EP3529318A1 - Self-adhesive composition for coating metal surfaces - Google Patents
Self-adhesive composition for coating metal surfacesInfo
- Publication number
- EP3529318A1 EP3529318A1 EP17797703.0A EP17797703A EP3529318A1 EP 3529318 A1 EP3529318 A1 EP 3529318A1 EP 17797703 A EP17797703 A EP 17797703A EP 3529318 A1 EP3529318 A1 EP 3529318A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- composition
- metal surface
- coating
- weight
- copolyamide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
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- 238000000576 coating method Methods 0.000 title claims description 74
- 229910052751 metal Inorganic materials 0.000 title claims description 67
- 239000002184 metal Substances 0.000 title claims description 67
- 239000011248 coating agent Substances 0.000 title claims description 57
- 239000000853 adhesive Substances 0.000 title abstract description 3
- 229920002647 polyamide Polymers 0.000 claims abstract description 64
- 239000004952 Polyamide Substances 0.000 claims abstract description 56
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 26
- 239000000843 powder Substances 0.000 claims abstract description 22
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- 238000002844 melting Methods 0.000 claims description 20
- 230000008018 melting Effects 0.000 claims description 20
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 13
- 229920006017 homo-polyamide Polymers 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
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- 230000007797 corrosion Effects 0.000 claims description 6
- 238000005260 corrosion Methods 0.000 claims description 6
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- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 2
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- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003873 salicylate salts Chemical class 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001612 separation test Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229960005137 succinic acid Drugs 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 239000001003 triarylmethane dye Substances 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
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
- C09D5/03—Powdery paints
- C09D5/033—Powdery paints characterised by the additives
-
- 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
- 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
- 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
- C09D7/65—Additives macromolecular
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
Definitions
- the invention relates to a self-adhering polyamide-based powder composition for coating metal surfaces.
- Metal surface coating is widely used in industry and has a wide variety of applications, including automotive, fluid transfer, electrical and electronic industries.
- Polyamides are commonly used for coating metal surfaces.
- adhesion primer an underlayer
- the international application WO 2008/029070 describes a self-adhering polyamide-based powder composition for coating metal surfaces, which does not require a primer.
- the adhesion is obtained thanks to a coating having a dry and / or wet modulus greater than or equal to 2200 MPa [NF EN ISO 527 standard], this module being itself affected by the presence of a high amount of charges in the composition.
- this high level of charge makes the coating brittle when dry. It is therefore an object of the present application to provide a polyamide-based composition for the coating of metal surfaces devoid of these defects. Summary of the invention
- the present invention results from the unexpected demonstration by the inventors that the addition of a hydrophobic agent, combined with an adhesion promoter of the ethylene-vinyl alcohol copolymer type, with a polyamide-based pulverulent composition, not having an epoxy and having a low charge ratio, allowed to obtain a metal surface coating having excellent adhesion and flexibility before and after immersion in water at 50 ° C for several weeks without modification the appearance of the coating.
- the present invention relates to a self-adhering powder composition
- a self-adhering powder composition comprising:
- the self-adhering powdery composition comprises:
- the composition according to the invention comprises: at least one homopolyamide and / or one copolyamide, and
- composition according to the invention comprises:
- At least one hydrophobic agent at least one load.
- composition according to the invention comprises:
- the base polyamide (PA) of the composition said composition according to the invention containing from 55 to 98.5% of PA homopolyamide and / or copolyamide, and said copolyamide present, if appropriate, in this PA of base having a melting point above 150 ° C.
- the melting temperature or melting point (Tf) of the copolyamide is measured according to ISO Standard 1,1357-3 Plastics - Differential scanning calorimetry (DSC) Part 3.
- the composition comprises less than 20% by weight of filler, preferably comprises from 0.01 to 12% by weight, preferably from 3 to 8% by weight, of filler relative to the total weight of the composition, in which the composition charge is preferably calcium carbonate.
- composition according to the invention does not comprise an epoxy compound.
- the present invention also relates to the use of a composition as defined above for coating a metal surface.
- the metal surface has not previously been coated with a layer of adhesion primer.
- the present invention also relates to a method of coating a metal surface, comprising a step of contacting a metal surface with a composition as defined above.
- the coating method according to the invention comprises the following steps:
- the coating method according to the invention comprises the following steps:
- the coating method according to the invention comprises the following steps:
- the coating method according to the invention does not include a step of coating the metal surface with a layer of adhesion primer prior to its contact with the composition.
- the present invention also relates to a material comprising a metal surface, the metal surface being coated with a coating obtained by melting a composition as defined above.
- the present invention also relates to a method of manufacturing a composition as defined above, comprising the following steps:
- the term “comprising” means “including”, “containing” or “encompassing”, that is to say that when an object “includes” one or more elements, d other elements than those mentioned can also be included in the object.
- the expression “consisting of” means “consisting of”, that is, when an object “consists of” one or more elements, the object can not include other elements than those mentioned.
- polyamide refers to any condensation product of lactam (s), amino acid (s) or diacid (s) and diamine (s) and, as a general rule, any polymer formed by units interconnected by amide functions.
- Polyamides are well known to those skilled in the art.
- the polyamide according to the invention may be a homopolyamide and / or a copolyamide (coPA). In the case where the polyamide comprises at least two different monomers, it forms a copolyamide.
- the term "monomer” in the present description of polyamides should be understood as “repetitive unit”. Indeed, the case where a repeating unit of the PA consists of the combination of a diacid with a diamine is particular.
- diacid in equimolar quantity, which corresponds to the monomer. This is because, individually, the diacid or diamine is only one structural unit, which is not sufficient on its own to polymerize.
- said polyamide powder comprises at least one monomer chosen from aminocarboxylic acids, preferably alpha, omega-aminocarboxylic acids, comprising from 4 to 18 carbon atoms, diamine pairs. diacid comprising from 4 to 36 carbon atoms, lactams comprising from 3 to 18 carbon atoms, and mixtures thereof.
- said polyamide-based particles comprise at least one polyamide and / or at least one copolyamide and / or their mixtures.
- copolyamide abbreviated as COPA
- COPA copolyamide
- amino-acid or aminocarboxylic acid monomers and preferably alpha, omega-aminocarboxylic acids
- Lactam type monomers having from 3 to 18 carbon atoms on the main ring and may be substituted;
- diacid derived from the reaction between an aliphatic diamine having 4 and 36 carbon atoms, preferably 4 to 18 carbon atoms and a dicarboxylic acid having 4 and 36 carbon atoms, preferably 4 to 18 carbon atoms ;
- alpha, omega-amino acids By way of examples of alpha, omega-amino acids, mention may be made of those having from 4 to 18 carbon atoms, such as aminocaproic acid, 7-aminoheptanoic acid, 1-aminoundecanoic acid, N-heptyl-11-aminoundecanoic acid and 12-Aminododecanoic.
- lactams include those having from 3 to 18 carbon atoms on the main ring and may be substituted. Examples that may be mentioned include ⁇ , ⁇ -dimethylpropriolactam, ⁇ , ⁇ -dimethylpropriolactam, amylolactam, caprolactam also known as lactam 6, capryllactam also known as lactam 8, oenantholactam and lauryllactam, also known as lactam 12.
- dicarboxylic acid there may be mentioned acids having 4 and 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) HOOC- (CH2) 10-COOH dodecanedioic acid, 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 salt of
- dimerized fatty acids or dimerized fatty acids are understood to mean the product of the fatty acid dimerization reaction (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 Cl 8 monoacids, from 60 to 99% of C36 diacids, and from 0.2 to 35% of C 54 or more triacids or polyacids.
- diamine there may be mentioned aliphatic diamines having from 4 to 36 atoms, preferably from 4 to 18 atoms, which may be aryl and / or saturated cyclic.
- hexamethylenediamine piperazine (abbreviated "Pip"), aminoethylenepiperazine, tetramethylenediamine, octamethylenediamine, decamethylene diamine, dodecamethylenediamine, 1,5 diaminohexane, , 2,4-trimethyl-1,6-diamino-hexane, diamine polyols, isophorone diamine (IPD), methyl pentamethylenediamine (MPMD), bis (aminocyclohexyl) methane (BACM), bis (3-methyl) 4-aminocyclohexyl) methane (BMACM), methaxylyenediamine, and bis-p-aminocyclohexylmethan
- diamines As an example of diamines. diacids, 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 6 at 36 carbon atoms.
- monomers of the type "diamine. diacid” include, in particular, the monomers: 6.6, 6.10, 6.1 1, 6.12, 6.14, 6.18. Mention may be made of the monomers resulting from the condensation of decanediamine with a C6 to C36 diacid, especially the monomers: 10.10, 10.12, 10.14, 10.18.
- the polyamide powders of the invention comprise at least one polyamide chosen from polyamides and copolyamides comprising at least one of the following monomers: 4.6, 4.T, 5.6, 5.9, 5.10, 5.12, 5.13, 5.14, 5.1.
- diacid according to the invention is selected from the group resulting from the condensation between, on the one hand (for X) hexamethylenediamine and / or decanediamine and / or dodecanediamine and, on the other hand (for Y) hexamethylenediacid and / or sebacic acid and / or dodecanedioic acid.
- composition according to the invention comprises at least one homopolyamide selected from the group consisting of PA 10.10, PA1 1 and PA12.
- PA10, PA1 1 and PA12 are well known to those skilled in the art.
- the PA10.10 according to the invention results in particular from the condensation of decanediamine with sebacic acid, a natural fatty acid obtained from castor oil.
- PA 10.10 according to the invention available commercially, it is possible to mention the Hiprolon® brand products from Arkema, such as Hiprolon® 200.
- the PA 1 1 according to the invention is a polyundecanamide resulting in particular from the condensation of 11-aminoundecanoic acid, an amino acid derived from castor oil.
- PA 1 1 according to the invention it is possible to cite the Rilsan® brand products from Arkema such as Rilsan® PA 1 1 BMNO and Rilsan® PA 1 1 BMFO.
- PA 12 according to the invention is a polylauramide resulting in particular from the condensation of lactam 12 or lauryllactam.
- PA 12 according to the invention it is possible to mention the Rilsamid® and Rilsan® range products from Arkema.
- copolyamides formed from the various types of monomers described above mention may be made of the copolyamides resulting from the condensation of at least two alpha, omega-aminocarboxylic acids or two lactams or a lactam and 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 e ⁇ of at least one other monomer chosen from aliphatic diamines different from the preceding one and aliphatic diacids different from the preceding one.
- copolyamides examples include copolymers of caprolactam and lauryllactam (PA 6/12), copolymers of caprolactam, hexamethylenediamine and adipic acid (PA 6 / 6.6), copolymers of caprolactam , lauryllactam, hexamethylenediamine and adipic acid (PA 6/12 / 6.6), copolymers of caprolactam, hexamethylenediamine and azelaic acid, 1-aminoundecanoic acid, and lauryllactam, ( PA 6 / 6.9 / 1 1/12), copolymers of caprolactam, adipic acid and hexamethylenediamine, 1 1 -aminoundecanoic acid, lauryllactam (PA 6 / 6.6 / 1 1/12), copolymers hexamethylene diamine, azelaic acid, and lauryllactam (PA 6.9 / 1 1/12), cop
- PA 6 / 6.6 / 12 whose mass ratios in corresponding monomers can be (in percentage): 40/20/40, 35/20/45, 45/35/20, 30/30/40, 22/18/60 40/25/35;
- PA 6 / 6.6 / 1 1/12 whose mass ratios in corresponding monomers can be for example (in percentage): 30/15/10/45, 30/20/20/30, or 15/25/25/35 ;
- copolyamides examples include those marketed under the name Platamid® and Platamid® Rnew by ARKEMA, Vestamelt® by Evonik, and Griltex® by EMS.
- the polyamide used in the present invention comprises at least one copolyamide chosen from: PA 6 / 6.6 / 12, PA 6 / 6.6 / 1 1/1 2, PA 6/1 2, PA 6.9 / 12, PA Pip. 9 / Pip.I 2/1 1, PA 6 / IPD.6 / 1 2, PA IPD.9 / 1 2, PA6 / MPMD.1 2/12, PA 6 / 6.12 / 1 2, PA 6 / Pip. 1 2/12, PA 6 / 6.6 / 6.10 / 6.1, PA 6.10 / Pip.1.0 / Pip.1.2, PA 6/1 1/12, PA Pip. 1 2/12, PA IPD.l 0/1 2, PA Pip.l 0/1 2, PA 6/1 1, PA Pip. 1 0/1 1 /Pip.9, PA 6 / 6.6 / 6.1 0, and in particular those whose mass ratios are defined above, and mixtures of these copolyamides.
- the melting point of the preferred COPA additives of the composition according to the invention is generally in the range of 80 to 150 ° C, preferably 100 to 130 ° C.
- self-adhesive pulverulent composition refers to a composition in the form of powder particles which can adhere to a surface without the addition of additional compounds.
- the ethylene-vinyl alcohol copolymer results from the condensation of polyethylene and polyvinyl alcohol.
- the ethylene-vinyl alcohol copolymer according to the invention is used in particular as an adhesion promoter.
- an ethylene-vinyl alcohol copolymer according to the invention it is possible to mention the Evasin products from Arkema, such as Evasin 3251 F and Evasin 4405F.
- the hydrophobic agent according to the invention possibly of all types known to those skilled in the art.
- the hydrophobic agent is a wax, especially selected from the group consisting of polyethylene waxes and / or polypropylene and / or ethylene bis stearamide.
- hydrophobing agent according to the invention mention may be made of those of the Ceridust (Clariant) brand or those of the Crayvallac (Arkema) brand.
- the composition according to the invention comprises at least one filler.
- the filler according to the invention may be of any type suitable for the preparation of compositions based on polyamides. However, it is preferred that the filler be selected from the group consisting of talc, calcium carbonates, manganese carbonates, potassium silicates, aluminum silicates, dolomite, magnesium carbonates, quartz, nitride. boron, kaolin, wollastonite, titanium dioxide, glass beads, mica, carbon black, mixtures of quartz, mica and chlorite, feldspar and dispersed nanometric fillers such as carbon nanotubes and silica. In a particularly preferred manner, the filler according to the invention is calcium carbonate.
- composition according to the invention comprises less than 30% by weight, more preferably less than 20% by weight, and even more preferably less than 10% by weight, of charge, the charge preferably consisting of calcium carbonate.
- the composition according to the invention further comprises at least one additional agent selected from the group consisting of a pigment, a dye, an anti-crater and / or spreading agent, a reducing agent, an antioxidant, a UV stabilizer, a fluidizing agent and a corrosion inhibitor.
- at least one additional agent selected from the group consisting of a pigment, a dye, an anti-crater and / or spreading agent, a reducing agent, an antioxidant, a UV stabilizer, a fluidizing agent and a corrosion inhibitor.
- the pigment according to the invention may be of any type known to those skilled in the art.
- the pigment according to the invention is selected from the group consisting of titanium dioxide, carbon black, cobalt oxide, nickel titanate, molybdenum disulfide, aluminum flake, oxide iron, zinc oxide, organic pigments, such as phthalocyanine and anthraquinone derivatives, and zinc phosphate.
- the dye according to the invention may 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 may be of any type known to those skilled in the art.
- the anti-cratering and / or spreading agent according to the invention is selected from the group consisting of polyacrylate derivatives.
- the UV stabilizer according to the invention is selected from the group consisting of resorcinol derivatives, benzotriazoles, phenyltriazine and salicylates.
- the antioxidants according to the invention may be of any type known to those skilled in the art.
- the antioxidants according to the invention are selected from the group consisting of copper iodide combined with potassium iodide, phenol derivatives and hindered amines.
- the fluidizing agent according to the invention 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.
- the corrosion inhibitors according to the invention may be of any type known to those skilled in the art.
- the corrosion inhibitors according to the invention are selected from the group consisting of phosphosilicates and borosilicates.
- the powder particles of the composition may have a spherical, spheroidal or nonspherical shape.
- the particle size of the pulverulent composition according to the invention is between 5 ⁇ and 1 mm, more preferably between 10 and 800 ⁇ and even more preferably between 80 and 200 ⁇ .
- the term "particle size” refers to the average diameter or D50 of the powder particles of the composition. In the context of this description, the term “diameter” is used to describe the diameter of the circumscribed circle of the particles.
- the D50 is the value of the particle size that divides the analyzed particle population into exactly two. In other words, 50% of the particles are smaller than the D50.
- the D50 is measured according to ISO 9276 - Parts 1 to 6: "Representation of data obtained by particle size analysis".
- a laser granulometer for example of the Malvern type
- the term "between” refers to a range including the cited boundaries.
- the composition is preferably carried out by mixing the constituents in the molten state, in particular in a kneader, and then grinding the mixture after its solidification. It is then possible to select the powder particles of the composition thus formed having a desired particle size.
- the powder particles having a particle size of between 5 ⁇ and 1 mm, more preferably between 10 and 800 ⁇ and even more preferably between 80 and 200 ⁇ , are selected.
- the temperature of the mixing step is between 150 and 300 ° C, more preferably between 180 and 270 ° C.
- grinding according to the invention can be carried out by any means.
- grinding according to the invention is selected from the group consisting of hammer milling, knife milling, disk milling, air jet milling and cryogenic milling.
- composition according to the invention is preferably used for coating metal surfaces.
- composition according to the invention can be applied to or contacted with a metal surface according to many coating techniques well known to those skilled in the art.
- the coating according to the invention is made by a method selected from the group consisting of fluidized bed dipping, electrostatic spraying and hot dusting.
- Fluidized bed dipping coating is well known to those skilled in the art.
- the metal surface to be coated is preheated to a temperature permitting the melting of the composition according to the invention.
- the metal surface is then immersed in a fluidized bed comprising a composition according to the invention.
- the composition according to the invention melts in contact with the object and forms a coating thereon.
- the coated object is then cooled in ambient air.
- the granulometry of the composition during a dip coating in a fluidized bed is between 10 and ⁇ ⁇ , and preferably between 80 and 200 ⁇ .
- the fluidized air for the fluidization of the composition is cold, clean and free of oil.
- the heating temperature of the metal surface is between 200 and 500 ° C, and preferably between 300 and 400 ° C.
- the soaking time of the metal surface in the fluidized bed is between 1 and 10 seconds, more preferably between 3 and 5 seconds.
- the thickness of the coating obtained by dipping in a fluidized bed is between 150 and 1000 ⁇ , and preferably between 200 and 700 ⁇ . It will be apparent to those skilled in the art that a thicker coating can be obtained by increasing the soaking time or by performing several successive soaks in the fluidized bed.
- Electrostatic spray coating is well known to those skilled in the art.
- the electrostatic spraying coating consists in depositing powder particles of the composition according to the invention electrostatically charged onto a metal surface, especially at room temperature.
- the composition according to the invention can be electrostatically charged during its passage through the nozzle of a projection equipment.
- the composition thus charged can then be projected on the object comprising the metal surface to be coated which is connected to a zero potential.
- the coated object can then be placed in an oven at a temperature to melt the composition.
- the material for the projection of the composition according to the invention can be of any type.
- the nozzle is brought to a high potential of between ten and a hundred kilovolts, of negative or positive polarity.
- the material allowing projection of the composition according to the invention is an electrostatic gun which charges the composition according to the invention by Corona effect and / or by triboelectrification.
- the particle size of the composition during an electrostatic spraying coating is between 5 and 100 ⁇ and, preferably, between 5 and 65 ⁇ .
- the powder flow rate in the blasting material is between 10 and 200 g / min, and more preferably between 50 and 120 g / min.
- the electrostatic application temperature of the powder is between 15 and 25 ° C.
- the residence time of the metal part in the oven is between 3 and 15 minutes.
- the melting temperature of the composition is from 200 to 250 ° C, more preferably from 210 to 220 ° C.
- the thickness of the coating obtained is preferably between 50 and 200 ⁇ , and more preferably between 80 and 150 ⁇ .
- the hot powdering generally comprises a step of spraying the composition according to the invention on a metal surface previously heated to a temperature permitting the melting of the composition.
- the part can then be cooled to room temperature.
- the thickness of the coating obtained by hot powdering is preferably between 200 and 1000 ⁇ , and preferably between 200 and 700 ⁇ .
- the sprayed composition during hot powdering can be electrostatically charged or not.
- the metal surface to be coated according to the invention can be of any type.
- the metal surface according to the invention is selected from the group consisting of ordinary or galvanized steel parts, aluminum parts or aluminum alloy.
- the metal surface of ordinary steel, aluminum or aluminum alloy could undergo one or more surface treatments well known to those skilled in the art and selected from the group consisting of a coarse degreasing, an alkaline degreasing , brushing, shot blasting or sandblasting, fine degreasing, hot rinsing, phosphating degreasing, iron / zinc / tri-cation phosphating, chromating, cold rinse and a chromic rinse.
- the metal surface to be coated according to the invention is selected from the group consisting of degreased steel, smooth or blasted, phosphated defatted steel, iron or zinc phosphated steel, Sendzimir galvanized steel, electro-galvanized steel, bath-galvanized steel, cataphoresis-treated steel, chromated steel, anodized steel, corundum sanded steel, defatted aluminum, smooth or blasted aluminum, aluminum chromate, cast iron and any other metal alloy.
- the material comprising a metal surface according to the invention is preferably intended for any market for which a metal part is coated.
- the material comprising a metal surface according to the invention is preferably intended:
- PA 1 polyamide 1 1 (PAU) Rilsan® (BMNO) (Arkema);
- PA 2 polyamide 1 1 (PA) Rilsan® (BMNO) (Arkema);
- CoPA PA 80/20 molar ratio IPD.10 / 12, copolyamide Platamid® (Arkema);
- EVOH 1 ethylene-vinyl alcohol copolymer comprising 32 mol% of ethylene (Evasin 3251 F) (Arkema);
- EVOH 2 ethylene-vinyl alcohol copolymer comprising 44 mol% of ethylene (Evasin 4405F) (Arkema);
- Palmarole AOOH 98 (Adeka Palmarole);
- Anti-scratch additive based on polyacrylate Byk-360-P (Byk);
- CaCO3 (Atomite, Imerys);
- Hydrophobic agent micronized wax of modified amide polypropylene (Ceridust wax 6721 from Clariant);
- E1 and E2 are examples according to the invention.
- C2 and C3 are comparative examples.
- C3 represents a composition according to the international patent application WO2008 / 029070. 1 .2. Preparation of compositions
- the constituents are mixed in an extruder at a temperature between 180 ° C and 300 ° C.
- the mixing time is adapted so that the mixture is homogeneous.
- the mixture is milled in a cryogenically cooled apparatus to obtain the desired particle size for application by a fluidized bed coating method having a mean diameter (D50) of about 100 ⁇ .
- the powder particles obtained are selected by sieving.
- compositions are used in a fluidized bed dipping coating process. Prior to the application of the composition, 100x100x3 mm steel plates are degreased and shot blasted. The steel plates are then heated for 10 minutes at 330 ° C and then quenched in the fluidized bed for 4 seconds. The coated plates are then cooled in ambient air.
- the metal substrate coating plays a role in protecting the metal against external aggressions. This protection is effective only if the adhesion to the metal is retained even when the coating is in prolonged contact with the water, which is why an adhesion test after immersion in water has been carried out.
- the abrasion resistance, impact and cathodic separation tests are conventional mechanical tests used in various international standards to characterize in particular the resistance to aging of coatings.
- Adhesion of the coating is evaluated after immersion in water at different temperatures.
- the adhesion test consists of a peel test of a sectioned strip in the coating and an evaluation of the peel strength. The test is performed at a temperature of 23 ° C ⁇ 2 ° C and a relative humidity of 50% ⁇ 10%. Using a sharp tool, cut the coating (to the metal) along two straight lines 10mm apart and of sufficient length to define a strip of at least 30mm length.
- a score of 0 to 4 is given as follows:
- the test consists in measuring the mass of coating abraded after 1000 cycles of rotation of the wheels Cs-17, with a weight of 1 kg.
- An impact resistance test according to the ASTM G14 standard has been carried out: it consists in evaluating the mechanical resistance of the coating following the fall of a metal ball (diameter and weight defined by the standard) of a certain height and evaluate the integrity of the coating after the ball has dropped by means of a low-voltage electrical detector (as described in ASTM G62 under the name "Low Voltage Holiday Detector.” The result is expressed in Joules. 1 .4.5. Cathodic detachment test (Australian standard).
- test is performed according to AS / NZS 4352, using test cell A or B at 23 ° C for 28 days.
- the test makes it possible to determine the ability of the coating applied to metallic substrates to resist cathodic detachment when the surface coating is likely to have discontinuities.
- compositions according to the invention have performances similar to those of the state of the art (C3) with significantly lower loading amounts.
- the comparison with Cl and C2 establishes that the presence of the hydrophobic agent makes it possible to explain these performances.
- the comparison of E2 with E1 shows that the presence of copolyamide, with a melting point in the range of 80 to 150 ° C according to the invention, makes it possible to improve the performance of the compositions according to the invention under the conditions of more drastic (immersion for 4 days in water at 70 ° C).
- the coating therefore has excellent abrasion resistance comparable to that of polyamide-based coatings 1 1. It allows in particular to comply with various international standards defining the properties of coatings for metals in contact with water, including drinking.
- the coating therefore has excellent impact resistance, similar to that of polyamide-based coatings 1 1. It allows in particular to comply with various international standards defining the properties of coatings for metals in contact with water, including drinking. 2.4. Cathodic detachment test (Australian standard)
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paints Or Removers (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1660302A FR3057875B1 (en) | 2016-10-24 | 2016-10-24 | SELF-ADHESIVE COMPOSITION FOR COATING METAL SURFACES |
PCT/FR2017/052929 WO2018078275A1 (en) | 2016-10-24 | 2017-10-24 | Self-adhesive composition for coating metal surfaces |
Publications (1)
Publication Number | Publication Date |
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EP3529318A1 true EP3529318A1 (en) | 2019-08-28 |
Family
ID=57485799
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP17797703.0A Withdrawn EP3529318A1 (en) | 2016-10-24 | 2017-10-24 | Self-adhesive composition for coating metal surfaces |
Country Status (6)
Country | Link |
---|---|
US (1) | US11667797B2 (en) |
EP (1) | EP3529318A1 (en) |
JP (1) | JP2019535852A (en) |
CN (1) | CN109863211A (en) |
FR (1) | FR3057875B1 (en) |
WO (1) | WO2018078275A1 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR3087775B1 (en) * | 2018-10-24 | 2022-12-02 | Arkema France | LOW MELTING TEMPERATURE COPOLYAMIDE POWDERS |
EP3851211A1 (en) * | 2020-01-14 | 2021-07-21 | Triarca A/S | Surface coating of electrical enclosures |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5144970B2 (en) * | 1972-05-29 | 1976-12-01 | ||
FR2707659B1 (en) * | 1993-06-30 | 1995-09-22 | Atochem Elf Sa | Polyamide-based powder composition for coating metallic substrates. |
FR2731005B1 (en) | 1994-12-29 | 1997-04-04 | Atochem Elf Sa | POLYAMIDE-BASED POWDER COMPOSITION FOR COATING METALLIC SUBSTRATES |
DE69704007T2 (en) | 1996-07-23 | 2001-06-07 | Atofina, Puteaux | Self-adhesive compositions with improved adhesion for coating metal substrates |
FR2751661B1 (en) * | 1996-07-23 | 1998-09-18 | Atochem Elf Sa | SELF-ADHESIVE COMPOSITIONS WITH IMPROVED FLOW RESISTANCE FOR USE IN THE COATING OF METAL SUBSTRATES |
JPH11269281A (en) * | 1998-03-20 | 1999-10-05 | Teijin Ltd | Hydrophilic film |
DE19823426A1 (en) * | 1998-05-26 | 1999-12-02 | Degussa | Electrostatic powder lacquer based on (co)polyamide for coating metal |
JP2001151918A (en) * | 1999-12-01 | 2001-06-05 | Yupo Corp | Porous resin film |
GB0002844D0 (en) * | 2000-02-08 | 2000-03-29 | Int Coatings Ltd | Powder coating compositions |
DE10216118A1 (en) * | 2002-04-12 | 2004-04-22 | Clariant Gmbh | Use of metallocene waxes in powder coatings |
JP2004288400A (en) * | 2003-03-19 | 2004-10-14 | Mitsui Chemicals Inc | Fuel cell |
FR2905700B1 (en) * | 2006-09-08 | 2008-11-14 | Arkema France | HIGH PERFORMANCE AUTOADHERENT POWDER WITHOUT ADHESION PROMOTER BASED ON POLYAMIDE |
FR2934864B1 (en) * | 2008-08-08 | 2012-05-25 | Arkema France | SEMI-AROMATIC POLYAMIDE WITH CHAIN TERMINATION |
DE102009026988A1 (en) | 2009-05-27 | 2010-12-02 | Evonik Degussa Gmbh | Hybrid components with reactive hot melt adhesives |
EP2359806A1 (en) | 2009-12-18 | 2011-08-24 | L'oreal S.A. | Composition containing an aqueous dispersion of polyurethane and an oil-soluble polar modified polymer |
CN105524536A (en) | 2015-12-25 | 2016-04-27 | 德清县金秋塑粉有限公司 | Powdery coating for automobile springs |
-
2016
- 2016-10-24 FR FR1660302A patent/FR3057875B1/en not_active Expired - Fee Related
-
2017
- 2017-10-24 US US16/344,268 patent/US11667797B2/en active Active
- 2017-10-24 JP JP2019522267A patent/JP2019535852A/en active Pending
- 2017-10-24 CN CN201780065861.XA patent/CN109863211A/en active Pending
- 2017-10-24 EP EP17797703.0A patent/EP3529318A1/en not_active Withdrawn
- 2017-10-24 WO PCT/FR2017/052929 patent/WO2018078275A1/en active Application Filing
Also Published As
Publication number | Publication date |
---|---|
US11667797B2 (en) | 2023-06-06 |
FR3057875A1 (en) | 2018-04-27 |
US20190264037A1 (en) | 2019-08-29 |
JP2019535852A (en) | 2019-12-12 |
CN109863211A (en) | 2019-06-07 |
WO2018078275A1 (en) | 2018-05-03 |
FR3057875B1 (en) | 2020-06-12 |
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