EP2492022B1 - Revêtement antiadhésif - Google Patents

Revêtement antiadhésif Download PDF

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Publication number
EP2492022B1
EP2492022B1 EP20110155715 EP11155715A EP2492022B1 EP 2492022 B1 EP2492022 B1 EP 2492022B1 EP 20110155715 EP20110155715 EP 20110155715 EP 11155715 A EP11155715 A EP 11155715A EP 2492022 B1 EP2492022 B1 EP 2492022B1
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EP
European Patent Office
Prior art keywords
layer
cover layer
stick coating
tetrafluoroethylene
base layer
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
Application number
EP20110155715
Other languages
German (de)
English (en)
Other versions
EP2492022A1 (fr
EP2492022B8 (fr
Inventor
Hans Georg Geisel
Bernhard Jakob Neppl
Dieter Kadel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Looser Holding AG
Original Assignee
Looser AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Looser AG filed Critical Looser AG
Priority to EP20110155715 priority Critical patent/EP2492022B8/fr
Priority to PCT/EP2012/051712 priority patent/WO2012113627A1/fr
Publication of EP2492022A1 publication Critical patent/EP2492022A1/fr
Publication of EP2492022B1 publication Critical patent/EP2492022B1/fr
Application granted granted Critical
Publication of EP2492022B8 publication Critical patent/EP2492022B8/fr
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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
    • B05D5/086—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 having an anchoring layer
    • 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
    • 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
    • B05D2601/00—Inorganic fillers
    • 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
    • B05D2601/00—Inorganic fillers
    • B05D2601/02—Inorganic fillers used for pigmentation effect, e.g. metallic effect
    • B05D2601/08—Aluminium flakes or platelets
    • 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
    • B05D2601/00—Inorganic fillers
    • B05D2601/20—Inorganic fillers used for non-pigmentation effect
    • B05D2601/26—Abrasives
    • 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

Definitions

  • the invention relates to a non-stick coating with significantly improved abrasion resistance.
  • Organic fluoropolymer coatings show very good non-stick properties due to their low surface energy and high temperature and chemical resistance due to the high C-F bond energies.
  • non-stick coatings for kitchen appliances such coatings are widely used.
  • the low hardness of the fluoropolymers used in these coatings means that these coatings are not very resistant to damage.
  • the adhesion of the layers following the base layer depends on the content of thermoplastic fluoropolymers present in the interface between the base layer and the subsequent layer. This is due to the fact that the adhesion between the base layer and subsequent layer is achieved by the fluoropolymers in the base layer during the firing process with the fluoropolymers of the next layer merge.
  • An advantage with respect to adhesion to the substrate is a gradient of fluoropolymers with as few fluoropolymers as possible in the interface between the substrate and the base layer and as many fluoropolymers as possible in the interface between the base layer and the subsequent layer.
  • PAI Polyamide-imides
  • hard inorganic fillers have been used in addition to the aforementioned improvement in adhesion to the substrate.
  • EP 1016466 A2 describes a multi-layer ceramic reinforced non-stick coating in which the base layer contains ceramic particles, but which are so large that they protrude from the cover layer and thereby keep the abrasive stress of the cover layer.
  • US 6,761,964 describes a multilayer non-stick coating comprising a base layer of fluoropolymers, primer polymers and large inorganic filler particles anchored in the base layer and projecting into the subsequent intermediate layer consisting of fluoropolymers and smaller ceramic filler particles and a cover layer consisting exclusively of fluoropolymers ,
  • a further possibility to improve the mechanical properties of non-stick coatings is the adhesion-promoting, relatively brittle polymer polyamide-imide (PAI) (elongation at break approx. 8%) at least partially against the more viscous, linear aromatic, partially crystalline polyetheretherketone (PEEK, FIG. 2 ) (Breaking elongation approx. 50%).
  • PAI polymer polyamide-imide
  • the coatings are less brittle and a force on the coating leads less quickly to breakage.
  • US 6,596,380 describes, for example, a multilayer coating which has a base layer consisting of min. 50% PEEK adhesion promoting polymers selected from polyamideimide (PAI), polyphenylene sulphide (PPS), polyetherimide (PEI) or polyimide (PI) and inert inorganic fillers, followed by an intermediate layer consisting of organic fluoropolymers and a topcoat of organic fluoropolymers.
  • PES polyphenylene sulphide
  • PEI polyetherimide
  • PI polyimide
  • WO 00/54895 a non-stick coating with improved scratch resistance with a base layer applied to a substrate consisting exclusively of polyetheretherketone (PEEK), which is characterized by one or more several cover layers which includes a fluoroplastic is covered.
  • the layer following the polyetheretherketone layer is an adhesion-promoting polyamideimide-containing layer.
  • the base layer is first melted at at least 340 ° C and cooled again, then the adhesion-promoting intermediate layer consisting of polyamide-imide (PAI) and PTFE and the possibly following outer layers is applied and baked the entire assembly at 400 to 420 ° C.
  • PAI polyamide-imide
  • DE 10 2005 004828 A1 describes a multilayer coating whose base layer comprises one or more high-performance polymers selected from polyaryl ether ketones (PEEK or PEK), liquid crystal polymers (LCP), polyphenylene sulfide (PPS) or mixtures thereof and the final covering layer of a high-performance thermoplastic selected from polyaryl ether ketones (PEEK or PEK), liquid crystal polymers ( LCP), polyphenylene sulfide (PPS) and 20-30% thermoplastic fluoropolymers.
  • a high-performance thermoplastic selected from polyaryl ether ketones (PEEK or PEK), liquid crystal polymers ( LCP), polyphenylene sulfide (PPS) and 20-30% thermoplastic fluoropolymers.
  • hard inorganic fillers may be contained in the layers lying below the top layer whose d 50 value of the particle size must be at most twice as large as the layer thickness of the finished baked layer.
  • US 5,536,583 describes an article comprising as a base layer a polyether resin layer and at least one cover layer consisting of a fluoropolymer resin and an additive such as polyphenylene sulfide (PPS) or inorganic crystalline powders.
  • PPS polyphenylene sulfide
  • fluoropolymers there have been used tetrafluoroethylene-perfluoro (alkyloxyvinyl ether) copolymer (PFA), poly (vinylidene fluoride) (PVDF), ethylene-chlorotrifluoroethylene copolymer (E-CTFE), ethylene-tetrafluoroethylene copolymer (E-TFE), perfluoroethylene-propylene copolymer (FEP) and poly (chlorotrifluoroethylene) (CTFE) or mixtures thereof, but not polytetrafluoroethylene (PTFE).
  • PFA tetrafluoroethylene-perfluoro (alkyloxyvinyl ether) copolymer
  • PVDF poly (vinylidene fluoride)
  • E-CTFE ethylene-chlorotrifluoroethylene copolymer
  • E-TFE ethylene-tetrafluoroethylene copolymer
  • FEP perfluoroethylene-propylene copo
  • PTFE has the highest non-stick effect among fluoropolymers. Due to its high melt viscosity above the crystallite melting range, PTFE is not easy to melt but only sinters at the grain boundaries. This makes it difficult to formulate a cover layer for polyether resin layers with PTFE contents> 30%. Topcoats with high PTFE contents have so far shown no sufficient adhesion to the underlying layer without the use of adhesion promoter layers.
  • An object of the present invention is to propose an improved non-stick coating for an article over the prior art.
  • the object of the invention is achieved by the non-stick coating according to claim 1.
  • This non-stick coating has at least three layers, with a cover layer having a dry film thickness of 10 to 50 .mu.m, preferably 20 and 30 .mu.m, an intermediate layer having a dry film thickness of 10 to 100 .mu.m, preferably 20 and 30 .mu.m, and a base layer with a Dry film thickness of 10 to 50 microns, preferably from 20 and 30 microns.
  • the top layer contains 40% to 90% organic fluoropolymers, wherein 20% to 50%, based on the top layer, polytetrafluoroethylene (PTFE) and 20% to 70%, based on the top layer, copolymers of tetrafluoroethylene with perfluoroalkyl vinyl ether with 1-3 C atoms in the alkyl group, namely MFA or PFA, or copolymers of tetrafluoroethylene with hexafluoropropylene (FEP) or mixtures thereof. Furthermore, the topcoat contains 10% to 60% poly (oxy-1,4, phenylenecarbonyl-1,4-phenylene) (PEK).
  • PEK poly (oxy-1,4, phenylenecarbonyl-1,4-phenylene)
  • the intermediate layer contains 20-30% of organic thermoplastic fluoropolymers selected from copolymers of tetrafluoroethylene with perfluoroalkyl vinyl ether having 1-3 C atoms in the alkyl group, namely MFA or PFA, copolymers of tetrafluoroethylene with hexafluoropropylene (FEP) or mixtures thereof, and poly ( oxy-1,4-phenylenecarbonyl-1,4-phenylene) (PEK), as well as inorganic fillers.
  • the fillers comprise particles with a size of 40 ⁇ m to 100 ⁇ m, preferably from 45 ⁇ m to 70 ⁇ m.
  • the particle size is selected so that at least some of the particles protrude partially into the cover layer, but do not penetrate this cover layer.
  • Copolymers of tetrafluoroethylene with perfluoroalkyl vinyl ether having 1-3 C atoms in the alkyl group (MFA or PFA)
  • copolymers of tetrafluoroethylene with hexafluoropropylene (FEP) or mixtures thereof) are possible in the cover layer and thereby an improved non-stick effect without the To lose adhesion to the underlying layer or to require an additional adhesion-promoting layer of polyamide-imide (PAI) or polyphenylene sulfide (PPS).
  • PAI polyamide-imide
  • PPS polyphenylene sulfide
  • a base layer which has more than 98% poly (oxy-1,4-phenylenecahonyl-1,4-phenylene) (PEK).
  • the inorganic fillers comprise ceramic hard materials from the series of oxides, carbides, nitrides, borides, in particular silicon carbide and / or aluminum oxide.
  • the particles of the inorganic fillers of the intermediate layer have at least partially penetrated into the base layer. This is a particular advantage of the invention.
  • FIG. 4 has a non-stick coating, in particular for a cookware three layers, namely a cover layer 6 with a dry film thickness of about 20 and 30 microns, an intermediate layer 4 with a dry film thickness of about 20 and 30 microns, and a base layer 2 with a Dry film thickness about 20 and 30 microns.
  • the cover layer 6 in this embodiment contains about 55% of organic fluoropolymers.
  • the cover layer 6 contains about 35% by weight of poly (oxy-1,4-phenylenecarbonyl-1,4-phenylene) (PEK).
  • the intermediate layer 4 contains about 30% of a copolymer of tetrafluoroethylene with perfluoroalkyl vinyl ether having 1-3 C atoms in the alkyl group, namely PFA and about 70% poly (oxy-1,4-phenylenecabonyl-1,4-phenylene) (PEK), as well as inorganic fillers 8.
  • the fillers have particles with a size of up to 70 ⁇ m. In this case, the particle size is selected so that at least some of the particles protrude partially into the cover layer 6, but do not penetrate this cover layer 6.
  • the base layer 2 of this preferred embodiment has greater than 98% poly (oxy-1,4-phenylenecarbonyl-1,4-phenylene) (PEK).
  • PEK polyetherketone
  • PEEK poly (oxy-1,4-phenylenecarbonyl-1,4-phenylene); for use as a non-stick coating for frying and cooking utensils; FIG. 3
  • PEEK polyetheretherketone
  • PEK has a higher glass transition temperature and a higher melting point, as compared with polyether ether ketone (PEEK; poly (oxy-1,4-phenyleneoxy-1,4-phenylenecarbonyl-1,4-phenylene), with comparable toughening elasticity.
  • the preferred method for applying the non-stick coating is such that the layers are applied by a wet-in-wet application, namely without intermediate drying, from aqueous dispersions and subsequent drying and melting.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)

Claims (5)

  1. Revêtement anti-adhésif d'une pièce, ce revêtement anti-adhésif comportant au moins trois couches, à savoir :
    - une couche de recouvrement (6) ayant une épaisseur de film sec de 10 à 50 µm de préférence de 20 à 30 µm,
    - une couche intermédiaire (4) ayant une épaisseur de film sec de 10 à 100 µm, de préférence de 20 à 30 µm, et
    - une couche de base (2) ayant une épaisseur de film sec de 10 à 50 µm, de préférence de 20 à 30 µm,
    la couche de recouvrement (6) renfermant 40 % à 90 % de fluoropolymères organiques 20 à 50 % de ces composés étant constitués par rapport à la couche de recouvrement (6) par du polytétrafluoréthylène (PTFE) tandis que 20 % à 70 % sont constitués, toujours par rapport à la couche de recouvrement par des copolymères de tétrafluoréthylène avec des perfluoralkyl vinyl éther dont le groupe alkyl renferme 1-3 atomes de carbone, à savoir MFA ou PFA ou des copolymères de polytétrafluoréthylène avec de l'hexafluorpropylène (FEP) ou des mélanges de ses composés, et la couche de recouvrement (6) renfermant 10 % à 60 % de poly(oxy-1,4-phénylène-carbonyl-1-4-phénylène) (PEK),
    la couche intermédiaire (4) renfermant 20 % à 30 % de fluoropolymères thermoplastique organique choisis dans le groupe formé par les copolymères de tétrafluoréthylène avec des perfluoralkyl vinyl éther dont le groupe alkyl renferme 1-3 atomes C, à savoir MFA ou PFA, des copolymères de tétrafluoréthylène avec de l'hexafluoropropylène (FEP) ou des mélanges de ses composés, et du poly(oxy-1,4-phénylène-carbonyl-1-4-phénylène) (PEK) et des charges minérales (8), ces charges minérales (8) renfermant des particules ayant une granulométrie de 40 µm à 100 µm, de préférence de 45 µm à 70 µm, et la granulométrie des particules étant choisie de manière qu'au moins certaines des particules pénètrent partiellement dans la couche de recouvrement (6) sans toutefois traverser cette couche de recouvrement (6).
  2. Revêtement anti-adhésif conforme à la revendication 1,
    caractérisé en ce que
    la couche de base (2) renferme plus de 98 % de poly(oxy-1,4-phénylène-carbonyl-1,4-phénylène) (PEK).
  3. Revêtement anti-adhésif conforme à la revendication 1 ou 2, caractérisé en ce que
    les charges minérales (8) renferment des substances dures céramiques choisies parmi les oxydes, les carbures, les nitrures et les borures.
  4. Revêtement anti-adhésif conforme à la revendication 3,
    caractérisé en ce que
    les charges minérales (8) renferment du carbure de silicium et/ou de l'oxyde aluminium.
  5. Revêtement anti-adhésif conforme à l'une des revendications 1 à 4, caractérisé en ce que
    les particules de charges minérales (8) de la couche intermédiaire pénètrent partiellement dans la couche de base.
EP20110155715 2011-02-23 2011-02-23 Revêtement antiadhésif Active EP2492022B8 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP20110155715 EP2492022B8 (fr) 2011-02-23 2011-02-23 Revêtement antiadhésif
PCT/EP2012/051712 WO2012113627A1 (fr) 2011-02-23 2012-02-01 Revêtement anti-adhésif, article doté d'un revêtement anti-adhésif et procédé pour appliquer un revêtement anti-adhésif

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP20110155715 EP2492022B8 (fr) 2011-02-23 2011-02-23 Revêtement antiadhésif

Publications (3)

Publication Number Publication Date
EP2492022A1 EP2492022A1 (fr) 2012-08-29
EP2492022B1 true EP2492022B1 (fr) 2013-03-13
EP2492022B8 EP2492022B8 (fr) 2013-04-24

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ID=44063148

Family Applications (1)

Application Number Title Priority Date Filing Date
EP20110155715 Active EP2492022B8 (fr) 2011-02-23 2011-02-23 Revêtement antiadhésif

Country Status (2)

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EP (1) EP2492022B8 (fr)
WO (1) WO2012113627A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102011119731A1 (de) 2011-11-30 2013-06-06 Rhenotherm Kunststoffbeschichtungs Gmbh PEK und/oder PEEK enthaltende Beschichtung

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1054595B (it) 1975-02-04 1981-11-30 Du Pont Dispersioni acquose di polimeri perfluoroolefinici contenti materiali filmogeni
US5536583A (en) 1986-07-01 1996-07-16 Edlon Products, Inc. Polymer metal bonded composite and method of producing same
US5240775A (en) 1991-09-23 1993-08-31 E. I. Du Pont De Nemours And Company Non-stick coating system with PTFE-PFA for concentration gradient
US5250356A (en) 1992-08-28 1993-10-05 E. I. Du Pont De Nemours And Company Cookware coating system
US6291054B1 (en) 1999-02-19 2001-09-18 E. I. Du Pont De Nemours And Company Abrasion resistant coatings
FR2791066A1 (fr) 1999-03-16 2000-09-22 Seb Sa Revetement anti-adhesif presentant une resistance amelioree a la rayure
FR2791065A1 (fr) 1999-03-16 2000-09-22 Seb Sa Revetement anti-adhesif presentant une resistance amelioree a la rayure
ATE432162T1 (de) 2000-08-17 2009-06-15 Whitford Corp Mehrschichtiges antihaft-beschichtungssystem und so beschichtete artikel
US6761964B2 (en) 2001-04-02 2004-07-13 E. I. Du Pont De Nemours And Company Fluoropolymer non-stick coatings
JP4364664B2 (ja) 2004-02-04 2009-11-18 シャープ株式会社 発光ダイオード駆動回路および光ファイバリンク用光送信機
US7858188B2 (en) * 2005-12-14 2010-12-28 Dupont-Mitsui Fluorochemicals Co Ltd Non-stick coating composition comprising diamond particles and substrate
US9903021B2 (en) * 2008-12-29 2018-02-27 Axalta Coatings Systems Ip Co., Llc Method for using 3-coat-1-bake waterborne coating composition

Also Published As

Publication number Publication date
WO2012113627A1 (fr) 2012-08-30
EP2492022A1 (fr) 2012-08-29
EP2492022B8 (fr) 2013-04-24

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