EP1419016A1 - Non-stick coating having improved scratch and abrasion resistance - Google Patents
Non-stick coating having improved scratch and abrasion resistanceInfo
- Publication number
- EP1419016A1 EP1419016A1 EP02700369A EP02700369A EP1419016A1 EP 1419016 A1 EP1419016 A1 EP 1419016A1 EP 02700369 A EP02700369 A EP 02700369A EP 02700369 A EP02700369 A EP 02700369A EP 1419016 A1 EP1419016 A1 EP 1419016A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- primary layer
- support
- coating according
- layers
- ceramic particles
- 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
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
- 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
- B05D7/58—No clear coat specified
- B05D7/582—No clear coat specified all layers being cured or baked together
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
- Y10T428/12556—Organic component
- Y10T428/12569—Synthetic resin
Definitions
- the present invention relates to a non-stick coating having improved resistance to scratching and abrasion.
- the invention also relates to articles, and in particular cooking utensils, comprising a coating according to the invention.
- the non-stick coatings commonly used to coat cookware are made from fluorocarbon resin, such as polytetrafluoroethylene (PTFE).
- fluorocarbon resin such as polytetrafluoroethylene (PTFE).
- PTFE polytetrafluoroethylene
- these coatings are formed by the application, directly to the support, of a first bonding layer based on fluorocarbon resin, commonly called “primary layer", this first layer being covered by one or more layers of finish, also based on fluorocarbon resin.
- Such PTFE-based coatings are known for their non-stick properties but also for their chemical and thermal resistance.
- a first solution consists in forming a hard undercoat or a hard base between the support and the primary layer, said underlay forming a barrier preventing scratches from reaching the surface of the support.
- a hard undercoat may in particular be formed by a polymer, such as polyamide-imide (PAI) and / or oxy-1,4-phenylene-oxy-1,4-phenylene-carbonyl-1,4-phenylene. (PEEK), as taught by international applications WO 00/54895 and WO 00/54896 in the name of the Applicant.
- PAI polyamide-imide
- PEEK oxy-1,4-phenylene-oxy-1,4-phenylene-carbonyl-1,4-phenylene.
- a hard base can in particular be enamel, stainless steel or alumina.
- a hard base formed of alumina can be deposited on the support by thermal plasma spraying.
- this hard alumina base can also be formed directly from the support, by anodic oxidation of the latter.
- a coating comprising such a hard base, and whose resistance to scratching and abrasion is particularly satisfactory, has been described by the Applicant in its application EP 0 902 105.
- a second solution for reinforcing PTFE-based coatings consists in introducing reinforcing fillers into one of the layers forming said coatings, especially in the primary layer.
- reinforcing fillers there may be mentioned inorganic particles such as mica particles (EP 0 389 966), silica, mullite (FR 2 756 875) or metallic flakes or metallic oxides, in particular particular aluminum (EP 0 656 831).
- the average dimensions of the inorganic particles indicated by the two European documents are of the order of 5 to 200 microns.
- EP 1 016 466 describes a coating the objective of which is to deflect the abrasive forces of the external surface of the coating: for this, it comprises a primary layer based on fluorocarbon resin and which contains ceramic inorganic particles which extend beyond this primary layer, the primary layer being applied to the support and covered by one or two upper layers based on fluorocarbon resin, these upper layers covering all the ceramic particles which can extend beyond the primary layer.
- the ceramic particles present in the primary layer taught by this prior art have dimensions such that they deform the surface of the upper layers and thus ensure the formation of deflection zones on the external surface of the coating, these deflection zones allowing then deflecting the abrasion forces, thereby increasing the abrasion resistance of the coating.
- the average dimensions of the ceramic particles allowing the formation of these deflection zones are a function of the total thickness of the dry coating, according to the following relationship: the ratio of this total thickness of dry coating over the longest diameter of said ceramic particles is between 0.8 and 2.0.
- This document specifies that such particles have an average dimension of at least 14 microns ( ⁇ m), advantageously at least, 20 ⁇ m and preferably at least 25 ⁇ m.
- This prior art certainly tends to respond to the problem of producing a non-stick coating which resists scratching and abrasion but indirectly since it tends to protect the surface of the coating by deflecting the abrasion forces, and thus avoids the perforation of the coating itself.
- the external surface of the coating is then by definition deformed by the presence of the deflection zones which, over time, will be eroded under the action of friction forces, this may eventually lead to the formation of bare zones, the non-stick coating properties partially decreasing.
- the object of the present invention is therefore to provide a coating which, while retaining excellent non-stick properties, has in itself and not by a deflection effect, improved resistance to scratching and abrasion , without deformation of its external surface and without necessarily resorting to the insertion of a hard undercoat or a specific hard base, in the particular application of culinary utensils.
- the subject of the present invention is therefore a coating comprising at least one primer layer containing a fluorocarbon resin and particles inorganic, the primer being applied to a support and covered by one or more topcoats based on fluorocarbon resin.
- the inorganic particles are ceramic particles having an average diameter of less than 4 microns ( ⁇ m) and are entirely included in the primary layer, the external surface of which is therefore not deformed by their presence.
- the ceramic particles which meet the object of the present invention have a high hardness which is greater than approximately 1500 Vickers and a remarkable melting resistance, with melting points greater than 2000 ° C.
- the average diameter of the ceramic particles is between 0.01 and 3 ⁇ m approximately, advantageously between 0.05 and 2 ⁇ m approximately, more advantageously between 0.1 and 1 ⁇ m approximately, preferably of the order of 0, 5 ⁇ m approximately.
- the ceramic particles of the invention give the coating a resistance to scratching and abrasion significantly greater than that of the coatings comprising inorganic particles described by the prior art, such as mica, mullite, metallic flakes, on the one hand and / or of dimensions greater, or even much greater, recommended by the prior art, on the other hand.
- This observation is all the more surprising and unexpected as the remarkable physical and chemical properties of the ceramic particles according to the invention, in particular extreme hardness combined with a high melting point, are expressed even for extremely small dimensions.
- the ceramic particles used in the context of the present invention comprise at least one element chosen from metallic carbides, metallic nitrides, metallic borides, metallic oxycarbons, metallic oxynitrides, metallic carbonitrides and metallic oxides.
- the metal is a refractory metal, or even a mixture of refractory metals.
- a refractory metal or even a mixture of refractory metals.
- the refractory metals are chosen from titanium (Ti), zirconium (Zr), hafnium (H), tantalum (Ta), niobium (Nb), tungsten (W), molybdenum (Mo ), boron (B), beryllium (Be), silicon (Si) and aluminum (Al).
- the ceramic particles described by EP 0 543 753 have a particularly high hardness, in this case greater than 2000
- Vickers associated with an equally high density, which can be between 5 and 16 approximately.
- the ceramic particles as taught by EP 0 543 753 make it possible to better resist the impact of the "large” particles which would strike the multilayer coating according to the invention.
- the metal is at least one of the elements chosen from Ti, Zr or Hf.
- TiN, ZrN or HfN combine both the characteristics of high hardness and high melting point mentioned above with those of metals, similar in particular in terms of thermal conductivity.
- the weight proportion of ceramic particles in the primary layer is, after firing, between 1 and 40%, advantageously between 3 and 25%, preferably between
- the invention also relates to a method for producing a coating on a support, this method comprising the following steps:
- - ceramic particles are incorporated homogeneously into a composition comprising a fluorocarbon resin to form a primary layer, - at least one primary layer containing the ceramic particles is applied to the support , the primary layer forming a smooth surface,
- topcoat (s) based on fluorocarbon resin are applied to this primer layer, then
- the invention relates in particular to cooking utensils coated inside and / or outside with a non-stick coating.
- the support of these utensils can be aluminum, steel, enamelled steel, stainless steel, glass, ceramic.
- This support may or may not undergo a preliminary treatment, depending on whether one wishes to have a rough or smooth support: it can thus be treated chemically, by acid attack for example, or mechanically, in particular by sanding.
- the primary and topcoats contain a fluorocarbon resin.
- This fluorocarbon resin can be PTFE, perfluoroalkoxy (PFA) or fluorinated ethylene-propylene (FEP), or a mixture of these compounds.
- the primary and finishing layers are deposited on the support, whether or not previously treated, by spraying (spraying), by screen printing, for example in accordance with the process described in document FR 2 689 037 in the name of the Applicant, by pad printing or by roller coating.
- spraying spraying
- screen printing for example in accordance with the process described in document FR 2 689 037 in the name of the Applicant, by pad printing or by roller coating.
- Example 1 The coating of this example 1 is constituted by a primary layer applied to the support, then covered by two finishing layers, formed by an intermediate layer, itself covered by a top finishing layer.
- the composition of each of the three layers, given in parts by weight, is shown below, by way of example:
- PAI polyamide-imide
- spreading agent emulsion and film former 4-10 dispersion of fluorocarbon resin (s) (from 50 to 60% of dry extract) 15-35
- colloidal silica (30% dry extract) 10-16
- TiC powder (0.1 to 1 ⁇ m) 1-10
- dispersion of PTFE (60% dry extract) 78-90.
- emulsion of spreading agent and film-forming agent 10-20.
- the primary layer is preferably formed by a homogeneous composition of the ceramic particles with the fluorocarbon resin.
- the titanium carbide (TiC) incorporated in the primary layer is made up of a mixture of ceramic particles whose average diameter is between 0.1 and 1 micron .
- the primary layer is deposited on the support to form a smooth surface, that is to say a flat external surface, devoid of any deflection zone.
- the primary layer is then dried to obtain a primary layer whose thickness is between 4 and 16 ⁇ m; the intermediate layer is then applied, then the upper finishing layer, the assembly consisting of the intermediate and upper finishing layers having a thickness of between 10 and 25 ⁇ m. After all three layers have dried, a sintering step is carried out at 400-420 ° C of the coating thus obtained, for 3 to 7 minutes.
- a coating is obtained, on the one hand strongly adhering to the support and, on the other hand, which exhibits scratch resistance performance.
- improved tests have shown that intensive cooking of food by means of metal spatulas on a culinary utensil, in this case a pan, covered with a coating conforming to the first example above, these cooking representing one to two years conventional use of a cooking utensil, practically did not scratch the coating, compared to identical intensive cooking carried out by means of plastic spatulas, on a utensil, the primary layer of which did not contain TiC particles.
- the coating may further comprise, between the support and the primer layer, a hard undercoat.
- the coating can also include at least two primary layers, each of which contains ceramic particles having an average diameter of less than 4 microns.
- This coating is produced by depositing: - a hard undercoat devoid of fluorocarbon resin as described by WO 00/54896 or WO 00/54896, this undercoat being directly applied to the support,
- the sublayer devoid of fluorocarbon resin, is based on polyetheretherketone or oxy-1,4-phenylene-oxy-1,4-phenylene-carbonyl-1,4-phenylene (PEEK).
- the two primary layers have a composition identical to that of the primary layer of Example 1, and both contain TiC consisting of a mixture of particles whose average diameter is between 0.1 and 1 micron.
- the total thickness formed by the two primary layers is between 4 and 16 ⁇ m.
- the intermediate and upper finishing layers have respective compositions identical to those described in Example 1 above.
- the support Before the application of the PEEK-based undercoat, the support may or may not be chemically or mechanically treated, to make its surface rough.
- the undercoat can be applied to the support by spraying in the form of an aqueous dispersion.
- WO 00/54895 or with at least 50% PEEK, the remainder being composed of pure thermostable polymers or in a mixture
- inert fillers selected from metal oxides, silica, mica particles, or lamellar fillers, as taught in
- the primary, intermediate and upper finishing layers are then successively applied, in accordance with the procedure described above for Example 1.
- the coating may further comprise, between the support and the primer layer, a hard base.
- a third exemplary embodiment of a coating combining a hard base and the application of two primary layers is given below.
- This coating consists of:
- the hard base can be of the ceramic type and formed on the support, for example, by plasma application of a layer of Al 2 O 3 / Ti0 2 . It can also be of metallic type, and produced on the support by plasma deposition of stainless steel powder.
- This hard base can also be obtained directly from the support, and prior to the application of the primary layer or layers, by carrying out a hard anodization or an anodization by micro-arcs as described in EP 0 902 105 in the name of the Applicant.
- the invention is not limited to the examples described above, and whose improved resistance to scratching and abrasion properties have been measured for cooking utensils having an inner surface intended to be in contact with the food, covered with a coating according to the invention.
- Such a coating can obviously be used more widely in the culinary field, to coat the interior and / or exterior of any type of culinary utensils, hobs, grill plates, ...; it can also be intended to coat any sliding surface, and in particular those of an iron for example.
Landscapes
- Cookers (AREA)
- Laminated Bodies (AREA)
- Polishing Bodies And Polishing Tools (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0110021A FR2827869B1 (en) | 2001-07-26 | 2001-07-26 | ANTI-ADHESIVE COATING HAVING ENHANCED SCRATCH AND ABRASION RESISTANCE |
FR0110021 | 2001-07-26 | ||
PCT/FR2002/000260 WO2003009947A1 (en) | 2001-07-26 | 2002-01-22 | Non-stick coating having improved scratch and abrasion resistance |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1419016A1 true EP1419016A1 (en) | 2004-05-19 |
EP1419016B1 EP1419016B1 (en) | 2006-07-12 |
Family
ID=8865957
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP02700369A Revoked EP1419016B1 (en) | 2001-07-26 | 2002-01-22 | Non-stick coating having improved scratch and abrasion resistance |
Country Status (8)
Country | Link |
---|---|
US (1) | US20040261932A1 (en) |
EP (1) | EP1419016B1 (en) |
AT (1) | ATE332762T1 (en) |
DE (1) | DE60213102T2 (en) |
ES (1) | ES2267976T3 (en) |
FR (1) | FR2827869B1 (en) |
TW (1) | TWI296640B (en) |
WO (1) | WO2003009947A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7270318B2 (en) | 2001-11-12 | 2007-09-18 | Stromsholmen Ab | Device at an energy accumulating piston-cylinder tool |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR200383502Y1 (en) * | 2005-02-22 | 2005-05-03 | 김명석 | a cooking pot having stone |
FR2897250B1 (en) * | 2006-02-13 | 2008-04-04 | Seb Sa | EASY-TO-CLEAN COOKING SURFACE AND HOUSEHOLD ARTICLE COMPRISING SUCH A SURFACE |
US8158251B2 (en) * | 2008-02-07 | 2012-04-17 | E. I. Du Pont De Nemours And Company | Article with non-stick finish and improved scratch resistance |
FR2982754B1 (en) * | 2011-11-21 | 2014-07-25 | Seb Sa | MACHINING-RESISTANT COOKING SURFACE AND CULINARY ARTICLE OR HOUSEHOLD APPLIANCE COMPRISING SUCH A COOKING SURFACE |
DE102012002608B4 (en) | 2012-02-13 | 2017-01-19 | Warimex Waren-Import Export Handels-Gmbh | Pan or saucepan |
DE202012001366U1 (en) | 2012-02-13 | 2013-02-14 | Warimex Waren-Import Export Handels-Gmbh | Pan or saucepan |
CN106661736A (en) | 2014-07-30 | 2017-05-10 | 惠普发展公司,有限责任合伙企业 | Wear resistant coating |
ITUA20161564A1 (en) * | 2016-03-11 | 2017-09-11 | Tvs Spa | CONTAINER FOR COOKING FOOD, AND PROCEDURE FOR ITS REALIZATION |
DE202016105515U1 (en) | 2016-10-05 | 2016-12-02 | Warimex Waren-Import Export Handels-Gmbh | Cookware |
DE102016118832A1 (en) | 2016-10-05 | 2018-04-05 | Warimex Waren-Import Export Handels-Gmbh | Cookware |
CN108968702B (en) * | 2017-06-01 | 2023-11-28 | 佛山市顺德区美的电热电器制造有限公司 | Non-stick coating, preparation method thereof, cooker and cooking equipment |
DE102018201715A1 (en) * | 2018-02-05 | 2019-08-08 | Federal-Mogul Nürnberg GmbH | Process for coating a sliding surface, in particular an engine piston |
CA3091641A1 (en) | 2018-02-06 | 2019-08-15 | Thermolon Korea Co. Ltd. | Non-stick ceramic coating comprising diamonds and coloured mica |
FR3112553A1 (en) * | 2020-07-17 | 2022-01-21 | Seb S.A. | Non-stick coating based on fluoropolymer with improved thermal conductivity properties |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5061548A (en) * | 1987-02-17 | 1991-10-29 | Rogers Corporation | Ceramic filled fluoropolymeric composite material |
JPH01194979A (en) * | 1987-09-25 | 1989-08-04 | Kansai Paint Co Ltd | Method of coating aluminum foil |
EP0389966B1 (en) * | 1989-03-25 | 1994-08-10 | Sumitomo Electric Industries, Ltd. | Fluororesin-coated article |
EP0574556A1 (en) * | 1991-08-26 | 1993-12-22 | Preemptive Technologies, Inc. | Surface finish compositions |
FR2684105B1 (en) * | 1991-11-21 | 1994-09-09 | Neyrpic | WEAR RESISTANT COMPOSITE MATERIALS AND PROCESS FOR THEIR MANUFACTURE. |
US5250356A (en) * | 1992-08-28 | 1993-10-05 | E. I. Du Pont De Nemours And Company | Cookware coating system |
JPH07251130A (en) * | 1994-03-11 | 1995-10-03 | Kansai Paint Co Ltd | Formation of water-repellent coating film |
US5562991A (en) * | 1994-10-31 | 1996-10-08 | E. I. Du Pont De Nemours And Company | Universal Primer for non-stick finish |
FR2744129B1 (en) * | 1996-01-29 | 1998-04-10 | Seb Sa | ANTI-ADHESIVE COATING FOR ALUMINUM KITCHEN UTENSILS |
WO1999017959A1 (en) * | 1997-10-08 | 1999-04-15 | E.I. Du Pont De Nemours And Company | Lustrous laminate film structures |
US6291054B1 (en) * | 1999-02-19 | 2001-09-18 | E. I. Du Pont De Nemours And Company | Abrasion resistant coatings |
US6403213B1 (en) * | 1999-05-14 | 2002-06-11 | E. I. Du Pont De Nemours And Company | Highly filled undercoat for non-stick finish |
-
2001
- 2001-07-26 FR FR0110021A patent/FR2827869B1/en not_active Expired - Fee Related
-
2002
- 2002-01-22 WO PCT/FR2002/000260 patent/WO2003009947A1/en active IP Right Grant
- 2002-01-22 DE DE60213102T patent/DE60213102T2/en not_active Revoked
- 2002-01-22 EP EP02700369A patent/EP1419016B1/en not_active Revoked
- 2002-01-22 ES ES02700369T patent/ES2267976T3/en not_active Expired - Lifetime
- 2002-01-22 US US10/484,761 patent/US20040261932A1/en not_active Abandoned
- 2002-01-22 AT AT02700369T patent/ATE332762T1/en not_active IP Right Cessation
- 2002-07-25 TW TW091116619A patent/TWI296640B/zh not_active IP Right Cessation
Non-Patent Citations (1)
Title |
---|
See references of WO03009947A1 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7270318B2 (en) | 2001-11-12 | 2007-09-18 | Stromsholmen Ab | Device at an energy accumulating piston-cylinder tool |
Also Published As
Publication number | Publication date |
---|---|
WO2003009947B1 (en) | 2004-05-27 |
DE60213102T2 (en) | 2007-02-15 |
DE60213102D1 (en) | 2006-08-24 |
ES2267976T3 (en) | 2007-03-16 |
TWI296640B (en) | 2008-05-11 |
FR2827869B1 (en) | 2007-04-13 |
EP1419016B1 (en) | 2006-07-12 |
ATE332762T1 (en) | 2006-08-15 |
FR2827869A1 (en) | 2003-01-31 |
US20040261932A1 (en) | 2004-12-30 |
WO2003009947A1 (en) | 2003-02-06 |
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