wherein the metal comprises aluminum, magnesium, tin, nickel, cobalt and/or manganese, wherein preferably the at least one particulate metal is selected as par ticulate aluminum and particulate zinc.
  • the at least one particulate metal is provided as metal flakes and having a diameter ranging from 1 pm to 100 pm, preferably from 5 pm to 30 pm.
  • the at least one particulate metal comprises particulate zinc at a concentration ranging from 31.5 wt.-% to 49.5 wt.-% based on the total weight of the coating composition
  • the at least one particulate metal comprises particulate aluminum at a concentration ranging from 2.6 wt.-% to 9.8 wt.-% based on the total weight of the coating composition.
  • the at least one particulate metal comprises particulate aluminum and particulate zinc preferably at a total concentration ranging from 20 wt.-% to 50 wt.-% based on the total weight of the coating composition, preferably from 30 wt.-% to 50 wt.-%.
  • the particulate aluminum and/or the particulate zinc are provided as aluminum flakes and/or zinc flakes, wherein preferably the aluminum flakes and/or the zinc flakes have a diameter from 1 pm to 100 pm, more preferably from 5 pm to 20 pm.
  • the coating composition comprises at least one organic solvent selected as alcohol, preferably as ethanol, iso-propanol, butanol, butan-1-ol, and/or iso-oc- tanol, as alkyl ether of glycol, preferably 1-methoxy-2-propanol, as mono-alkyl ether of eth ylene glycol, as diethylene glycol, as propylene glycol, as ketone, preferably methyl ethyl ketone and/or methyl isobutyl ketone, as iso-phorone, as ester or ether, preferably 2-ethox- yethyl acetate and/or 2-ethoxyethanol, as aromatic hydrocarbon, preferably benzene, tolu ene and/or xylene, and/or as aromatic solvent blends derived from petroleum, preferably hydrogen-treated heavy naphta oil, and/or a mixture of aliphatic and naphtenic hydrocarbons with a solvent blends
  • the coating composition comprises the at least one organic solvent at a total concentration ranging from 3 wt.-% to 25 wt.-% based on the total weight of the coating composition, preferably from 4 wt.-% to 15 wt.-%.
  • the coating composition comprises at least one thickening agent, wherein preferably the thickening agent is selected from the group comprising ethers of hy- droxyethylcellulose, methylcellulose, methylhydroxypropylcellulose, ethyl-hydroxyethyl- cellulose, methylethylcellulose, xanthan gum, urethane-based thickening agent, organically modified clays, more preferably organically modified hectorite and/or organically modified smectite clays, fumed silica, hydrophilic fumed silica, modified urea and mixtures thereof.
  • the thickening agent is selected from the group comprising ethers of hy- droxyethylcellulose, methylcellulose, methylhydroxypropylcellulose, ethyl-hydroxyethyl- cellulose, methylethylcellulose, xanthan gum, urethane-based thickening agent, organically modified clays, more preferably organically modified hector
  • the coating composition comprises at least one wetting agent, wherein preferably the wetting agent is selected as a non-ionic agent, more preferably as non-ionic alkylphenol polyethoxy adducts and/or alkoxylated polyalkylenes, and/or prefera bly as an anionic wetting agent, more preferably as organic phosphate esters, and/or a diester sulfosuccinate, even more preferably as sodium bistridecyl sulfosuccinate, and/or more preferably as a low molecular polymethylalkylsiloxane, most preferably polydime- thylsiloxane, and modifications thereof, even more preferably as methylalkylpolysiloxane, polyethersiloxane and/or polyestersiloxane.
  • the wetting agent is selected as a non-ionic agent, more preferably as non-ionic alkylphenol polyethoxy adducts and/or alkoxyl
  • the coating composition comprises the at least one thickening agent and/or the at least one wetting agent at a total concentration ranging from 0.1 wt.-% to 5 wt.-% based on the total weight of the coating composition, preferably from 0.5 wt.-% to 4.0 wt.-%.
  • the at least one binding agent is selected as at least one silane agent, preferably selected as 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxy- silane, N-(3-(trimethoxysilyl)propyl)ethylenediamine, N-(3-(triethoxysilyl)propyl)-ethylenedi- amine, vinyltrimethoxysilane, vinyltriethoxysilane, (3-glycidyloxypropyl)trimethoxysilane, (3- glycidyloxy-propyl)-triethoxysilane, monomers and/or oligomers of silica acid ester, more preferably tetramethylorthosilicate, tetraethylorthosilicate, tetrapropylorthosilicate, tetrabu- ty I orth os i I i cate , and mixtures, oligomers and/
  • the at least one binding agent is selected as at least one silane agent at a total concentration ranging from 1 wt.-% to 50 wt.-% based on the total weight of the coating composition, preferably from 2 wt.-% to 35 wt.-%.
  • the at least one binding agent is selected as at least one titanate compound, which is preferably selected as titanium alkoxide, and/or titanium chelate and/or titanate oligomer formed by partial hydrolysis of titanate monomer, wherein more preferably the titanium alkoxide comprises tetra-n-propyl titanate, tetra-iso-propyl titanate, tetra-n-butyl titanate, tetra-tert-butyl titanate and/or tetra-2-ethylhexyl titanate, wherein more preferably the titanium chelate comprises complexes of titanium with at least one dicarbonyl com pound, even more preferably titanium di-iso-propoxide-bis-(acetylacetonate), titanium oxy- acetylacetonate, titanium di-iso-propoxide-bis-(2,2,6,6-tetramethyl-3,5-heptanedionate), ti tanium bis
  • the at least one binding agent is selected as at least one titanate compound at a total concentration from 1 wt.-% to 50 wt.-% based on the total weight of the coating composition, even more preferably from 10 wt.-% to 45 wt.-%.
  • the at least one binding agent is selected as at least one silane agent and at least one titanate compound, wherein the total concentration of the at least one silane agent and the at least one titanate compound ranges from 1 wt.-% to 50 wt.-% based on the total weight of the coating composition, preferably from 20 wt.-% to 45 wt.-%.
  • the organic solvent is free of water or wherein the amount of water in the organic solvent is less than 1 wt.-%, preferably less than 0.1 wt.-%.
  • the present invention is directed to a method for coating a sur face of a metal substrate, the method comprising the steps
  • composition (B) providing an organic-solvent based coating composition for coating a surface of a metal substrate, the composition comprising
  • organic-solvent based coating composition preferably described as being preferred
  • a method according to the third aspect is preferred, wherein at least steps (B), (C), and (D) are repeated, preferably at least a second time. This is preferred if after steps (B), (C), and (D) are utilized a first time, a thicker coating is desired. This can be achieved if preferably the method is carried out two times with a substrate that has already a coating as a result from carrying out the method a first time.
  • the metal substrate is pre-treated, preferably by sandblasting the surface of the metal substrate or by phospha- tizing the surface of the metal substrate.
  • the surface of the metal substrate can be efficiently modified to improve the contact between the surface of the metal substrate and the coating.
  • step (C) the metal substrate is rotated to remove an excess of the coating composition from the metal substrate.
  • step (D) the metal substrate is heated to a temperature ranging from 150 °C to 350 °C, preferably from 200 °C to 300 °C.
  • step (C) the organic-solvent based coating composition is sprayed on the surface of the metal substrate during a spray ing process, and/or during step (C) the metal substrate is immersed in the organic-solvent based coating composition during an immersion process.
  • the metal substrate comprises a metal screw, a metal nut, a metal clamp and/or a metal spring.
  • the coated surface of the metal sub strate obtained after step (D) comprises a K-value from 0.3 to 0.5.
  • the metal of the metal substrate is a ferrous metal, preferably iron or steel.
  • step (C) no electrical current is applied.
  • the present invention is directed to a metal substrate with a surface, wherein the surface of the metal substrate comprises a coating obtained by a method for coating according to the third aspect.
  • the metal substrate comprises a metal screw, a metal nut, a metal clamp and/or a metal spring.
  • the coated surface of the metal substrate comprises a K-value from 0.3 to 0.5.
  • K-value from 0.3 to 0.5.
  • the metal of the metal substrate is a ferrous metal, preferably iron or steel.
  • an organic-solvent based coating com position which comprises particulate zinc, particulate aluminum, at least one additive, at least one binding agent, which comprises at least one titanate compound and at least one silane agent, and at least one organic solvent.
  • the particulate zinc and particulate aluminum are provided as flakes having a diameter ranging at least from 5 pm to 15 pm. This is in general a very preferred diameter for the particulate metal utilized in the present invention.
  • the at least one additive comprises hydrophilic fumed silica as thickening agent and polymethylalkylsiloxane as wetting agent.
  • the at least one titanate compound is selected as tetra-n-butyl titanate, polybutyl titanate, titanium bis-(ethyl-acetoacetato)-di-iso-propoxide, and tetra-2-ethylhexyl titanate, tetra-n-propyl titanate, tetra-iso-propyl titanate and tetra-tert- butyl titanate.
  • the at least one silane is selected as (3-glycidyloxypropyl)trimethox- ysilane, (3-glycidyloxy-propyl)-triethoxysilane, 3-aminopropyltriethoxysilane or 3-ami- nopropyltrimethoxy-silane
  • the at least one organic solvent is selected as hydrogen-treated heavy naphta oil, isooctanol, butan-1-ol, and a mixture of aliphatic and naphtenic hydrocarbons with a content of aromatic compounds less than 0.5 wt.-%.
  • At least one metal carbide is added, preferably tungsten carbide (D50: 200 nm), abbreviated as WC, and/or silicon carbide, abbreviated as SiC.
  • said organic-solvent based coating composition all components are added in a defined order into a container and are mixed by using a dissolver during a pre-dispersion step, which allows for crushing of agglomerated components.
  • a dissolver during a pre-dispersion step, which allows for crushing of agglomerated components.
  • the at least one organic solvent is added
  • the at least one additive is added
  • the solid components including the particulate aluminum, the particulate zinc, the at least one titanate compound and the at least one silane is added.
  • reaction mixture After adding each component, the reaction mixture is stirred. Afterwards, the mixture is fil tered through a sieve with a defined mesh size to obtain the organic solvent based coating composition. Afterwards composition parameters, in particular viscosity, density, average particle size and/or solid content, of the organic solvent based coating composition are measured.
  • the organic-solvent based coating compositions allow for coating a surface of a metal sub strate for increasing the coefficient of friction of the surface of the metal substrate.
  • the metal substrates to be coated comprise metal screws, metal nuts, metal clamps and/or metal springs.
  • the metal substrate which is typically lubricated, is cleaned, preferably by an alkaline degreasing agent.
  • the cleaned metal substrate is pre-treated, preferably by sandblasting the surface of the metal substrate.
  • the pre-treated metal substrate is immersed in the corresponding coating composition according to the specific example to apply the coating composition to the surface of the metal substrate.
  • the pre-treated metal substrate is immersed at 10°C to 35°C for 30 sec to 1 min, and afterwards the pre-treated metal substrate is im mersed at 15°C to 28°C for 30 sec to 1 min.
  • the pre-treated metal substrate is moved in the corresponding coating compositions during immersion.
  • a fourth coating step the metal substrate is rotated to remove an excess of coating com position from the metal substrate, so that only a thin film of coating composition remains on the surface of the metal substrate.
  • the metal substrate comprising the film of coating composition is heated for a predetermined time to a temperature ranging from 300 °C, preferably at 230 °C for 30 min, to remove volatile components from the coating composition and to allow for a chemical reaction of the remaining components of the coating composition to form a coating on the surface of the metal substrate.
  • the coefficient of friction of the coated surfaces of the various metal substrates is determined according to the norm DIN EN ISO 16047.
  • the coefficient of friction (CoF) and the K-value are proportionally related to each other.
  • the K-value as well as the CoF are measured and evaluated.
  • the CoF was also determined based on DIN EN ISO 16047.
  • the metal substrate in particular the metal screw and/or metal nut, are arranged in the test stand, wherein the test stand is adapted to apply a torque value to the metal substrate, and wherein the test stand is adapted to measure a variety of experimental values such as various coefficients of friction.
  • the test stand is adapted to apply a torque value to the metal substrate
  • the test stand is adapted to measure a variety of experimental values such as various coefficients of friction.
  • Table 1 shows conducted experiments for organic-solvent based coating compositions in accordance with embodiments of the present invention
  • Table 2 shows comparative experiments for organic-solvent based coating compositions.
  • Table 2 Comparative experiments for organic-solvent based coating compositions
  • adding a metal carbide i.e. silicon carbide (see example 1) and/or tungsten car bide (see examples 2 to 5)
  • the at least one metal carbide at a total concentration ranging from 0.1 wt.-% to 5 wt.-%, based on the total weight of the coating composition, and the at least one particulate metal provided as metal flakes and having a diameter ranging from 1 pm to 100 pm is very important for obtaining the increased K-value (correspondingly CoF).
  • the absence of said at least one metal carbide results in a reduced, insufficient K-value (correspondingly CoF).
  • Similar undesired results are obtained if particu late metal flakes are used having a significantly smaller diameter, e.g. significantly below 1 pm, e.g. as a powder.

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Abstract

La présente invention porte sur une composition de revêtement à base de solvant organique pour le revêtement d'une surface d'un substrat métallique pour l'augmentation du coefficient de frottement de la surface du substrat métallique, la composition comprenant (i) au moins un solvant organique ; (ii) au moins un métal particulaire sous forme de paillettes métalliques et ayant un diamètre allant de 1 pm à 100 µm ; (iii) au moins un carbure métallique en une concentration totale allant de 0,1 % en poids à 5 % en poids par rapport au poids total de la composition de revêtement ; et (iv) au moins un agent liant.
PCT/EP2020/074773 2019-09-04 2020-09-04 Composition de revêtement à base de solvant organique pour le revêtement d'une surface d'un substrat métallique pour l'augmentation du coefficient de frottement de la surface du substrat métallique WO2021043985A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2022514566A JP2022546769A (ja) 2019-09-04 2020-09-04 金属基板の表面の摩擦係数を増加させるために金属基板の表面をコーティングするための有機溶媒ベースのコーティング組成物
CN202080067127.9A CN114514291A (zh) 2019-09-04 2020-09-04 用于涂覆金属基底的表面以增加所述金属基底的表面的摩擦系数的以有机溶剂为主的涂料组合物

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EP19195263 2019-09-04
EP19195263.9 2019-09-04

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WO2021043985A1 true WO2021043985A1 (fr) 2021-03-11

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Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1212424A (en) 1967-05-12 1970-11-18 Chanden Coatings Polymeric compositions and protective coatings
GB1380748A (en) 1971-12-30 1975-01-15 Stauffer Chemical Co Coating composition
GB1499556A (en) 1975-11-06 1978-02-01 Zirconal Processes Ltd Method of hydrolysing ethyl silicate
US4209555A (en) 1979-01-26 1980-06-24 A. O. Smith Corporation Corrosion resistant galvanic coating
US5593773A (en) * 1992-07-23 1997-01-14 Silberline Limited Metal powder pigment
EP0808883A2 (fr) 1996-05-20 1997-11-26 Metal Coatings International Inc. Composition de revêtement aqueuse pour la protection contre la corrosion
EP1233043A2 (fr) * 2001-02-14 2002-08-21 Metal Coatings International Inc. Revêtement contenant un alliage métallique particulaire pour protéger contre la corrosion
EP1280863A1 (fr) 2000-05-11 2003-02-05 Dow Corning Corporation Composition de revetement
EP1644451B1 (fr) 2003-07-15 2007-08-08 Dacral Utilisation d'yttrium, de zirconium, de lanthane, de cerium, de praseodyme et/ou de neodyme comme agent de renfort dans une composition de revetement anticorrosion
US20070259172A1 (en) 2006-05-02 2007-11-08 Scott Matthew S Coating compositions exhibiting corrosion resistance properties, related coated articles and methods
US20100028690A1 (en) * 2008-03-04 2010-02-04 Richard Parks Corrosion Technologies, Inc. High-Temperature Non-Skid Coating Composition
WO2015128802A1 (fr) * 2014-02-25 2015-09-03 Altshuler Kenneth Peintures industrielles à base de carbure de silicium
US20170101716A1 (en) * 2015-10-09 2017-04-13 Ewald Dörken Ag Corrosion control coating
CN107141863A (zh) * 2017-05-16 2017-09-08 江南大学 一种高强防腐涂料及其制备方法与应用

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008051883A1 (de) * 2008-10-16 2010-04-22 Nano-X Gmbh Beschichtung zum kathodischen Korrosionsschutz von Metall, Verfahren zum Herstellen der Beschichtung und Verwendung der Beschichtung.
DE102009023402A1 (de) * 2009-05-29 2010-12-02 Esk Ceramics Gmbh & Co. Kg Suspension zur Herstellung einer reibwerterhöhenden Schicht, Formkörper mit einer solchen reibwerterhöhenden Schicht, Verfahren zu dessen Herstellung und dessen Verwendung
CN107337987A (zh) * 2017-07-07 2017-11-10 合肥新意境材料有限责任公司 一种新型高耐磨无铬达克罗涂料及其制备方法

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1212424A (en) 1967-05-12 1970-11-18 Chanden Coatings Polymeric compositions and protective coatings
GB1380748A (en) 1971-12-30 1975-01-15 Stauffer Chemical Co Coating composition
GB1499556A (en) 1975-11-06 1978-02-01 Zirconal Processes Ltd Method of hydrolysing ethyl silicate
US4209555A (en) 1979-01-26 1980-06-24 A. O. Smith Corporation Corrosion resistant galvanic coating
US5593773A (en) * 1992-07-23 1997-01-14 Silberline Limited Metal powder pigment
EP0808883A2 (fr) 1996-05-20 1997-11-26 Metal Coatings International Inc. Composition de revêtement aqueuse pour la protection contre la corrosion
EP1280863A1 (fr) 2000-05-11 2003-02-05 Dow Corning Corporation Composition de revetement
EP1233043A2 (fr) * 2001-02-14 2002-08-21 Metal Coatings International Inc. Revêtement contenant un alliage métallique particulaire pour protéger contre la corrosion
EP1644451B1 (fr) 2003-07-15 2007-08-08 Dacral Utilisation d'yttrium, de zirconium, de lanthane, de cerium, de praseodyme et/ou de neodyme comme agent de renfort dans une composition de revetement anticorrosion
US20070259172A1 (en) 2006-05-02 2007-11-08 Scott Matthew S Coating compositions exhibiting corrosion resistance properties, related coated articles and methods
US20100028690A1 (en) * 2008-03-04 2010-02-04 Richard Parks Corrosion Technologies, Inc. High-Temperature Non-Skid Coating Composition
WO2015128802A1 (fr) * 2014-02-25 2015-09-03 Altshuler Kenneth Peintures industrielles à base de carbure de silicium
US20170101716A1 (en) * 2015-10-09 2017-04-13 Ewald Dörken Ag Corrosion control coating
CN107141863A (zh) * 2017-05-16 2017-09-08 江南大学 一种高强防腐涂料及其制备方法与应用

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