EP2747903B1 - Utensil mit einer antihaftbeschichtung mit verbesserten eigenschaften zur anhaftung am untergrund - Google Patents
Utensil mit einer antihaftbeschichtung mit verbesserten eigenschaften zur anhaftung am untergrund Download PDFInfo
- Publication number
- EP2747903B1 EP2747903B1 EP12756795.6A EP12756795A EP2747903B1 EP 2747903 B1 EP2747903 B1 EP 2747903B1 EP 12756795 A EP12756795 A EP 12756795A EP 2747903 B1 EP2747903 B1 EP 2747903B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- utensil
- support
- layer
- stick coating
- plasma
- 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.)
- Active
Links
- 238000000576 coating method Methods 0.000 title claims description 48
- 239000011248 coating agent Substances 0.000 title claims description 45
- 239000000203 mixture Substances 0.000 claims description 37
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 28
- 229920005989 resin Polymers 0.000 claims description 28
- 239000011347 resin Substances 0.000 claims description 28
- 239000011230 binding agent Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 18
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 17
- 238000009832 plasma treatment Methods 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 15
- 238000011282 treatment Methods 0.000 claims description 13
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
- 150000004703 alkoxides Chemical class 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 229920002312 polyamide-imide Polymers 0.000 claims description 9
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004962 Polyamide-imide Substances 0.000 claims description 7
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 6
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 6
- 229920006393 polyether sulfone Polymers 0.000 claims description 5
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 5
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 4
- 239000000839 emulsion Substances 0.000 claims description 4
- 229920001643 poly(ether ketone) Polymers 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 229920002530 polyetherether ketone Polymers 0.000 claims description 4
- 229920001601 polyetherimide Polymers 0.000 claims description 4
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000000049 pigment Substances 0.000 claims description 3
- BZPCMSSQHRAJCC-UHFFFAOYSA-N 1,2,3,3,4,4,5,5,5-nonafluoro-1-(1,2,3,3,4,4,5,5,5-nonafluoropent-1-enoxy)pent-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)=C(F)OC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)F BZPCMSSQHRAJCC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 2
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 2
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003921 oil Substances 0.000 claims description 2
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 claims description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 2
- 230000008878 coupling Effects 0.000 claims 11
- 238000010168 coupling process Methods 0.000 claims 11
- 238000005859 coupling reaction Methods 0.000 claims 11
- 229920000265 Polyparaphenylene Polymers 0.000 claims 1
- 238000010411 cooking Methods 0.000 claims 1
- 239000000945 filler Substances 0.000 claims 1
- 150000003568 thioethers Chemical class 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 description 29
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 29
- 239000000758 substrate Substances 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 14
- 239000010935 stainless steel Substances 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- 229910000838 Al alloy Inorganic materials 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 101150006573 PAN1 gene Proteins 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- 238000004873 anchoring Methods 0.000 description 2
- 230000001680 brushing effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000005495 cold plasma Effects 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 229910052756 noble gas Inorganic materials 0.000 description 2
- 150000002835 noble gases Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000005488 sandblasting Methods 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 230000007480 spreading Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- 241000467686 Eschscholzia lobbii Species 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229920004482 WACKER® Polymers 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000021168 barbecue Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229940082150 encore Drugs 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002663 nebulization Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 235000014594 pastries Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000007592 spray painting technique Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
Images
Classifications
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- 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
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
- B05D5/083—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface involving the use of fluoropolymers
-
- 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
- B05D1/62—Plasma-deposition of organic layers
-
- 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
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
-
- 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
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/52—Two layers
- B05D7/54—No clear coat specified
-
- 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
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/56—Three layers or more
-
- 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
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/14—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by electrical means
- B05D3/141—Plasma treatment
- B05D3/142—Pretreatment
-
- 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
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/52—Two layers
Definitions
- the present invention relates generally to articles comprising a non-stick coating having improved properties of adhesion to the support.
- the present invention also relates to a method of manufacturing such a cookware.
- the targeted field is primarily that of cookware such as pots and pans, but the present invention may also relate to any other type of surface provided with a non-stick coating such as the sole of an iron.
- a relatively thick coating typically having a total thickness comprised between 10 and 50 ⁇ m
- fluorocarbon resin for example PTFE
- Such coatings are known not only for their non-stick properties, but also for their resistance to chemical or thermal attack.
- such coatings have limited adhesion to metal supports, especially aluminum, stainless steel or cast iron supports.
- a bonding primer comprising a bonding binder such as PAI
- chemical surface treatments for example of the chemical pickling type
- mechanical for example by brushing or sandblasting
- the patent EP1391249 describes a culinary article coated with a network of metallic oxide in which a hydrophobic substance is uniformly distributed.
- the substrate on which the metal oxide coating is applied can be activated beforehand by a plasma treatment.
- a chemical surface treatment of the pickling type involves the use of polluting chemical baths and a mechanical surface treatment of the brushing or sandblasting type. (slightly) deforms the surface, which requires an additional shaping operation.
- the sanding medium or brushes must be regenerated or landfilled at the end of their life, which generates pollution.
- the Applicant has developed a plasma surface treatment which allows the formation of a chemically activated interface layer between the support and the non-stick coating (generally obtained by spraying or by screen printing, roller, etc.), this interface layer allowing the anchoring of such a thickness of non-stick coating, which thus allows the latter to ensure a long-term non-stick function without the risk of delamination.
- the subject of the present invention is an article comprising a support having an at least partially metallic contact surface and which is covered by a non-stick coating comprising at least one thermostable binder.
- the contact surface comprises an interface layer chemically activated by plasma and formed by plasma polymerization
- the thermostable binder of the non-stick coating is a fluorocarbon resin or a mixture of fluorocarbon resins, alone or as a mixture. with a thermostable bonding binder and resistant to at least 200 ° C, the fluorocarbon resin and, if necessary, the thermostable bonding binder forming a sintered network.
- the non-stick coating has a thickness of 400 nm or more, and preferably between 2 and 50 ⁇ m.
- the fact that the interface layer is chemically activated allows the anchoring on the support of a thick non-stick coating. If the interface layer was not chemically activated, for example simply roughened and cleaned by a plasma treatment as taught by international applications WO 03/035154 and WO 2008/146025 , it would not be possible to deposit such thick layers of fluorocarbon resin.
- the fluorocarbon resin can be chosen from polytetrafluoroethylene (PTFE), the copolymer of tetrafluoroethylene and perfluoropropylvinylether (PFA), and the copolymer of tetrafluoroethylene and hexafluoropropylene (FEP), the copolymers comprising at least 50% by mole of tetrafluoro , and mixtures thereof.
- PTFE polytetrafluoroethylene
- PFA perfluoropropylvinylether
- FEP hexafluoropropylene
- the article according to the present invention comprises either an entirely metallic support (in this case, the contact surface is entirely metallic), or a metallic support partially or completely covered with a hard base. (in the case of a partially metallic contact surface, the complement being constituted by the hard base), the hard base preferably being enamel or ceramic.
- the metal part of the support is advantageously made of aluminum or aluminum alloy, cast aluminum (or foundry aluminum alloy), or stainless steel.
- the article according to the invention is a culinary article.
- culinary articles in accordance with the present invention, mention may in particular be made of culinary articles such as pots and pans, woks and frying pans, casseroles and pots, crepe makers, grills , baking molds and plates, barbecue plates and grills, preparation bowls.
- the interface layer of the support is a thin layer formed by plasma polymerization (plasma treatment with precursor), preferably a layer obtained from metal alkoxide, and better still from alkoxysilane, siloxane or silazane.
- the interface layer of the support is obtained by chemical grafting via a plasma treatment (without precursor) under atmospheric pressure or under a partial vacuum between 0.133 Pa (10 -3 mm Hg) and atmospheric pressure, then plasma polymerization ( treatment with precursor), which is preferably a layer obtained from metal alkoxide, and preferably from alkoxysilane, siloxane or silazane.
- the bonding binder of the non-stick coating according to the invention (based on fluorocarbon resin) can be advantageously chosen from polyamide imides (PAI), polyether imides (PEI), polyamides (PI), polyetherketones (PEK), polyetheretherketones (PEEK), polyethersulfones (PES) and polyphenylene sulfides (PPS).
- PAI polyamide imides
- PEI polyether imides
- PI polyamides
- PEK polyetherketones
- PEEK polyetheretherketones
- PES polyethersulfones
- PPS polyphenylene sulfides
- the non-stick coating of the article according to the invention can comprise a bonding primer layer and at least one finishing layer, the primer layer comprising, in addition to the sintered network of fluorocarbon resin, at least one binder of hanging.
- the bonding binder in the primer layer can be a polyamide imide (PAI).
- the contact surface is a surface previously treated chemically or mechanically.
- Such treatment also makes it possible to modify the surface states and in particular to achieve surface tensions of the order of 72 mN / m on aluminum supports, which improves the wettability of the substrate. In the particular case of aluminum alloys, this treatment creates an oxidation layer which is favorable to adhesion. It is then possible, by virtue of this preliminary treatment of the layer formed by plasma polymerization, to use a non-stick coating essentially free of bonding binder (for example comprising only one or more finishing layers).
- the composition based on fluorocarbon resin (s) is applied in a layer having a total dry thickness of at least 400 nm, and preferably between 2 and 50 ⁇ m.
- the application of such a layer can be done conventionally (spraying, screen printing, spray painting, roller, dip, curtain).
- the support, the fluorocarbon resin and the thermostable bonding binder are as defined above.
- the method according to the invention comprises, prior to the formation of the non-stick coating, a step of producing a hard base on said face of the support.
- the interface layer is a layer formed by plasma polymerization (with precursor).
- a precursor in liquid or gaseous form is added at the outlet of the plasma torch, so that the molecules are broken down into high-energy fragments whose pieces react with each other on the substrate and which form a more or less strongly crosslinked layer.
- the substrate which is at least partially metallic
- the interface layer is a layer formed by a plasma polymerization treatment, which follows a plasma treatment at atmospheric pressure or under a partial vacuum between 10 -3 mm Hg and atmospheric pressure (without precursor).
- a plasma treatment consists in exposing a surface to a plasma which is composed either of inert gases (noble gases), or of molecules containing atoms which are not capable of forming chains (for example N 2 , 0 2 , NH 3 ) .
- Plasma produces high energy particles as high energy, but also ions always leads to a modification of electrons, radiation of and excited particles which from the surface: bonds are broken and active sites on the material are created . These active sites (radicals) can react with each other and thus cause additional crosslinking in the surface area.
- the interface layer is a layer of metal polyalkoxide formed from at least one precursor of the metal alkoxide type chosen from the group consisting of alkoxysilanes, aliphatic or cyclic siloxanes, pure or in aqueous emulsion.
- alkoxysilanes which can be used in the process of the invention, of methyltrimethoxysilane (MTMS), methyltrimethoxysilane (MTMS), tetraethoxysilane (TEOS) and 3-Glycidoxypropyltrimethoxysilane (GLYMO).
- MTMS methyltrimethoxysilane
- MTMS methyltrimethoxysilane
- TEOS tetraethoxysilane
- GLYMO 3-Glycidoxypropyltrimethoxysilane
- the aliphatic or cyclic siloxane pure or in aqueous emulsion, can be chosen from the group consisting of hexamethyldisiloxane, octamethylsiloxane, decamethylsiloxane, PDMS oils optionally modified with a viscosity of less than 100 mPa.s, silazanes.
- the contact surface may also be advantageous for the contact surface to be treated chemically (for example degreased or satin-finished) or mechanically (in particular brushed) .
- a pan 1 comprising a metal support 2 in the form of a hollow cap and a grip handle 5.
- the support 2 comprises an inner face 21 (surface of contact) which is the side facing the side of the food likely to be received in the pan 1, and an external side 22 which is intended to be disposed towards an external heat source.
- the inner face 21 is coated with a non-stick coating 3, which successively comprises, from the support 2, a primer layer 30 for attachment and two finish layers 31, 32.
- the primer layers 30, finish 31 and decor 32 are based on PTFE.
- the support 2 of the pan shown on the figure 1 has not been plasma treated in accordance with the present invention, while that of the pan shown in the figure 2 was treated by plasma polymerization from a metal alkoxide precursor, leading to the formation of a polymer layer 210 on the contact surface 21 of the support.
- the support 2 of the pan shown on the figure 3 a prior to plasma polymerization, has been treated by plasma under atmospheric pressure and has an interface layer 210 just below the contact surface 21 in the upper part of the support 2, on which a layer has been deposited of polymer 210 identical to that deposited on the support 2 of the figure 2 .
- Plasma treatment step 1 cold plasma treatment step at atmospheric pressure (optional step)
- Plasma treatment step 2 plasma polylmerization step
- All of the wafers were coated with a non-stick coating 3, whether or not comprising a primer composition (CP1, CP2) and a finishing composition (CF1 or CF2), after having been previously or not subjected to a treatment by plasma according to the process according to the invention.
- a primer composition CP1, CP2
- CF1 or CF2 finishing composition
- results presented in this table show a significant improvement in the adhesion of a fluorinated coating in a thick layer when the support is treated with a plasma polymerization, both with TEOS and with HMDSO.
- the plasma polymerization treatment makes it possible to dispense with the use of a primer or in the case of difficult supports makes it possible to reinforce the adhesion at a high level which guarantees better durability of the coated articles.
- Table 1 results of the adhesion test ⁇ /u> Type of support
- Non-stick coating Atmospheric plasma treatment plasma / precursor polymerization treatment
- Grip Smooth aluminum plates CF1 thickness 19 pm NO NO 0% Smooth aluminum plates CF1 thickness 19 pm NO YES / TEOS 99% Smooth aluminum plates CP1 + CF1 total thickness 30pm NO YES / TEOS 100% Smooth aluminum plates CP2 + CF1 total thickness 30pm NO YES / TEOS 100% Satin aluminum plates CF1 thickness 20pm NO YES / TEOS 100% Brushed aluminum plates CF1 thickness 20pm NO NO 0% Brushed aluminum plates CF1 thickness 20pm NO YES / TEOS 99% Brushed aluminum plates CP1 + CF1 total thickness 35pm NO NO 95% Brushed aluminum plates
Landscapes
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Laminated Bodies (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
- Adhesives Or Adhesive Processes (AREA)
Claims (24)
- Utensil (1), umfassend einen Untergrund (2), der eine mindestens teilweise metallische Kontaktfläche (21) aufweist und der von einer Antihaftbeschichtung (3) bedeckt ist, die mindestens ein thermostabiles Bindemittel umfasst,
dadurch gekennzeichnet, dass:- die Kontaktfläche (21) eine Grenzflächenschicht (210) umfasst, die chemisch plasmaaktiviert und durch Plasmapolymerisation gebildet wird,- das thermostabile Bindemittel ein Fluorkohlenstoffharz oder ein Gemisch aus Fluorkohlenstoffharzen ist, allein oder als Gemisch mit einem Haftbindemittel, das thermostabil und gegen mindestens 200 °C beständig ist, wobei das Fluorkohlenstoffharz und, gegebenenfalls, das thermostabile Haftbindemittel ein gesintertes Netz bilden. - Utensil (1) nach Anspruch 1, dadurch gekennzeichnet, dass die Antihaftbeschichtung eine Dicke aufweist, die gleich oder größer 400 nm ist und vorzugsweise zwischen 2 und 50 µm beträgt.
- Utensil nach einem der Ansprüche 1 und 2, dadurch gekennzeichnet, dass das Fluorkohlenstoffharz gewählt wird aus Polytetrafluorethylen (PTFE), dem Copolymer aus Tetrafluorethylen und Perfluorpropylvinylether (PFA) und dem Copolymer aus Tetrafluorethylen und Hexafluorpropylen (FEP), wobei die Copolymere mindestens 50 Mol-% Tetrafluorethylen umfassen, und ihren Gemischen.
- Utensil (1) nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass der Untergrund (2) entweder ein vollständig metallischer Untergrund ist oder ein metallischer Untergrund, der teilweise oder gänzlich von einer harten Basis bedeckt ist.
- Utensil (1) nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die Grenzflächenschicht (210) eine Schicht ist, die ausgehend von Metallalkoxid und vorzugweise ausgehend von Alkoxysilan, von Siloxan oder von Silazan erhalten wird.
- Utensil (1) nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass die Grenzflächenschicht (210) eine Schicht ist, die sukzessive durch chemisches Pfropfen über eine Plasmabehandlung unter atmosphärischem Druck oder unter einem Teilvakuum zwischen 0,133 Pa und dem atmosphärischen Druck, danach Plasmapolymerisation erhalten wird.
- Utensil (1) nach Anspruch 6, dadurch gekennzeichnet, dass die Grenzflächenschicht (210) eine Schicht umfasst, die ausgehend von Metallalkoxid und vorzugweise ausgehend von Alkoxysilan, von Siloxan oder von Silazan erhalten wird.
- Utensil (1) nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass das Haftbindemittel gewählt wird aus Polyamidimiden (PAI), Polyetherimiden (PEI), Polyamiden (PI), Polyetherketonen (PEK), Polyetheretherketonen (PEEK), Polyethersulfonen (PES) und Polyphenylensulfiden (PPS).
- Utensil (1) nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass die Antihaftbeschichtung (3) eine Haftgrundierung (30) und mindestens eine Deckschicht (31, 32) umfasst, wobei die Grundierung (30) außer dem gesinterten Netz aus Fluorkohlenstoffharz mindestens ein Haftbindemittel umfasst.
- Utensil (1) nach Anspruch 9, dadurch gekennzeichnet, dass die Grundierung (30) ein Polyamidimid (PAI) als Haftbindemittel umfasst.
- Utensil (1) nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass die Kontaktfläche (21) eine chemisch oder mechanisch behandelte Oberfläche ist.
- Utensil (1) nach Anspruch 11, dadurch gekennzeichnet, dass die Antihaftbeschichtung (3) frei von Haftbindemittel ist.
- Utensil (1) nach einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, dass die Antihaftbeschichtung (3) Füllstoffe und/oder Pigmente umfasst.
- Utensil (1) nach einem der Ansprüche 1 bis 13, dadurch gekennzeichnet, dass es ein Kochutensil darstellt.
- Verfahren zur Herstellung eines Utensils (1), umfassend folgende Schritte:- Bereitstellen eines Untergrunds (2), der mindestens teilweise metallisch ist und zwei gegenüberliegende Flächen (21, 22) aufweist;- Bilden einer Antihaftbeschichtung (3) auf einer der Flächen (21) des Untergrunds (2), umfassend:wobei das Verfahren dadurch gekennzeichnet ist, dass es des Weiteren, vor dem Bilden der Antihaftbeschichtung (3) auf der Fläche (21), einen Schritt des chemischen Aktivierens mittels Plasmabehandlung und der Plasmapolymerisation der Fläche (21) umfasst, um eine Grenzflächenschicht (210) zu erzeugen, die chemisch aktiviert ist und mittels Plasmapolymerisation auf dieser Fläche (21) gebildet wird.▪ Vorbereiten mindestens einer Zusammensetzung auf Basis mindestens eines Fluorkohlenstoffharzes in Partikelform, wobei das Fluorkohlenstoffharz allein oder in Gemisch mit einem thermostabilen Haftbindemittel ist, das gegen mindestens 200 °C beständig ist; und▪ Auftragen der Zusammensetzung auf eine der Flächen (21) des Untergrunds (2), um eine Schicht aus Fluorkohlenstoffharz zu bilden;▪ Brennen des so beschichteten Utensils (1) bei einer Temperatur zwischen 350 °C und 450 °C, um die Fluorkohlenstoffharzschicht zu sintern, sodass eine Antihaftbeschichtung (3) erhalten wird, die ein durchgehendes Netz bildet,
- Verfahren nach Anspruch 15, dadurch gekennzeichnet, dass die Zusammensetzung auf Basis von Fluorkohlenstoffharz(en) in einer Schicht, die eine trockene Dicke von mindestens 400 nm und vorzugsweise zwischen 2 und 50 µm aufweist, aufgetragen wird.
- Verfahren nach den Ansprüchen 15 oder 16, dadurch gekennzeichnet, dass es, vor dem Bilden der Antihaftbeschichtung (3), einen Schritt des Ausführens einer harten Basis auf der Fläche (21) des Untergrunds (2) umfasst.
- Verfahren nach einem der Ansprüche 15 bis 17, dadurch gekennzeichnet, dass, vor der Plasmapolymerisation, die Fläche (21) des Untergrunds (1) einer Plasmabehandlung unter atmosphärischem Druck oder unter einem Teilvakuum zwischen 0,133 Pa (10-3 mm Hg) und dem atmosphärischen Druck unterzogen wird, um eine durch chemisches Pfropfen funktionalisierte Grenzflächenschicht (210) zu bilden, die mit dem Untergrund einen einzigen Teil bildet.
- Verfahren nach Anspruch 18, dadurch gekennzeichnet, dass die Fläche (21) des Untergrunds (1) einer Plasmapolymerisationsbehandlung ausgehend von mindestens einem Präkursor vom Typ Metallalkoxid unterzogen wird, gewählt aus der Gruppe bestehend aus Alkoxysilanen und aliphatischen oder zyklischen Siloxanen, rein oder als wässrige Emulsion.
- Verfahren nach Anspruch 19, dadurch gekennzeichnet, dass das Metallalkoxid ein Alkoxysilan ist, gewählt aus Methyltrimethoxysilan (MTMS), Tetraethoxysilan (TEOS) und 3-Glycidoxypropyltrimethoxysilan (GLYMO).
- Verfahren nach Anspruch 19, dadurch gekennzeichnet, dass das Metallalkoxid ein aliphatisches oder zyklisches Siloxan ist, rein oder als wässrige Emulsion, gewählt aus der Gruppe bestehend aus Hexamethyldisiloxan, Octamethylsiloxan, Decamethylsiloxan, eventuell modifizierten PDMS-Ölen mit einer Viskosität von weniger als 100 mPa.s und Silazanen.
- Verfahren nach einem der Ansprüche 15 bis 21, dadurch gekennzeichnet, dass das Bilden der Antihaftbeschichtung (3) umfasst:- Auftragen, auf die Fläche (21) des Untergrunds (2), einer Haftgrundierungszusammensetzung, um eine Haftgrundierung (30) zu bilden, wobei die Grundierungszusammensetzung mindestens ein Fluorkohlenstoffharz in Partikelform und optional ein Haftbindemittel umfasst, das thermostabil ist und gegen mindestens 200 °C beständig ist; und- Auftragen, auf die Grundierung (30), mindestens einer Deckzusammensetzung, um eine Deckschicht (31, 32) zu bilden, wobei die Deckzusammensetzung mindestens ein Fluorkohlenstoffharz in Partikelform umfasst.
- Verfahren nach einem der Ansprüche 15 bis 22, dadurch gekennzeichnet, dass die Kontaktfläche (21) eine chemisch oder mechanisch behandelte Oberfläche ist.
- Verfahren nach Anspruch 23, dadurch gekennzeichnet, dass die Kontaktfläche (21) gebürstet, entfettet oder satiniert ist.
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FR1157579A FR2979214B1 (fr) | 2011-08-26 | 2011-08-26 | Article comportant un revetement antiadhesif presentant des proprietes ameliorees d'adherence au support |
PCT/FR2012/051940 WO2013030503A2 (fr) | 2011-08-26 | 2012-08-27 | Article comportant un revêtement antiadhesif presentant des proprietes ameliorees d'adherence au support |
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DE102014219979A1 (de) | 2014-10-01 | 2016-04-07 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Verbund aus Substrat, plasmapolymerer Schicht, Mischschicht und Deckschicht |
CN104457165A (zh) * | 2014-11-14 | 2015-03-25 | 广德林峰科技有限公司 | 一种萤石间接式回转干燥机 |
CN108720621B (zh) * | 2017-04-25 | 2021-08-10 | 佛山市顺德区美的电热电器制造有限公司 | 不粘涂层及其制备方法以及锅具和煮食设备 |
DE102017130353A1 (de) | 2017-12-18 | 2019-06-19 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Sol-Gel-basierte Haftvermittlungsschicht für PTFE-basierte Beschichtungen und Verfahren zur Herstellung derselben |
WO2020256210A1 (ko) | 2019-06-20 | 2020-12-24 | 주식회사 쿼드마이너 | 네트워크 포렌식 시스템 및 이를 이용한 네트워크 포렌식 방법 |
CN111100513B (zh) * | 2019-12-27 | 2021-08-03 | 杭州吉华高分子材料股份有限公司 | 一种碳纳米管复合陶瓷网络改性水性不粘涂料的制备方法 |
FR3126608B1 (fr) * | 2021-09-03 | 2023-09-08 | Seb Sa | Element de cuisson revetu par un film polymerique fluore antiadhesif pelable |
KR102409467B1 (ko) * | 2022-03-25 | 2022-06-16 | 리나스대성(주) | 다단계 표면 처리된 국솥 또는 부침기 |
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GB0125380D0 (en) * | 2001-10-23 | 2001-12-12 | Glaxo Group Ltd | Medicament dispenser |
JP2003211084A (ja) * | 2001-10-26 | 2003-07-29 | Seiko Instruments Inc | フッ素系樹脂コーティング方法およびこの方法を用いた摺動部材、気体圧縮機 |
DE10236728A1 (de) * | 2002-08-09 | 2004-02-26 | Schott Glas | Reinigungsfreundliche Vorrichtung |
MXPA05006547A (es) * | 2002-12-20 | 2005-08-16 | Ciba Sc Holding Ag | Metodo para formar recubrimientos reactivos. |
FR2869817B1 (fr) * | 2004-05-04 | 2008-05-30 | Seb Sa | Procede de fabrication d'un revetement anti-adhesif et d'un article culinaire ainsi revetu |
FR2904206B1 (fr) * | 2006-07-31 | 2008-09-26 | Seb Sa | Article culinaire presentant des proprietes hydrophobes ameliorees et procede de fabrication d'un tel article |
DE602007005017D1 (de) * | 2006-10-20 | 2010-04-08 | 3M Innovative Properties Co | Verfahren für leicht zu reinigende substrate und artikel daraus |
GB0710488D0 (en) * | 2007-06-01 | 2007-07-11 | Innovatek Medical Ltd | Methods of treating components of a medical dispenser device |
FR2923696B1 (fr) * | 2007-11-16 | 2012-08-17 | Seb Sa | Article culinaire comprenant un revetement antiadhesif resistant a la corrosion et a la rayure |
FR2937236B1 (fr) * | 2008-10-16 | 2010-11-26 | Seb Sa | Article culinaire comportant un revetement antiadhesif presentant des proprietes ameliorees d'adherence au support |
BRPI1007653A2 (pt) * | 2009-05-06 | 2019-09-24 | 3M Innovative Properties Co | "dispositivos para inalação de insumos medicinais e componentes dos mesmos" |
CN102460635B (zh) * | 2009-05-06 | 2014-12-24 | 3M创新有限公司 | 对容器进行等离子体处理的装置和方法 |
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CN103764303B (zh) | 2016-05-18 |
WO2013030503A2 (fr) | 2013-03-07 |
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