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
  • 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
  • C09D7/63—Additives non-macromolecular organic
• • 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
  • C23C22/07—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 containing phosphates
  • C23C22/08—Orthophosphates
• • 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
  • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
  • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
  • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
  • C23G1/08—Iron or steel
  • C23G1/088—Iron or steel solutions containing organic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
  • C08K5/098—Metal salts of carboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/10—Esters; Ether-esters
  • C08K5/101—Esters; Ether-esters of monocarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/10—Esters; Ether-esters
  • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids

Definitions

• the invention relates to a rust treatment agent, and more specifically to a rust converting agent, as well as to its applications.
• this rust converter agent as a rust converter additive.
• a rust converting agent is a compound or a mixture of compounds capable of transforming iron oxides and in particular iron hydroxide constituting essential rust, friable and resulting from the corrosion of iron or an alloy based on iron, in a more resistant compound, especially oxidation, and forming a protective barrier vis-à-vis a source of aggression.
• the traditional active ingredients are tannic acid, pyrogallol, oxalic acid, phosphoric acid and their derivatives, and are used alone or in mixtures.
• the most commonly used compounds are tannic acid and phosphoric acid which, in contact with rust, react with the iron oxides to form iron tannate and iron phosphate FePO 4 , respectively .
• a drying time of the rust converting agent layer of the order of 1 to 3 days must be respected, in particular before the application of an aqueous phase paint;
• Treatment with such agents does not confer any protection of the metal support with respect to subsequent oxidation; for example, phosphoric acid forms a layer of iron phosphate on the treated metal, but it is too thin and too weak to be truly protective;
• the invention provides a rust converter agent for overcoming all of the above disadvantages.
• the rust converting agent according to the invention consists of one or more hydroxylated organic acid salts and / or one or more salts of an organic acid derivative. hydroxylated, at least one of a passivating compound and a sequestering compound, and a solvent, the hydroxylated organic acid or acids or the derivative (s) being chosen from hydroxylated carboxylic acids and their derivatives, different from the tannic acid, and whose carboxylic functions are chosen from free carboxylic functions, ester functions, lactone functions and anhydride functions.
• the agent of the invention comprises at least one passivating compound, and optionally a sequestering compound.
• This agent is only slightly acidic and is not colored.
• such an agent is suitable for any support; as an additive, it can also incorporate any type of treatment product and / or coating a support, to overcome a prior stage of rust treatment, rust processing and treatment and / or the coating of the support being simultaneous.
• an agent of the invention to any treatment product and / or coating does not affect the properties of said agent and precisely its ability to transform rust.
• hydroxy carboxylic acid any organic compound comprising at least one free carboxylic function -CQGH and at least one hydroxyl function -OH, primary, secondary or tertiary.
• salt of a hydroxyl carboxylic acid is meant the compound resulting from the reaction between one or more of the carboxylic functions of said hydroxylated carboxylic acid and a base, the anion of the salt consisting of the hydroxylated carboxylic acid residue and the cation being constituted by the rest of the base.
• hydroxy carboxylic acid derivative is meant any organic compound comprising at least one carboxylic function selected from ester functions, lactone functions and anhydride functions, and at least one hydroxyl function -OH, primary, secondary or tertiary. Said derivative may further comprise one or more free carboxylic functions.
• ester function is meant a function - COOR in which R represents any hydrocarbon group. Such a group may be an alkyl group, for example having from 1 to 20 carbon atoms.
• Lactone function means a R'-C (O) -OR function in which R and R 'together form an optionally substituted hydrocycled ring, for example having from 3 to 20 carbon atoms.
• salt of a hydroxylated carboxylic acid derivative is meant the compound resulting from the reaction between one or more of the carboxyl functions of said hydroxylated carboxylic acid derivative and a base, the anion of the salt consisting of the remainder of the dicarboxylic acid derivative. hydroxylated carboxylic acid and the cation consisting of the remainder of the base.
• a salt according to the invention may comprise several anions.
• a passivative compound has the effect of forming a protective film on the treated area, significantly slowing the rate of corrosion of this area relative to what it would be in the absence of this film.
• a sequestering compound, or chelating agent is a compound capable of forming bonds with a metal, generally a transition metal, and in the context of the invention, iron in Fe 3+ ferric form, optionally in Fe 2 ferrous form. ⁇ , in order to form a stable and insoluble complex in the additive or the product in which the additive is present. Thus complexed, the iron will be protected from oxidation.
• Some compounds have both passivating and sequestering properties, such as certain polyphosphates.
• the hydroxylated carboxylic acid or the hydroxylated carboxylic acid derivative of the salt of the invention comprises by definition at least one carboxylic function. It may be in free form -COOH, in ester form, in lactone form or in anhydride form.
• a derivative may comprise at least one free carboxylic function and at least one carboxylic function chosen from ester, lactone and anhydride functions.
• An acid salt whose carboxyl function (s) is free may be a gluconic acid salt, a tartaric acid salt, a citric acid salt or a salt of oxo-gluconic acid.
• the hydroxylated organic acid is gluconic acid.
• An acid derivative salt whose carboxylic function (s) are in lactone form may be a salt of ascorbic acid, a salt of erythorbic acid.
• the cation or salts of hydroxylated or deduced derivative organic acid salts may be chosen from any metal cation whose metal is an alkali metal, an alkaline earth metal, a transition metal, a lean metal and from the ammonium ion and primary, secondary or tertiary ammonium ions.
• the cation or cations are selected from sodium, potassium, calcium, copper, aluminum, ethanolammonium and triethanolammonium ions, the ion derived from ethanolamine.
• Preferred hydroxylated or derivatized organic acid salts are selected from the following:
• any acid differing from the above acids by the presence of substituents, such as hydrocarbon groups for example of the alkyl type, such as alkyls having from 1 to 20 carbon atoms, preferably from 1 to 6 carbon atoms. carbon.
• substituents such as hydrocarbon groups for example of the alkyl type, such as alkyls having from 1 to 20 carbon atoms, preferably from 1 to 6 carbon atoms. carbon.
• the proportion (m / m) of the hydroxylated or deduced derivative organic acid salt or salts ranges from 10 to 25% relative to the mass of said agent. This is essentially to adjust to the amount of rust to neutralize.
• the passivating compounds are preferably chosen from sodium nitrite, sodium or potassium phosphate, sodium or potassium tripolyphosphate, monoethanolamine phosphate, triethanolamine phosphate, sodium or potassium hexametaphosphate and phosphonate.
• the sequestering compounds are preferably chosen from sodium or potassium tripolyphosphate, monoethanolamine phosphate, triethanolamine phosphate, sodium or potassium hexametaphosphate, sodium or potassium phosphonate, sodium or potassium dodecyl phosphonate.
• the proportion (m / m) of the passivating and / or sequestering compound (s) ranges from 5 to 10% relative to the mass of said agent.
• the compound (s) may affect the formulation of the product in which the additive would be added. For example, in the case of a water-based paint (or water-based paint), an excess of these compounds would produce an immobilization of metal ions present in the paint, such as calcium, by chelation, thus generating lumps . When the proportion of this or these compounds is too low, even if we observe a certain effectiveness of the rust converter additive, it is less.
• the choice of the solvent is adapted to the hydroxylated or derivatized carboxylic acid salt (s), in that this or these latter will be soluble therein at least partially, advantageously completely.
• the solvent will preferably be aqueous, or even be water; when the cation is an ammonium, the solvent may be aqueous but also organic, preferably a hydroxylated organic solvent, for example an alcohol, such as ethanol.
• the invention also resides in all applications of a rust converter agent as described above.
• This agent can indeed be used as an additive to add to coatings of different types, paints, varnishes, coatings, adhesives, sealants, so that they can be applied directly to rust.
• the additive is added directly to the coating formulation. It converts the rust and prevents it from going up through the film left by the coating.
• the additive is not an anticorrosion agent, it does not prevent the formation of rust consequent on contact with an aqueous medium with a metal, and in an antirust indication, it will be used advantageously in combination with a corrosion inhibitor .
• an antirust product for the treatment of a rusty or rust-resistant support comprising a rust converter agent according to the invention and a corrosion inhibiting agent. It has been observed that the combination of these two agents allowed to improve the anti-corrosion properties of the corrosion inhibiting agent.
• It also provides a product that can be in the form of a paint, a varnish, a coating, an adhesive, a putty.
• the additive is particularly suitable for aqueous formulations of these products and in this is very advantageous.
• the invention also relates to the use of an agent or additive as defined above, for a coating product of a rusty or rust-resistant support, such as a paint, a varnish, an adhesive, a coating, a putty.
• a coating product of a rusty or rust-resistant support such as a paint, a varnish, an adhesive, a coating, a putty.
• the agent When applied to a rusted metal, treatment with such a product converts rust, protects the metal from further oxidation, and provides a primer capable of retaining rust already formed on the surface of the metal so that it does not go back through the layers of finished product like paint, applied later. If the paint or varnish is in aqueous phase, the agent should preferably be associated with a corrosion inhibitor.
• the proportion of additive of the invention in a product can vary according to the nature of the product, the nature of the treatment, the support.
• a suitable proportion (m / m) oscillates between 2 and 5% relative to the weight of the paint. In another product, it may be higher or lower.
• Example 1 Formulations of a rust converter according to the invention
• a rusty steel support is divided into three zones, among which a first is pretreated by a rust converter of the invention, a second is pretreated by a rust converter based on tannic acid, the third is not pretreated .
• the other two areas have rust spots resulting from rust rising after application of the paint layer.
• a rusty steel support is divided into three zones, of which a first is coated with a layer of a paint of the invention which contains a rust converting agent of the invention, a second is coated with a coating of a paint containing a rust converter based on tannic acid, the third is coated with a coat of paint containing no rust converter.
• the second zone is darkened by tannic acid and has rust spots that have migrated to the surface of the layer.
• the third zone is white but has rust spots that have migrated to the surface of the layer.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Mechanical Engineering (AREA)
• Metallurgy (AREA)
• Life Sciences & Earth Sciences (AREA)
• Wood Science & Technology (AREA)
• Preventing Corrosion Or Incrustation Of Metals (AREA)

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• 2017
  • 2017-04-04 FR FR1752896A patent/FR3064631B1/fr active Active
• 2018
  • 2018-04-04 WO PCT/FR2018/050833 patent/WO2018185429A1/fr not_active Ceased
  • 2018-04-04 CN CN201880023635.XA patent/CN110546213A/zh active Pending
  • 2018-04-04 EP EP18726848.7A patent/EP3607010A1/de active Pending

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