EP2747903A2 - Utensil comprising a non-stick coating having improved properties of adhesion to the support - Google Patents
Utensil comprising a non-stick coating having improved properties of adhesion to the supportInfo
- Publication number
- EP2747903A2 EP2747903A2 EP12756795.6A EP12756795A EP2747903A2 EP 2747903 A2 EP2747903 A2 EP 2747903A2 EP 12756795 A EP12756795 A EP 12756795A EP 2747903 A2 EP2747903 A2 EP 2747903A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- article
- support
- layer
- fluorocarbon resin
- stick coating
- 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.)
- Granted
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 48
- 239000011248 coating agent Substances 0.000 title claims abstract description 45
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229920005989 resin Polymers 0.000 claims abstract description 29
- 239000011347 resin Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 20
- 230000008569 process Effects 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 26
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- 239000011230 binding agent Substances 0.000 claims description 22
- 239000002243 precursor Substances 0.000 claims description 20
- 238000006116 polymerization reaction 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 15
- 238000011282 treatment Methods 0.000 claims description 14
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 12
- 150000004703 alkoxides Chemical class 0.000 claims description 11
- 229920002312 polyamide-imide Polymers 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 239000004962 Polyamide-imide Substances 0.000 claims description 8
- 230000015572 biosynthetic process Effects 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
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 6
- 229920006393 polyether sulfone Polymers 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 4
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 4
- 125000000217 alkyl 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
- 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
- 229920000069 polyphenylene sulfide 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
- 230000004913 activation Effects 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
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 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
- 150000002739 metals Chemical class 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical class 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims 1
- 150000003949 imides Chemical class 0.000 claims 1
- 229920000570 polyether Polymers 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 28
- 239000000758 substrate Substances 0.000 description 18
- 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
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 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
- 239000002253 acid Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 235000012431 wafers Nutrition 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
- 229910000831 Steel Inorganic materials 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
- 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
- 238000010411 cooking Methods 0.000 description 2
- 238000004132 cross linking Methods 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
- 229920001601 polyetherimide Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002360 preparation method 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
- 239000010959 steel Substances 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
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 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
- 238000004873 anchoring Methods 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
- 230000032798 delamination 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
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011888 foil Substances 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
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000011221 initial treatment Methods 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
- 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
- 238000005554 pickling Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000013519 translation Methods 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
Classifications
-
- 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 generally relates to articles having a non-stick coating having improved adhesion properties to the carrier.
- the present invention also relates to a method of manufacturing such a culinary article.
- the field in question is primarily that of culinary articles such as stoves or saucepans, but the present invention may also relate to any other type of surface provided with a non-stick coating such as the soleplate of an iron.
- a relatively thick coating typically having a total thickness of between 10 and 50 ⁇
- fluorocarbon resin is used as a release coating on the inside of a culinary article.
- Such coatings are known not only for their non-stick properties, but also for their resistance to chemical or thermal attack. However, such coatings have limited adhesion to metal substrates, including aluminum, stainless steel or cast iron supports.
- a primer comprising a bonding binder such as PAI
- chemical surface treatments for example of the chemical stripping type
- mechanical for example by brushing or sandblasting
- a chemical surface treatment of the pickling type involves the use of polluting chemical baths and a mechanical surface treatment of the brushing or sanding type deforms
- the Applicant has developed a plasma surface treatment which allows the forming a chemically activated interface layer between the support and the non-stick coating (generally obtained by spraying or screen printing, roll, etc.), this interface layer allowing the anchoring of such a thickness of non-stick coating, thus allowing the latter to provide a long-term function of anti-adhesiveness without risk of delamination.
- the present invention relates to an article comprising a support having a contact surface at least partially metallic and which is covered by a non-stick coating comprising at least one thermostable binder.
- the contact surface comprises a plasma-chemically activated interface layer
- the thermostable binder of the non-stick coating is a fluorocarbon resin or a mixture of fluorocarbon resins, alone or in admixture with a binder. thermostable bond and resistant to at least 200 ° C, the fluorocarbon resin and, where appropriate, the thermostable bonding binder forming a sintered network.
- the release coating has a thickness equal to or greater than 400 nm, and preferably between 2 and 50 ⁇ .
- the fact that the interface layer is chemically activated makes it possible to anchor a thick non-stick coating on the support. If the interface layer were not chemically activated, for example simply roughened and cleaned by plasma treatment as taught by international applications WO 03/035154 and WO 2008/146025, it would not be possible to deposit resin layers. fluorocarbon also thick.
- the fluorocarbon resin may 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 mol% of tetrafluoroethylene , and their mixtures.
- 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 metal support partially or completely covered with a hard base (in the case of a surface partially metallic contact complement being constituted by the hard base), the hard base being preferably enamel or ceramic.
- the metal part of the support is preferably aluminum or aluminum alloy, cast aluminum (or foundry aluminum alloy), or stainless steel.
- the article according to the invention is a culinary article.
- cooking utensils As non-limiting examples of cooking utensils according to the present invention, mention may in particular be made of culinary articles such as pots and pans, oks and sauté-pans, facts-wholes and pots, crepe makers, grills. , molds and plates for baking, barbecue plates and grills, bowls for preparation.
- culinary articles such as pots and pans, oks and sauté-pans, facts-wholes and pots, crepe makers, grills. , molds and plates for baking, barbecue plates and grills, bowls for preparation.
- 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 from alkoxysilane, siloxane or silazane.
- the interface layer of the support is obtained by chemical grafting by plasma treatment (without precursor) under atmospheric pressure or under a partial vacuum between 0.133 Pa (10 -3 mmHg) and atmospheric pressure, and then plasma polymerization ( precursor treatment), which is preferably a layer obtained from metal alkoxide, and preferably from alkoxysilane, siloxane or silazane.
- plasma treatment without precursor
- plasma polymerization precursor treatment
- the binder for adhering the non-stick coating according to the invention may advantageously be chosen from polyamide imides (PAI), polyether imides (PEI), polyamides (PI) and 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 may comprise a layer of primer and at least one topcoat, 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 may be a polyamide imide (PAI).
- the contact surface is a surface previously treated chemically or mechanically.
- Such a treatment also makes it possible to modify the surface states and to reach, in particular, surface tensions of the order of 72 ⁇ m / m on aluminum supports, which improves the wettability of the substrate.
- this treatment creates an oxidation layer that is favorable to adhesion. It is then possible, thanks to this pretreatment 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 topcoats).
- the present invention also relates to a method of manufacturing an article according to the invention, comprising the following steps:
- ⁇ preparing at least one composition based on at least one fluorocarbon resin in particulate form, said fluorocarbon resin being alone or in admixture with a thermostable bonding binder and resistant to at least 200 ° C;
- said method being characterized in that it further comprises, before the formation of the non-stick coating on one of the faces of the support, a step of chemical activation by plasma treatment of this face, so as to create an interface layer chemically activated on this face.
- 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 ⁇ .
- the application of such a layer can be done conventionally (spraying, screen printing, pistolsammlung, roll, tempered, 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 decomposed 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 substrate receives a deposit of a coating of a thickness between a few nanometers up to a few hundred nanometers which has been formed by the atmospheric reactive plasma. Ultra-thin layers of coatings are thus deposited by plasma.
- the interface layer is a layer formed by a plasma polymerization treatment (according to the second embodiment of the process of the invention), which follows a plasma treatment under atmospheric pressure or under a partial vacuum between ⁇ 3 mm Hg and atmospheric pressure (without precursor).
- a plasma treatment consists in exposing a surface to a plasma which consists of either inert gases (noble gases) or molecules containing atoms which are not capable of forming chains (for example N 2 , O 2 , NH 3) .
- Plasma produces high energy particles such as electrons, high energy radiation, but also excited ions and particles, which always leads to a surface modification: bonds break and active sites on the material are created. .
- active sites can react with each other and thus cause additional crosslinking in the surface area. They remain partly in the surface of high crosslinking and thus form an activated surface capable of spontaneous reactions p. ex. with atmospheric oxygen. Gases that are not noble gases such as N 2 , O 2 or NH 3 can additionally be introduced on the surface of the atoms they comprise. Characteristics such as the adhesive power, the adhesion of the varnish, the wettability and the surface energy are thus significantly improved (compared to a simple polymerization). Activation and cleaning are two phenomena that usually occur at the same time.
- the interface layer is a metal polyalkoxide layer formed from at least one metal alkoxide precursor selected from the group consisting of:
- n being an integer corresponding to the maximum valence of the metals M lr M 2 or M 3
- Mi M 2 or M 3 denoting a metal chosen from Si, Zr, Ti, Sn, Al, Ce, Nb Hf, Mg or Ln,
- the metal alkoxide is an alkoxysilane.
- alkoxysilanes that may be used in the process of the invention, mention may especially be made of methyltrimethoxysilane (MTMS), methyltrimethoxysilane (MTMS), tetraethoxysilane (TEOS) and 3-glycidoxypropyltrimethoxysilane (GLYMO).
- MTMS methyltrimethoxysilane
- MTMS methyltrimethoxysilane
- TEOS tetraethoxysilane
- GLYMO 3-glycidoxypropyltrimethoxysilane
- the metal alkoxide an aliphatic or cyclic siloxane, pure or in aqueous emulsion, which can be selected from the group consisting of hexamethyldisiloxane, octamethylsiloxane, decamethylsiloxane, optionally modified PDMS oils of viscosity less than 100mPa.s, silazanes.
- the formation of the non-stick coating on one of the faces of the support (contact surface) can advantageously comprise the following steps:
- the primer composition comprising at least one fluorocarbon resin in particulate form and at least one thermostable bonding binder and resistant to at least 200 ° C;
- the primer layer at least one finishing composition to form a topcoat, the finishing composition comprising at least one fluorocarbon resin in particulate form.
- the contact surface may also be advantageous for the contact surface to be chemically treated (for example degreased or satinized) or mechanically (especially brushed).
- FIG. 1 represents a diagrammatic sectional view of an example of a culinary article according to the invention according to the prior art (non-plasma treated support and primer);
- FIG. 2 represents a schematic sectional view of a culinary article according to the invention according to a first embodiment variant of the process of the invention (support treated by plasma polymerization with a primer);
- FIG. 3 is a diagrammatic cross-sectional view of a culinary article according to the invention according to a second alternative embodiment of the process of the invention (support treated successively by the plasma route under atmospheric pressure, then by plasma polymerization, with primary treatment; hanging).
- the identical elements shown in FIGS. 1 to 3 are identified by identical reference numerals.
- FIGS. 1 to 3 show, by way of example of an article according to the invention, a pan 1 comprising a metal support 2 in the form of a hollow cap and a gripping handle 5.
- the support 2 comprises a inner face 21 (contact surface) which is the side oriented side of the food receptive to the pan 1, and an outer face 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 comprises successively from the support 2 a primer coat 30 and two topcoats 31, 32.
- the primer layers 30, finish 31 and decor 32 are based on PTFE.
- the support 2 of the pan shown in FIG. 1 has not been plasma treated in accordance with the present invention, whereas that of the pan shown in FIG. 2 has been treated by plasma polymerization from a precursor of metal alkoxide type, leading to the formation of a polymer layer 210 on the contact surface 21 of the support.
- the support 2 of the pan shown in FIG. 3 has, prior to the plasma polymerization, been treated with 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 was deposited a polymer layer 210 identical to that deposited on the support 2 of Figure 2.
- the roughness of the treated surfaces has an arithmetical average roughness Ra measured between 4 and 6 ⁇ .
- TEOS tetraethoxysilane
- HMDSO hexamethyldisiloxane
- Pigments in fluorinated formulations pigment flakes (mica and titanium oxide) marketed by Merck under the trade names Iriodin 153
- LUDOX AM30 (colloidal silica in 30% water): 21.5 g PTFE (60% PTFE dispersion) 78 g
- PAI resin (29% dry in CIP): 58.9 g
- LUDOX AM30 (colloidal silica in water 30%): 19.3 g
- Stage 1 of the plasma treatment step of treatment with cold plasma under atmospheric pressure (optional step) o device by ionization of air marketed by PLASMATREAT under the trade name
- FG3001 it is a robot equipped with a nozzle head and applying a movement of translation of the nozzle on the substrate operating according to the following operating conditions:
- Plasma flow rate 10 to 40 l / min
- Step 2 of the plasma treatment plasma polylmerization step
- Plasma flow rate 10 to 40 l / min
- one of the faces of the aluminum substrates is conventionally coated as follows:
- ⁇ is sprayed on this inner face a thin layer of primer composition (CP1 or CP2) and / or finishing (CF1 or CF2) so as to obtain a layer of dry thickness greater than 3 ⁇ ;
- the wet primer layer thus formed is then dried at a temperature of about 65 ° C to no longer be tacky;
- the finishing composition is sprayed directly onto the substrate (in fact on the plasma-polymerized layer obtained by prior plasma treatment) or on the primer layer to give a minimum dry thickness greater than 5 ⁇ m, generally of the order of 16 ⁇ (stronger thicknesses can also be obtained by superimposing several topcoats, preferably from 1 to 3 layers). In both cases (application on substrate treated by plasma or on the primer), care is taken not to exceed a time of 15 minutes between the treatment and the application of the first fluorinated layer and preferably less than 5 minutes,
- a grid test is performed according to ISO 2409 followed by immersion of the article for 9 hours (3 cycles of 3 hours in boiling water). Then, it is observed whether or not the non-stick coating has a detachment.
- the quotation is as follows:
- the adhesion of the non-stick coating on the support is considered industrially acceptable if one has a value equal to or greater than 95 this level of adhesion is suitable for all types of cookware regardless of its level of mechanical stress.
- All the platelets were coated with a non-stick coating 3, comprising or not 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 method according to the invention.
- a non-stick coating 3 comprising or not 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 method according to the invention.
- Plasma polymerization treatment makes it possible to overcome the use of a primer or in the case of difficult substrates makes it possible to reinforce the adhesion to a high level which guarantees a better durability of the coated articles.
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)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1157579A FR2979214B1 (en) | 2011-08-26 | 2011-08-26 | ARTICLE COMPRISING ANTI-ADHESIVE COATING HAVING IMPROVED SUPPORT ADHESION PROPERTIES |
PCT/FR2012/051940 WO2013030503A2 (en) | 2011-08-26 | 2012-08-27 | Utensil comprising a non-stick coating having improved properties of adhesion to the support |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2747903A2 true EP2747903A2 (en) | 2014-07-02 |
EP2747903B1 EP2747903B1 (en) | 2020-07-01 |
Family
ID=46829829
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP12756795.6A Active EP2747903B1 (en) | 2011-08-26 | 2012-08-27 | Utensil comprising a non-stick coating having improved properties of adhesion to the support |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP2747903B1 (en) |
KR (1) | KR102023211B1 (en) |
CN (1) | CN103764303B (en) |
FR (1) | FR2979214B1 (en) |
WO (1) | WO2013030503A2 (en) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102014219979A1 (en) | 2014-10-01 | 2016-04-07 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Composite of substrate, plasma polymer layer, mixed layer and cover layer |
CN104457165A (en) * | 2014-11-14 | 2015-03-25 | 广德林峰科技有限公司 | Fluorite indirect-type rotating drying machine |
CN108720621B (en) * | 2017-04-25 | 2021-08-10 | 佛山市顺德区美的电热电器制造有限公司 | Non-stick coating, preparation method thereof, pot and cooking equipment |
DE102017130353A1 (en) | 2017-12-18 | 2019-06-19 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Sol-gel based primer layer for PTFE-based coatings and methods of making same |
WO2020256210A1 (en) | 2019-06-20 | 2020-12-24 | 주식회사 쿼드마이너 | Network forensic system and network forensic method using same |
CN111100513B (en) * | 2019-12-27 | 2021-08-03 | 杭州吉华高分子材料股份有限公司 | Preparation method of carbon nanotube composite ceramic network modified water-based non-stick coating |
FR3126608B1 (en) * | 2021-09-03 | 2023-09-08 | Seb Sa | COOKING ELEMENT COATED WITH A PEELABLE NON-STICK FLUORINATED POLYMERIC FILM |
KR102409467B1 (en) * | 2022-03-25 | 2022-06-16 | 리나스대성(주) | Surface treated soup kettle or frying pan by multi step surface treating method |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB0125380D0 (en) * | 2001-10-23 | 2001-12-12 | Glaxo Group Ltd | Medicament dispenser |
JP2003211084A (en) * | 2001-10-26 | 2003-07-29 | Seiko Instruments Inc | Method for applying fluorocarbon resin, sliding member using the method and gas compressor |
DE10236728A1 (en) * | 2002-08-09 | 2004-02-26 | Schott Glas | Easy to clean device |
CN1729237A (en) * | 2002-12-20 | 2006-02-01 | 西巴特殊化学品控股有限公司 | Method for forming reactive coatings |
FR2869817B1 (en) * | 2004-05-04 | 2008-05-30 | Seb Sa | METHOD FOR MANUFACTURING AN ANTI-ADHESIVE COATING AND A CULINARY ARTICLE SO COATED |
FR2904206B1 (en) * | 2006-07-31 | 2008-09-26 | Seb Sa | CULINARY ARTICLE HAVING IMPROVED HYDROPHOBIC PROPERTIES AND METHOD OF MANUFACTURING SUCH ARTICLE |
CN101528975B (en) * | 2006-10-20 | 2012-05-23 | 3M创新有限公司 | Method for easy-to-clean substrates and articles therefrom |
GB0710488D0 (en) * | 2007-06-01 | 2007-07-11 | Innovatek Medical Ltd | Methods of treating components of a medical dispenser device |
FR2923696B1 (en) * | 2007-11-16 | 2012-08-17 | Seb Sa | CULINARY ARTICLE COMPRISING ANTI-ADHESIVE COATING RESISTANT TO CORROSION AND SCRATCH |
FR2937236B1 (en) * | 2008-10-16 | 2010-11-26 | Seb Sa | CULINARY ARTICLE COMPRISING ANTI-ADHESIVE COATING HAVING IMPROVED MEDIA ADHESION PROPERTIES |
US10410838B2 (en) * | 2009-05-06 | 2019-09-10 | 3M Innovative Properties Company | Apparatus and method for plasma treatment of containers |
WO2010129758A1 (en) * | 2009-05-06 | 2010-11-11 | 3M Innovative Properties Company | Medicinal inhalation devices and components thereof |
-
2011
- 2011-08-26 FR FR1157579A patent/FR2979214B1/en not_active Expired - Fee Related
-
2012
- 2012-08-27 WO PCT/FR2012/051940 patent/WO2013030503A2/en active Application Filing
- 2012-08-27 EP EP12756795.6A patent/EP2747903B1/en active Active
- 2012-08-27 CN CN201280041616.2A patent/CN103764303B/en active Active
- 2012-08-27 KR KR1020147007497A patent/KR102023211B1/en active IP Right Grant
Non-Patent Citations (1)
Title |
---|
See references of WO2013030503A2 * |
Also Published As
Publication number | Publication date |
---|---|
KR102023211B1 (en) | 2019-09-19 |
WO2013030503A3 (en) | 2013-07-11 |
CN103764303B (en) | 2016-05-18 |
CN103764303A (en) | 2014-04-30 |
FR2979214B1 (en) | 2014-04-25 |
WO2013030503A4 (en) | 2013-09-06 |
WO2013030503A2 (en) | 2013-03-07 |
EP2747903B1 (en) | 2020-07-01 |
KR20140074301A (en) | 2014-06-17 |
FR2979214A1 (en) | 2013-03-01 |
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