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
  • C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
  • C09D177/06—Polyamides derived from polyamines and polycarboxylic acids
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D1/00—Processes for applying liquids or other fluent materials
  • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
  • B05D1/04—Processes for applying liquids or other fluent materials performed by spraying involving the use of an electrostatic field
  • B05D1/06—Applying particulate materials
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D1/00—Processes for applying liquids or other fluent materials
  • B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
  • B05D1/22—Processes for applying liquids or other fluent materials performed by dipping using fluidised-bed technique
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
  • C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
• • 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
  • C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
• • 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
  • C09D5/03—Powdery 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
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/03—Powdery paints
  • C09D5/031—Powdery paints characterised by particle size or shape

Definitions

• the present invention relates to powders based on copolyamide of low melting temperature and the use of these powders for coating surfaces.
• the coating of metal surfaces is widespread in the industry and has a wide variety of applications, particularly in the automotive, fluid transfer and electrical and electronic industries.
• Polyamides are commonly used for coating metallic surfaces or other surfaces.
• document EP 0 866 736 describes a method of coating an aluminum or steel substrate with the aid of a powder formed from a polyamide comprising a branched amine.
• Document FR 2304998 relates to powdery plastic coatings obtained by the reaction of an epoxy compound with a copolyamide.
• the surface to be coated may be heat sensitive.
• the surface can be made of heat-sensitive metals such as a zinc-aluminum alloy, or have undergone a heat-sensitive chemical treatment.
• the heat sensitivity of these surfaces precludes the use of high coating application temperatures, which could damage the surface to be coated.
• the invention relates firstly to a copolyamide-based powder intended to form a coating on a surface, having an inherent viscosity greater than or equal to 0.8 (g / 100 g) -1 , in which the copolyamide has a temperature of melting less than or equal to 160 ° C.
• the copolyamide is chosen from the group consisting of copolyamide 6/1 1, copolyamide 6/12, copolyamide 6.6 / 1 1, copolyamide 6.6 / 12, copolyamide 6.10 / 1 1, copolyamide 6 / 12/1 1, copolyamide Pip.12 / 12, Pip representing piperazine, copolyamide 6 / 6.6 / 12, copolyamide 6 / Pip.12 / 12, or a combination thereof.
• the copolyamide is present, relative to the total mass of the powder, in an amount greater than or equal to 80% by mass, preferably greater than or equal to 90% by mass, more preferably greater than or equal to 95% by mass.
• the powder also comprises a second polymer having a melting temperature lower than that of the copolyamide.
• the second polymer is a second copolyamide and / or an epoxy resin.
• the second polymer has a melting temperature less than or equal to 130 ° C. According to embodiments, the second polymer is present, relative to the total mass of the powder, in an amount less than or equal to 10% by mass, preferably less than or equal to 5% by mass.
• the powder also comprises one or more additives chosen from the group consisting of pigments or dyes, anti-crater agents or spreading agents, reducing agents, antioxidants, reinforcing fillers, stabilizers UV, fluidizing agents and corrosion inhibitors.
• the mass quantity of the additive (s), relative to the total mass of the powder is from 0 to 30%, preferably from 0 to 10%, more preferably from 0 to 5%.
• the copolyamide has a melting temperature less than or equal to 150 ° C., preferably less than or equal to 145 ° C.
• the powder has an inherent viscosity greater than or equal to 0.9, preferably greater than or equal to 1, in (g / 100 g) 1 .
• the powder comprises particles based on copolyamide having a volume median diameter Dv50 of 10 to 400 ⁇ m, preferably of 50 to 200 ⁇ m.
• the invention also relates to a film capable of being obtained by melting the powder as described above.
• the invention also relates to the use of a powder as described above for coating a surface, the coating having an inherent viscosity greater than or equal to 0.8 (g / 100 g) 1 .
• the surface is a metallic surface, possibly treated.
• the coating is a film having a thickness of 100 to 550 ⁇ m, preferably 200 to 500 ⁇ m.
• the invention also relates to a method for coating a surface, preferably a metal surface, comprising the following steps:
• the step of bringing the surface into contact with the powder comprises the steps of: - Heating the surface to a temperature above the melting temperature of the copolyamide, preferably at least 30 ° C higher than the melting temperature of the copoamide;
• the step of bringing the surface into contact with the powder comprises the steps of:
• the step of bringing the surface into contact with the powder comprises the steps of:
• the invention also relates to an object comprising a surface covered with a coating capable of being obtained by melting the powder as described above.
• the present invention makes it possible to meet the need expressed above. It more particularly provides a polyamide powder allowing both an application at a relatively low temperature (and thus suitable for coating heat-sensitive surfaces such as heat-sensitive metal surfaces), and obtaining a coating having an increased thickness and good properties. mechanical.
• the invention relates to a powder based on copolyamide having an inherent viscosity greater than or equal to 0.8 (g / 100 g) 1 in which the copolyamide has a melting temperature less than or equal to 160 ° C.
• This powder is intended to form a coating on a surface.
• the melting temperature can be measured according to ISO 1 1357-3 Plastics - Differential scanning calorimetry (DSC) Part 3.
• the inherent viscosity is measured using an Ubbelhode tube. The measurement is carried out at 20 ° C on a 75 mg sample at a concentration of 0.5% (m / m) in m-cresol. The inherent viscosity is expressed in (g / 100 g) -1 and is calculated according to the following formula:
• This measurement corresponds to the ISO 307 standard except that the measurement temperature is 20 ° C instead of 25 ° C.
• copolyamide means the polymerization products of at least two different monomers chosen from:
• diamine.diacid the “diamine.diacid” type monomers resulting from the reaction between an aliphatic diamine having from 2 to 36 carbon atoms, preferably from 4 to 18 carbon atoms and a dicarboxylic acid having from 4 to 36 carbon atoms, preferably from 4 to 18 carbon atoms;
• copolyamides should be taken in the sense of "repeating unit”. Indeed, the case where a unit repetitive polyamide (PA) consists of the association of a diacid with a diamine is particular. It is considered that it is the association of a diamine and a diacid, that is to say the diamine couple. diacid (in equimolar quantity), which corresponds to the monomer. This is explained by the fact that individually, the diacid or the diamine is only one structural unit, which by itself is not sufficient to polymerize.
• PA unit repetitive polyamide
• alpha, omega-amino acids mention may be made of those having 4 to 18 carbon atoms, such as aminocaproic, 7-aminoheptanoic, 1 1 -aminoundecanoic, N-heptyl-1 1 -aminoundecanoic acids and 12-aminododecanoic.
• lactams of those having 3 to 18 carbon atoms on the main ring and which may be substituted. Mention may be made, for example, of b, b-dimethylpropriolactam, a, a-dimethylpropriolactam, amylolactam, caprolactam also called lactam 6, capryllactam also called lactam 8, enantholactam and lauryllactam also called lactam 12.
• dicarboxylic acid examples include acids having from 4 to 36 carbon atoms. Mention may be made, for example, of adipic acid, sebacic acid, azelaic acid, suberic acid, isophthalic acid, butanedioic acid, 1,4 cyclohexyldicarboxylic acid, terephthalic acid, sodium or lithium salt of sulphoisophthalic acid, dimerized fatty acids (these dimerized fatty acids have a dimer content of at least 98% and are preferably hydrogenated) and dodecanedioic acid HOOC- (CH2) IO- COOH, and tetradecanedioic acid.
• adipic acid sebacic acid, azelaic acid, suberic acid
• isophthalic acid butanedioic acid
• 1,4 cyclohexyldicarboxylic acid 1,4 cyclohexyldicarboxylic acid
• terephthalic acid sodium or lithium
• fatty acid dimers or dimerized fatty acids is understood more particularly to mean the product of the dimerization reaction of fatty acids (generally containing 18 carbon atoms, often a mixture of oleic and / or linoleic acid). It is preferably a mixture comprising from 0 to 15% of C18 monoacids, from 60 to 99% of C36 diacids, and from 0.2 to 35% of C54 triacids or polyacids or more.
• a diamine By way of example of a diamine, mention may be made of aliphatic diamines having from 2 to 36 atoms, preferably from 4 to 18 atoms, which may be saturated aryl and / or cyclic. Examples include hexamethylenediamine, piperazine (abbreviated "Pip"), aminoethylene piperazine, tetramethylene diamine, octamethylene diamine, decamethylene diamine, dodecamethylene diamine, 1,5 diaminohexane, 2,2,4-trimethyl-1,6-diamino-hexane, polyol diamines, isophorone diamine (IPD), methyl pentamethylenediamine (MPMD ), bis (aminocyclohexyl) methane (BACM), bis (3-methyl-4 aminocyclohexyl) methane (BMACM), methaxylyenediamine, and bis-p aminocyclohexylmethane.
• diamines.diacids there may be mentioned more particularly those resulting from the condensation of 1, 6-hexamethylenediamine with a dicarboxylic acid having from 6 to 36 carbon atoms and those resulting from the condensation of 1, 10 - decamethylenediamine with a diacid having from 6 to 36 carbon atoms.
• diamine.diacid type monomers
• X.Y X represents the number of carbon atoms derived from diamine residues
• Y represents the number of carbon atoms derived from diacid residues, in a conventional manner.
• the copolyamide preferably comprises at least one of the following monomers: 4.6, 4.T, 5.6, 5.9, 5.10, 5.12, 5.13, 5.14, 5.16, 5.18, 5.36, 6, 6.6, 6.9, 6.10, 6.12, 6.13, 6.14, 6.16, 6.18, 6.36, 6 .T, 9, 10.6, 10.9, 10.10, 10.12, 10.13, 10.14, 10.16, 10.18, 10.36, 10.T, 1 1, 12, 12.6, 12.9, 12.10, 12.12, 12.13, 12.14 , 12.16, 12.18, 12.36, 12.T, and their mixtures.
• copolyamides formed from the different types of monomers described above mention may be made of copolyamides resulting from the condensation of at least two alpha, omega-aminocarboxylic acids or two lactams or a lactam and of an alpha, omega-aminocarboxylic acid. Mention may also be made of the copolyamides resulting from the condensation of at least one alpha, omega-aminocarboxylic acid (or a lactam), at least one diamine and at least one dicarboxylic acid.
• copolyamides resulting from the condensation of an aliphatic diamine with an aliphatic dicarboxylic acid and of at least one other monomer chosen from aliphatic diamines different from the previous one and aliphatic diacids different from the previous one.
• the copolyamide according to the invention is copolyamide 6/1 1, copolyamide 6/12, copolyamide 6.6 / 1 1, copolyamide 6.6 / 12, copolyamide 6.10 / 1 1, copolyamide 6/12/1 1, copolyamide Pip.12 / 12, copolyamide 6 / 6.6 / 12, copolyamide 6 / Pip.12 / 12, or a combination thereof.
• X represents the number of carbon atoms derived from the amino acid or lactam residues.
• Numeral notations X / Y, PA Z.Z ’/ Y, etc. relate to copolyamides in which X, Y, Z. Z ’, etc. represent homopolyamide units as described above.
• the powder comprises at least 50% by mass of copolyamide.
• the powder comprises an amount of copolyamide greater than or equal to 55% by mass, or greater than or equal to 60% by mass, or greater than or equal to 65% by mass, or greater than or equal to 70 % by mass, or greater than or equal to 75% by mass, or greater than or equal to 80% by mass, or greater than or equal to 85% by mass, or greater than or equal to 90% by mass, or greater than or equal to 95 % by mass, or greater than or equal to 98% by mass, or greater than or equal to
• the copolyamide according to the invention has a melting temperature less than or equal to 160 ° C.
• the copolyamide has a melting temperature less than or equal to 150 ° C., more preferably a lower melting point of 145 ° C.
• the copolyamide can also have a melting temperature less than or equal to 155 ° C. 140 ° C, or less than or equal to 135 ° C, or less than or equal to 130 ° C, or less than or equal to 125 ° C.
• the powder according to the invention has an inherent viscosity greater than or equal to 0.8.
• it has an inherent viscosity greater than or equal to 0.9, and even more preferably greater than or equal to 1.
• the powder has an inherent viscosity greater than or equal to 0.85, or greater than or equal to 0.95, or greater than or equal to 1.05, or greater than or equal to 1, 1, or greater or equal to 1, 15, or greater than or equal to 1, 2, or greater than or equal to 1.25, or greater than or equal to 1, 3.
• the inherent viscosity is expressed in (g / 100 g) 1 .
• the volume median diameter Dv50 of the copolyamide-based particles of the powder is from 10 to 400 ⁇ m, more preferably from 50 to 200 ⁇ m.
• the Dv50 of the copolyamide-based particles of the powder of the invention can be from 10 to 50 ⁇ m, or from 50 to
• the Dv50 corresponds to the particle size at the 50 th percentile (in volume) of the cumulative distribution of particle sizes. It can be determined by laser particle size.
• the powder may also comprise, in addition to the copolymer having a melting temperature less than or equal to 160 ° C., a second polymer having a melting temperature lower than that of the copolyamide.
• this second polymer can allow better heat transfer to the powder and make it possible to improve the melting of the powder particles during the application of the coating.
• the particles of the second polymer may, during the coating process, melt before the particles of the copolyamide.
• the second molten polymer will then allow the particles of the copolyamide to agglomerate, which will improve their fusion. This will make it possible to obtain a coating with an increased thickness, compared to a coating obtained with a powder devoid of second polymer.
• the presence of this second polymer can make it possible to improve the adhesion of the coating to the surface, in particular if it is a metallic surface, and can also help to obtain a coating having a satisfactory aspect.
• the second polymer can be a second copolyamide, such as those mentioned above.
• the second copolyamide can be a copolyamide 6 / 6.6 / 1 1/12, a copolyamide 6/1 1, a copolyamide 6/12, a copolyamide 6.6 / 1 1, a copolyamide 6.6 / 12, a copolyamide 6.10 / 1 1, a copolyamide 6/12/1 1, a copolyamide Pip.12 / 12, a copolyamide 6 / 6.6 / 12, a copolyamide 6 / Pip.12 / 12, or a combination thereof.
• the second polymer can also be an epoxy resin.
• An example of epoxy resins which can be used in the invention is the sulfonamide resins. Mention may also be made, as epoxy resins which can be used in the invention, of the diglycidyl ethers of bisphenol A, the diglycidyl esters of bisphenol F, the glycidyl ethers of novolak resin, the cresolic novolak epoxy resins, the phenolic novolak epoxy resins, the epoxy resins alkylphenolic novolaks, acrylic epoxy resins, hydrogenated diglycidyl ethers of bisphenol A, hydrogenated diglycidyl ethers of bisphenol AD, polyol diglycidyl ethers such as propylene glycol or pentaerythrytol, epoxy resins obtained by the carboxylic acid reaction aliphatic or aromatic with epichlorohydrin, epoxy resins obtained by the reaction of an aliphatic or aromatic amine with epichlorohydrin, heterocyclic epoxy resin
• the second polymer can also be a mixture of these.
• the second polymer may have a melting temperature less than or equal to 155 ° C, or less than or equal to 150 ° C, ⁇ DI less than or equal to 145 ° C, or less than or equal to 140 ° C, or less than or equal to 135 ° C, or less than or equal to 130 ° C, or less than or equal to 125 ° C, or less than or equal to 120 ° C, or less than or equal to 1 15 ° C, or less than or equal to 1 10 ° C
• the second polymer at a melting temperature less than or equal to 130 ° C.
• the second polymer is present, relative to the total mass of the powder, in an amount less than or equal to 10% by mass, more preferably in an amount less than or equal to 5% by mass.
• the second polymer may be present, relative to the total mass of the powder, in a mass amount ranging from 0 to 1%, or from 1 to 2%, or from 2 to 3%, or from 3 to 4 %, or 4 to 5%, or 5 to 6%, or 6 to 7%, or 7 to 8%, or 8 to 9%, or 9 to 10%.
• the powder according to the invention can also comprise one or more additives chosen from the group consisting of pigments or dyes, anti-crater agents or spreading agents, reducing agents, antioxidants, reinforcing fillers, UV stabilizers, fluidizing agents, corrosion inhibitors, or mixtures thereof.
• additives are preferably present in a mass amount, relative to the total mass of the powder, from 0 to 30%, more preferably from 0 to 10%, even more preferably from 0 to 5%, for example from 0 to 5 %, or from 5 to 10%, or from 10 to 15%, or from 15 to 20%, or from 20 to 25%, or from 25 to 30%.
• the reinforcing filler can be of any type suitable for the preparation of powders based on polyamides.
• the filler be selected from the group consisting of talc, calcium carbonates, manganese carbonates, potassium silicates, aluminum silicates, dolomite, magnesium carbonates, quartz, boron nitride, kaolin, wollastonite, titanium dioxide, glass beads, mica, carbon black, mixtures of quartz, mica and chlorite, feldspar and nanometric dispersed fillers such as nanotubes carbon and silica.
• the filler is calcium carbonate.
• the pigment can be of any type known to those skilled in the art.
• the pigment is selected from the group consisting of titanium dioxide, carbon black, cobalt oxide, nickel titanate, molybdenum disulfide, aluminum flakes, iron oxide, zinc oxide, organic pigments, such as phthalocyanine and anthraquinone derivatives, and zinc phosphate.
• the dye can be of any type known to those skilled in the art.
• the dye according to the invention is selected from the group consisting of azo dyes, anthraquinone dyes, dyes derived from indigo, triarylmethane dyes, chlorine dyes and polymethine dyes.
• the anti-crater and / or spreading agent can be of any type known to a person skilled in the art.
• the anti-crater and / or spreading agent is selected from the group consisting of polyacrylate derivatives.
• the UV stabilizer may be of any type known to those skilled in the art.
• the UV stabilizer is selected from the group consisting of resorcinol derivatives, benzotriazoles, phenyltriazines and salicylates.
• Antioxidants can be of any type known to those skilled in the art.
• the antioxidants are selected from the group consisting of copper iodide combined with potassium iodide, phenol derivatives and hindered amines.
• the fluidizing agent may be of any type known to those skilled in the art.
• the fluidizing agent is selected from the group consisting of aluminas and silicas.
• Corrosion inhibitors can be of any type known to those skilled in the art.
• the corrosion inhibitors are selected from the group consisting of phosphosilicates and borosilicates.
• the powder according to the invention essentially consists, or consists, of the copolyamide, optionally the second polymer, and optionally one or more additives as described above.
• the invention also relates to a film capable of being obtained by melting the powder described above.
• the film has a thickness of 100 to 550 ⁇ m, more preferably 200 to 500 ⁇ m.
• the film is 100 to 150 ⁇ m thick, or 150 to 200 ⁇ m, or 200 to 250 ⁇ m, or 250 to 300 ⁇ m, or 300 to 350 ⁇ m, or 350 to 400 pm, or from 400 to 450 pm, or from 450 to 500 pm, or from 500 to 550 pm.
• the powder according to the invention can be prepared by the mixture of the constituents (that is to say copolyamide having a melting temperature less than or equal to 160 ° C. and any other constituents such as the second polymer having a temperature of lower than that of copolyamide, pigments or dyes, anti-crater agents or spreading agents, reducing agents, antioxidants, reinforcing fillers, UV stabilizers, fluidizing agents and corrosion inhibitors) to the molten state, in particular in a mixer.
• the powder contains only the copolyamide, it is melted.
• the mixture (or the copolyamide alone) is then ground after it has solidified.
• the constituents including the copolyamide having a melting temperature less than or equal to 160 ° C.
• the polymer constituents is mixed in the molten state and then ground after solidification.
• the particles obtained are then dry mixed with the other constituents in the form of a powder, for example the pigments.
• the temperature of the melt mixing step is between 150 and 300 ° C, more preferably between 180 and 270 ° C.
• the grinding can be carried out by any means.
• the grinding is selected from the group consisting of hammer grinding, knife grinding, disc grinding, air jet grinding and cryogenic grinding.
• the preparation process can also include a step of selecting the powder particles having the desired particle size.
• the invention relates to the use of a powder as described above for coating a surface.
• the surface can be coated in whole or in part.
• the coating has an inherent viscosity greater than or equal to 0.8 (g / 100 g) -1 .
• the inherent viscosity is determined as described above.
• the inherent viscosity of the coating may be different from that of the powder.
• the inherent viscosity of the coating may be higher than that of the powder, since one or more polymerization reactions may to some extent take place or resume upon application of the coating.
• the use of the powder according to the invention for coating a surface is distinguished from a use as a sealant or adhesive. Indeed, after application, the coating often forms a solid layer essentially not deformable. In addition, the coating is not used to bond two substrates together.
• the surface is preferably a metallic surface.
• metallic surface is meant a surface which comprises, consists essentially of or consists of, one or more metals.
• the metal surface can be of any type.
• the metal surface is the surface of a part selected from the group consisting of ordinary or galvanized steel parts, aluminum or aluminum alloy parts.
• the surface preferably metallic, more preferably surface of ordinary steel, aluminum or aluminum alloy part, could have undergone one or more of the surface treatments well known to those skilled in the art and preferably selected from the group consisting of coarse degreasing, alkaline degreasing, brushing, shot blasting or sandblasting, fine degreasing, hot rinsing, phosphating degreasing, iron / zinc phosphating / tri-cations, chromating, cold rinsing and chromic rinsing.
• the powder can be used for coating treated or untreated metal surfaces.
• the present invention is particularly advantageous for coating heat-sensitive surfaces, in particular heat-sensitive metal surfaces.
• thermalsensitive means: “capable of being altered by the application of temperatures above 250 ° C.”
• Such surfaces are for example surfaces comprising an alloy of zinc and aluminum. It can also be surfaces which have undergone a heat-sensitive treatment.
• the present invention may also allow the coating of surfaces liable to be altered by the application of temperatures below 250 ° C., for example the invention may allow the coating of surfaces liable to be altered by the application of higher temperatures at 230 ° C.
• the surface intended to be coated is selected from the group consisting of degreased, smooth or shot-blasted steel, degreased phosphated steel, phosphated iron or zinc steel, Sendzimir galvanized steel, electrogalvanized steel, l galvanized steel, cataphoresis treated steel, chromated steel, anodized steel, corundum sandblasted steel, degreased aluminum, smooth or shot-blasted aluminum, chromated aluminum, cast iron and all other metal alloy.
• the coating has an inherent viscosity greater than or equal to 0.85, or greater than or equal to 0.9, or greater than or equal to 0.95, or greater than or equal to 1.05, or greater than or equal to 1, or greater than or equal to 1, 1, or greater than or equal to 1.15, or greater than or equal to 1.2 , or greater than or equal to 1.25, or greater than or equal to 1.3.
• the inherent viscosity is expressed in (g / 100 g) - 1 .
• the coating is a film 100 to 550 ⁇ m thick, more preferably 200 to 500 ⁇ m thick.
• the film is 100 to 150 ⁇ m thick, or 150 to 200 ⁇ m, or 200 to 250 ⁇ m, or 250 to 300 ⁇ m, or 300 to 350 ⁇ m, or 350 to 400 pm, or from 400 to 450 pm, or from 450 to 500 pm, or from 500 to 550 pm.
• the subject of the invention is also a method of coating a surface comprising the following steps:
• the powder can be applied to or brought into contact with a surface according to numerous coating techniques well known to those skilled in the art.
• the coating according to the invention is produced by a method selected from the group consisting of soaking in a fluidized bed, electrostatic spraying and hot dusting.
• the coating can in particular be produced by soaking in a fluidized bed.
• the step of bringing the surface into contact with the powder may include the steps of:
• the surface to be coated is preheated to a temperature allowing the powder according to the invention to melt.
• the surface is then immersed in a fluidized bed comprising a powder according to the invention.
• the powder melts on contact with the surface and forms a coating on it.
• the coated surface is then preferably cooled, for example with ambient air.
• the fluidized air for fluidizing the composition is cold, clean and free of oil.
• the surface heating temperature is less than or equal to 250 ° C, more preferably less than or equal to 230 ° C.
• the surface heating temperature can be from 150 to 250 ° C, preferably from 170 to 230 ° C. More preferably, the heating of the surface is carried out at a temperature at least 30 ° C higher than the melting temperature of the copolyamide, more preferably at a temperature higher than 30 to 120 ° C than the melting temperature of the copolyamide.
• the duration of soaking the surface in the fluidized bed is from 1 to 10 seconds, more preferably from 3 to 7 seconds.
• the soaking of the surface in the fluidized bed can take place one or more times (each soaking preferably having a duration of 1 to 10 s, more preferably 3 to 7 s).
• the coating can be produced by electrostatic spraying.
• the step of bringing the surface into contact with the powder can then include the steps of:
• Electrostatic spray coating consists of depositing electrostatically charged powder particles on a surface, in particular at room temperature.
• the powder can be electrostatically charged as it passes through the nozzle of spraying equipment.
• the composition thus loaded can then be projected onto the object comprising the surface to be coated which is connected to a zero potential.
• the coated object can then be placed in an oven at a temperature allowing the composition to melt.
• the material allowing the projection (or spraying) of the powder can be of any type.
• the nozzle is brought to a high potential of between ten and one hundred kilovolts, of negative or positive polarity.
• the material allowing the projection of the powder is an electrostatic gun which charges the powder by Corona effect and / or by triboelectrification.
• the flow rate of powder in the spraying equipment is from 10 to 200 g / min, and more preferably, from 50 to 120 g / min.
• the electrostatic application temperature of the powder is 15 to 25 ° C.
• the residence time of the surface in the oven is 3 to 15 minutes.
• the heating temperature of the surface covered with powder can be less than or equal to 250 ° C., more preferably less than or equal to 230 ° C.
• the surface heating temperature can be from 150 to 250 ° C, preferably from 170 to 230 ° C.
• the heating temperature of the powder-coated surface may preferably be at least 30 ° C higher than the melting temperature of the copolyamide, more preferably 30 to 60 ° C higher than the melting temperature of the copolyamide.
• the surface can then be cooled, for example to room temperature.
• the coating is made by hot dusting.
• the step of bringing the surface into contact with the powder then comprises the steps of:
• the heating temperature of the surface can be as described above in relation to the coating by soaking in a fluidized bed. It is in particular preferably at least 30 ° C higher than the melting temperature of the copolyamide, more preferably 30 to 120 ° C higher than the melting temperature of the copolyamide.
• the surface can then be cooled, for example to room temperature.
• the powder sprayed can be charged electrostatically or not.
• the invention relates to an object comprising a surface covered with a coating capable of being obtained by melting the powder as described above.
• This object is preferably intended:
• the raw materials i.e. copolyamides
• the medium is inerted by creating a vacuum and introducing nitrogen 4 times in succession.
• the medium is then stirred and heated under autogenous pressure at a temperature of 280 ° C, for 3 h.
• FU an expansion at atmospheric pressure is applied according to a ramp in 2 h, the temperature being gradually lowered to 230 ° C.
• the medium is then stirred under nitrogen sweep and increases in viscosity until reaching the stirring torque longed for.
• the medium is then drained through a die in the form of a rod in a water tank, then in a granulator.
• the granules are then freeze-ground in the form of powder.
• the Dv50 is 100 pm.
• compositions Preparation of the compositions (coating powders):
• compositions are prepared, by dry mixing of the components in the quantities (indicated in parts) specified in the table below:
• Pip piperazine.
• the polyamides used have the following melting temperatures and inherent viscosities:
• a coating is deposited on a metal by soaking in a fluidized bed with the various compositions (powders) described above.
• the thickness of the coating is determined.
• the inherent viscosity is measured as described above.
• the gloss is measured according to ISO 2813.
• the breaking stress, the flow threshold and the elongation at break are measured according to ISO 527-3.
• compositions 11 and 12 correspond to counterexamples.
• the coating film obtained is brittle and does not have good mechanical properties. It is also noted that the application of a coating at low temperature (230 ° C) is not possible when the coating powder is a polyamide powder with relatively high melting point (186 ° C).

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Health & Medical Sciences (AREA)
• Engineering & Computer Science (AREA)
• Life Sciences & Earth Sciences (AREA)
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• Manufacturing & Machinery (AREA)
• Proteomics, Peptides & Aminoacids (AREA)
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• 2018
  • 2018-10-24 FR FR1859818A patent/FR3087775B1/fr active Active
• 2019
  • 2019-10-23 EP EP19813378.7A patent/EP3870665A1/fr active Pending
  • 2019-10-23 TW TW108138286A patent/TW202033609A/zh unknown
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