# US 10,479,067 B2 · Multilayer articles comprising a release surface and methods thereof > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,479,067 B2 - Document ID: US10479067B2 - Status: Granted - Kind: B2 - Application number: 15/561,082 - Filed: 2016-04-01 - Published: 2018-09-13 - Granted: 2019-11-19 - Earliest claimed: 2015-04-01 - Assignees: 3M Innovative Properties Company - Applicants: 3M Innovative Properties Company - Inventors: Peter Bissinger; Michael C. Dadalas; Philipp Doebert; Rainer A. Guggenberger; Klaus Hintzer; Tilman C. Zipplies - Web page: https://patentgrep.com/patent/US10479067B2 ## CPC - B32B 37/24: with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate (B32B37/15 takes precedence) - A47J 36/025: {Vessels with non-stick features, e.g. coatings} - B05D 3/0254: {After-treatment} - B05D 5/086: {having an anchoring layer} - B05D 7/542: {the two layers being cured or baked together} - B32B 15/18: comprising iron or steel {(B32B15/011, B32B15/012 and B32B15/013 take precedence)} - B32B 15/20: comprising aluminium or copper {(B32B15/016 and B32B15/017 take precedence)} - B32B 27/14: next to a particulate layer - B32B 37/26: with at least one layer which influences the bonding during the lamination process, e.g. release layers or pressure equalising layers - C08K 3/013: Fillers, pigments or reinforcing additives - C08K 5/17: Amines; Quaternary ammonium compounds - C08K 5/54: Silicon-containing compounds {(C08K5/0091 takes precedence)} - C08L 27/12: containing fluorine atoms - C09D 127/18: Homopolymers or copolymers of tetrafluoroethene - B05D 2202/10: based on Fe - B05D 2506/10: Fluorinated polymers - B32B 2037/243: {Coating} - B32B 2037/268: {Release layers} - B32B 2255/06: on metal layer - B32B 2255/10: on synthetic resin layer or on natural or synthetic rubber layer - B32B 2255/20: Inorganic coating - B32B 2255/26: Polymeric coating - B32B 2264/102: Oxide or hydroxide - B32B 2264/105: Metal - B32B 2264/108: Carbon, e.g. graphite particles - B32B 2307/702: Amorphous - B32B 2311/24: Aluminium - B32B 2311/30: Iron, e.g. steel - C08L 2205/025: containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure - C08L 2207/53: Core-shell polymer - B32B: LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM - A47J: KITCHEN EQUIPMENT; COFFEE MILLS; SPICE MILLS; APPARATUS FOR MAKING BEVERAGES - B05D: PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL (conveying articles or workpieces through baths of liquid B65G, e.g. B65G49/02) - C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09) - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) - 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) ## Abstract Described herein is multilayer article made by the process comprising: delivering particles comprising a silicon compound from at least one fluid jet to a metal surface to embed the metal surface with the silicon compound to form a silicon compound layer; coating the silicon compound layer with an aqueous fluoropolymer dispersion to form a fluoropolymer layer and thereby forming a multilayered article, wherein the aqueous fluoropolymer dispersion comprises (i) a modifying agent; and (ii) a fluorinated polymer, wherein the fluorinated polymer comprises at least one of (a) a partially fluorinated polymer capable of forming a carbon-carbon double bond, (b) a functionalized fluorinated polymer, and (c) combinations thereof; and sintering the multilayered article to form the release surface coated substrate. ## Claims ### Claim 1 A release surface coated substrate made by a process comprising: delivering abrasive particles comprising a silicon compound from at least one gaseous fluid jet in the absence of liquids to a metal surface to embed the metal surface with the silicon compound to form a silicon compound layer, wherein the abrasive particles have a particle size ranging from 0.1 to 10000 microns and a Mohs hardness of from 3 to 10; coating the silicon compound layer with an aqueous fluoropolymer dispersion to form a fluoropolymer layer and thereby forming a multilayered article, wherein the aqueous fluoropolymer dispersion comprises (i) a modifying agent and (ii) a fluorinated polymer, wherein the fluorinated polymer comprises at least one of (a) a partially fluorinated polymer capable of forming a carbon-carbon double bond, (b) a functionalized fluorinated polymer, and (c) combinations thereof; and sintering the multilayered article to form the release surface coated substrate. ### Claim 2 (depends on 1) The release surface coated substrate of claim 1, wherein the modifying agent is selected from a coupling agent, an activating agent, and combinations thereof. ### Claim 3 (depends on 2) The release surface coated substrate of claim 2, wherein the activating agent is selected from a base, an amine-containing compound, a hydroxyl-containing compound, and combinations thereof. ### Claim 4 (depends on 3) The release surface coated substrate of claim 3, wherein the aqueous fluoropolymer dispersion comprises 0.1 to 30% by weight of the activating agent relative to the fluorinated polymer. ### Claim 5 A release surface coated substrate made by a process comprising: delivering abrasive particles comprising a silicon compound from at least one gaseous fluid jet in the absence of liquids to a metal surface to embed the metal surface with the silicon compound to form a silicon compound layer, wherein the abrasive particles have a particle size ranging from 0.1 to 10000 microns and a Mohs hardness of from 3 to 10; coating the silicon compound layer with a coating comprising a coupling agent to form a coupling agent layer; coating the coupling agent layer with an aqueous fluoropolymer dispersion to form a fluoropolymer layer and thereby forming a multilayered article, wherein the aqueous fluoropolymer dispersion comprises a fluorinated polymer, wherein the fluorinated polymer comprises at least one of (a) a partially fluorinated polymer capable of forming a carbon-carbon double bond, (b) a functionalized fluorinated polymer, and (c) combinations thereof; and sintering the multilayered article to form the release surface coated substrate. ### Claim 6 (depends on 2) The release surface coated substrate of claim 2, wherein the coupling agent comprises at least one of a silane, a titanate, a zirconate, and combinations thereof. ### Claim 7 (depends on 2) The release surface coated substrate of claim 2, wherein the coupling agent comprises at least one of: a trimethoxy silane, a triethoxy silane, and combinations thereof. ### Claim 8 (depends on 2) The release surface coated substrate of claim 2, wherein the coupling agent comprises at least one of: vinyl trimethoxysilane, vinyl triethoxysilane, γ-glycidoxypropyl trimethoxysilane, γ-methacroyloxy propyltrimethoxysilane, tetramethyl divinyl silazane, 3-aminopropyl tri-methoxy silane, and combinations thereof. ### Claim 9 (depends on 1) The release surface coated substrate of claim 1, wherein the aqueous fluoropolymer dispersion is substantially free of a binder. ### Claim 10 (depends on 1) The release surface coated substrate of claim 1, wherein the silicon compound comprises at least one of: amorphous silica, silicic acid, silicon dioxide, and combinations thereof. ### Claim 11 (depends on 1) The release surface coated substrate of claim 1, wherein the aqueous fluoropolymer dispersion comprises a fluoropolymeric core-shell particle with the fluorinated polymer shell and a perfluorinated polymer core. ### Claim 12 (depends on 1) The release surface coated substrate of claim 1, wherein the functionalized fluorinated polymer comprises at least one of (a) —COX groups, wherein X is OH, ONa, OK, NH2, F, or Cl; (b) —SO2X where X is OH, ONa, OK, NH2, F, or Cl; (c) —CH2OSO2Y where Y═OH, ONa, or OK; (d) —CH2OH; (e) phosphate group; (f) —CN, (g) a halogen selected from Br, I, and Cl; and (h) combinations thereof. ### Claim 13 (depends on 1) The release surface coated substrate of claim 1, wherein the particles comprise an abrasive particle having an outer surface comprising the silicon compound. ### Claim 14 (depends on 1) The release surface coated substrate of claim 1, wherein the aqueous fluoropolymer dispersion further comprises an inorganic filler. ### Claim 15 (depends on 1) The release surface coated substrate of claim 1, wherein when the aqueous fluoropolymer dispersion comprises a fluorinated polymer having at least 30 reactive groups per 1,000,000 carbon atoms. ### Claim 16 (depends on 1) The release surface coated substrate of claim 1, wherein the metal substrate includes at least one of steel, high-carbon steel, stainless steel, aluminized steel, aluminum, and aluminum alloys. ### Claim 17 (depends on 1) The release surface coated substrate of claim 1, wherein the particle is selected from silica, alumina, zirconia, barium titanate, calcium titanate, sodium titanate, titanium oxide, glass, biocompatible glass, diamond, silicon carbide, calcium phosphate, calcium carbonate, metallic powders, carbon fiber composites, polymeric composites, titanium, stainless steel, hardened steel, carbon steel chromium alloys, or any combination thereof. ### Claim 18 (depends on 1) The release surface coated substrate of claim 1, further comprising an additional layer that is disposed on top of the fluoropolymer layer. ### Claim 19 A process for making a release surface coated substrate comprising: delivering abrasive particles comprising a silicon compound from at least one gaseous fluid jet in the absence of liquids to a metal surface to embed the metal surface with the silicon compound to form a silicon compound layer, wherein the abrasive particles have a particle size ranging from 0.1 to 10000 microns and a Mohs hardness of from 3 to 10; coating the silicon compound layer with an aqueous fluoropolymer dispersion to form a fluoropolymer layer and thereby forming a multilayered article, wherein the aqueous fluoropolymer dispersion comprises (i) a modifying agent and (ii) a fluorinated polymer, wherein the fluorinated polymer comprises at least one of (a) a partially fluorinated polymer capable of forming a carbon-carbon double bond, (b) a functionalized fluorinated polymer, and (c) combinations thereof; and sintering the multilayered article to form the release surface coated substrate. ### Claim 20 A process for making a release surface coated substrate comprising: delivering abrasive particles comprising a silicon compound from at least one gaseous fluid jet in the absence of liquids to a metal surface to embed the metal surface with the silicon compound to form a silicon compound layer, wherein the abrasive particles have a particle size ranging from 0.1 to 10000 microns and a Mohs hardness of from 3 to 10; coating the silicon compound layer with a coating comprising a coupling agent to form a coupling agent layer; coating the coupling agent layer with an aqueous fluoropolymer dispersion to form a fluoropolymer layer and thereby forming a multilayered article, wherein the aqueous fluoropolymer dispersion comprises a fluorinated polymer, wherein the fluorinated polymer comprises at least one of (a) a partially fluorinated polymer capable of forming a carbon-carbon double bond, (b) a functionalized fluorinated polymer, and (c) combinations thereof; and sintering the multilayered article to form the release surface coated substrate.