# US 2014/0034651 A1 · Metal-Oxide Nanofiller, Method for Synthesising Same, and Use Thereof in a Fluorocarbon-Resin Non-Stick Coating

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- Number: US 2014/0034651 A1
- Document ID: US20140034651A1
- Status: Published application
- Kind: A1
- Application number: 13/990,431
- Filed: 2011-11-30
- Published: 2014-02-06
- Earliest claimed: 2010-11-30
- Assignees: Specific Polymers; Seb S.A.
- Inventors: Nelly Durand; Bernard Boutevin; Bruno Ameduri; Cedric Loubat; Barbara Gantillon; Jean-Luc Perillon
- Web page: https://patentgrep.com/patent/US20140034651A1

## CPC

- C09D 7/63: organic
- A47J 36/025: {Vessels with non-stick features, e.g. coatings}
- B82Y 30/00: Nanotechnology for materials or surface science, e.g. nanocomposites
- C09C 1/3072: {Treatment with macro-molecular organic compounds}
- C09C 1/3081: {Treatment with organo-silicon compounds}
- C09C 1/309: {Combinations of treatments provided for in groups C09C1/3009 - C09C1/3081}
- C09C 1/407: {Aluminium oxides or hydroxides}
- C09C 3/006: {Combinations of treatments provided for in groups C09C3/04 - C09C3/12}
- C09C 3/10: Treatment with macromolecular organic compounds {(C09C3/006 takes precedence)}
- C09C 3/12: Treatment with organosilicon compounds {(C09C3/006 takes precedence)}
- C09D 7/41: Organic pigments; Organic dyes
- B05D 5/083: {involving the use of fluoropolymers}
- C01P 2002/86: by NMR- or ESR-data
- C01P 2004/61: Micrometer sized, i.e. from 1-100 micrometer
- C01P 2004/62: Submicrometer sized, i.e. from 0.1-1 micrometer
- C01P 2004/64: Nanometer sized, i.e. from 1-100 nanometer
- C01P 2006/12: Surface area
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- A47J: KITCHEN EQUIPMENT; COFFEE MILLS; SPICE MILLS; APPARATUS FOR MAKING BEVERAGES
- B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- C09C: TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES (treatment of materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone C04B14/00, C04B18/00, C04B20/00); PREPARATION OF CARBON BLACK {; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS}
- B05D: PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL (conveying articles or workpieces through baths of liquid B65G, e.g. B65G49/02)
- C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS

## Abstract

Provided is a metal-oxide nanofiller including at least two graft chains, at least one of the chains being hydrophilic and the other being a hydrophobic chain compatible with fluorinated polymers. The hydrophobic chain is an oligomer, the weight-average molar mass Mw of which is between 300 and 20,000 g/mol−1. Also provided is a non-stick coating comprising such a filler, as well as to a culinary article provided with such a coating.

## Claims

### Claim 1

A nanofiller of a metal-oxide comprising at least two graft chains, at least one of the chains being hydrophilic and the other being a hydrophobic chain compatible with fluorinated polymers, wherein the hydrophobic chain is an oligomer, the weight-average molar mass Mw of which is between 300 and 20.000 g/mol'1.

### Claim 2 (depends on 1)

The nanofiller according to claim 1, wherein the hydrophobic chain is an oligomer, the weight-average molar mass Mw of which is between 500 and 10.000 g/mol−1.

### Claim 3 (depends on 2)

The nanofiller according to claim 2, wherein the hydrophobic chain is an oligomer, the weight-average molar mass Mw of which is between 1000 and 5000 g/mol−1.

### Claim 4 (depends on 1)

The nanofiller according to claim 1, wherein the metal oxide is selected among the group constituted of silica, alumina, cerium oxide, zinc oxide, vanadium oxide, zirconium oxide, and titanium dioxide.

### Claim 5 (depends on 4)

The nanofiller according to claim 4, wherein the metal oxide is silica, colloidal silica or pyrogenic silica.

### Claim 6 (depends on 1)

The nanofiller according to claim 1, wherein the hydrophilic chain is a derivative of polyalkylene glycol modified by:
either an alkoxysilane,
or an acid or a phosphonic ester,
or an acid or phosphinic ester,
or a carboxylic acid.

### Claim 7 (depends on 6)

The nanofiller according to claim 6, wherein the polyalkylene glycol derivative is a polyethylene-glycol (PEG) derivative or a polypropylene glycol (PPG) derivative.

### Claim 8 (depends on 6)

The nanofiller according to claim 6, wherein the hydrophilic chain is a derivative of polyethylene glycol modified by an alkoxysilane.

### Claim 9 (depends on 1)

The nanofiller according to claim 1, wherein the hydrophobic chain or chains is (or are) an oligomer of hexafluoropropylene oxide (HFPO), of vinylidene fluoride (VDF), of tetrafluoroethylene (TFE) or co-oligomers VDF-TFE, VDF-hexafluoropropylene, VDF-chlorotrifluoroethylene, alone or in mixtures and modified by an alkoxysilane.

### Claim 10 (depends on 5)

The nanofiller according to claim 5, wherein it is constituted of silica comprising two graft chains:
one of the chains being a hydrophilic chain consisting in a derivative of polyethylene glycol modified by a triethoxysilane, and
the other chain being an oligomer of the hexafluoropropylene oxide (HFPO) modified by a triethoxysilane or a methyldiethoxysilane.

### Claim 11 (depends on 1)

A dispersion in aqueous phase of at least a fluorocarbon resin comprising a nanofiller such as defined according to claim 1.

### Claim 12 (depends on 11)

The dispersion according to claim 11, wherein the fluorocarbon resin is selected among the polytetrafluoroethylene (PTFE), the copolymer of tetrafluoroethylene and perfluoro propylvinylether (PFA), and the copolymer of tetrafluoroethylene and hexafluoropropylene (FEP), the polyvinylidene fluoride (PVDF), the MVA (copolymer of TFE/PMVE), the terpolymer TFE/PMVE/FAVE, the ETFE and their mixtures.

### Claim 13 (depends on 11)

The dispersion according to claim 11 wherein it further comprises pigments, and/or additives selected among the thickening agents, surfactants, stabilizers and cosolvents.

### Claim 14

A method of synthesis of a silica nanofiller comprising a hydrophilic chain consisting in a derivative of polyalkylene glycol modified by an alkoxysilane and a hydrophobic chain consisting in a hydrophobic oligomer of HFPO, and/or a VDF and/or a TFE modified by an alkoxysilane, said method comprising the following steps:
providing a polyalkylene glycol modified by an alkoxysilane;
the oligomerization of said hydrophobic oligomer, followed by its functionalization by an alkoxysilane;
the grafting on the silica nanofiller on the one hand of said hydrophobic oligomer functionalized by an alkoxysilane, and on the other hand of polyalkylene glycol modified by an alkoxysilane.

### Claim 15 (depends on 14)

The method according to claim 14 wherein the grafting is a two-step grafting, in which:
first, the functionalized hydrophobic oligomer HFPO is grafted on the silica nanofiller; then
second, the modified polyalkylene glycol is grafted on the silica nanofiller.

### Claim 16 (depends on 14)

The method according to claim 14, wherein the grafting of the functionalized hydrophobic oligomer and the modified polyalkylene glycol is achieved simultaneously on the silica nanofiller.

### Claim 17 (depends on 1)

A non-stick coating comprising at least a layer comprising at least a fluorocarbon resin alone or mixed with a thermally stable bonding resin and resistant to at least 200° C., this (these) resin(s) forming a continuous fritted lattice, wherein it comprises a nanofiller such as defined according to claim 1.

### Claim 18 (depends on 17)

The non-stick coating according to claim 17 wherein the fluorocarbon resin is selected among the polytetrafluoroethylene (PTFE), the copolymer of tetrafluoroethylene and perfluoro propylvinylether (PFA), and the copolymer of tetrafluoroethylene and hexafluoropropene (FEP), the polyvinylidene fluoride (PVDF), the MVA (copolymer of TFE/PMVE), the terpolymer TFE/PMVE/FAVE, the ETFE and their mixtures.

### Claim 19 (depends on 17)

The non-stick coating according to claim 17, wherein the bonding resin is selected among polyamides imids (PAT), polyether-imids (PEI), polyamids (PA), polyimids (PI), polyetherketones (PEK), polyetheretherketones (PEEK), polythersulfones (PES), polyphenylene sulfides (PPS), polybenzimidazoles (PBI).

### Claim 20 (depends on 17)

The non-stick coating according to claim 17, wherein it comprises a bonding primer layer and at least a finishing layer.

### Claim 21 (depends on 17)

A culinary article comprising a support exhibiting an inner side able to receive foods and an outer side intended to be disposed towards the source of heat, wherein the inner side is coated with a non-stick coating such as defined according to claim 17.

### Claim 22 (depends on 21)

The culinary article according to claim 21, wherein the support is a hollow bowl having a base and a lateral wall rising from said base.

### Claim 23 (depends on 21)

The culinary article according to claim 21, wherein the support is achieved in a material selected among the metals, wood, glass, ceramics and plastic material.

### Claim 24 (depends on 23)

The culinary article according to claim 23, wherein the support is a metal support in anodized aluminum or unanodized aluminum, or in polished, brushed or microbeaded aluminum, or cast aluminum, or in beaten or polished copper.

### Claim 25 (depends on 17)

A method for achieving a non-stick coating such as defined according to claim 17, wherein it comprises the following steps:
a step of introducing a nanofiller in a dispersion in aqueous phase of at least a fluorinated polymer, then
a step of applying on a substrate said dispersion comprising the fluorinated polymer and said nanofiller.