IE41763B1 - Articles coated with cured fluorocarbon polymer compositios - Google Patents

Articles coated with cured fluorocarbon polymer compositios

Info

Publication number
IE41763B1
IE41763B1 IE2100/74A IE210074A IE41763B1 IE 41763 B1 IE41763 B1 IE 41763B1 IE 2100/74 A IE2100/74 A IE 2100/74A IE 210074 A IE210074 A IE 210074A IE 41763 B1 IE41763 B1 IE 41763B1
Authority
IE
Ireland
Prior art keywords
polymer
acid
article according
weight
fluorocarbon polymer
Prior art date
Application number
IE2100/74A
Other versions
IE41763L (en
Original Assignee
Du Pont
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 Du Pont filed Critical Du Pont
Publication of IE41763L publication Critical patent/IE41763L/en
Publication of IE41763B1 publication Critical patent/IE41763B1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09D157/00—Coating compositions based on unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47J—KITCHEN EQUIPMENT; COFFEE MILLS; SPICE MILLS; APPARATUS FOR MAKING BEVERAGES
    • A47J36/00—Parts, details or accessories of cooking-vessels
    • A47J36/02—Selection of specific materials, e.g. heavy bottoms with copper inlay or with insulating inlay
    • 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
    • B05D7/52—Two layers
    • B05D7/54—No clear coat specified
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C08L33/064—Copolymers with monomers not covered by C08L33/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Food Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

1482652 Coated products E I DU PONT DE NEMOURS & CO 11 Oct 1974 [12 Oct 1973] 44147/74 Heading B2E An article bearing (a) a primer coating which comprises a fluorocarbon polymer, overlaid with (b) a cured topcoat obtained from a composition which comprises (i) a fluorocarbon polymer which is a polymer of hydrocarbon monomer(s) completely substituted with fluorine atoms or a combination of fluorine atoms and chlorine atoms, (ii) a polymer of monethylenically unsaturated monomer(s) which depolymerises and whose depolymerisation products vapourise at a temperature of from 150‹C below the fusion temperature of the fluorocarbon polymer to the decomposition temperature of the fluorocarbon polymer, (iii) a liquid carrier, b(i) is preferably polytetrafluoroethylene and b(ii) may be a polymer of an ethylenically unsaturated monomer(s) which contain at least one monoethylenically unsaturated acid or acid anhydride unit. b(i) may be in an amount of 25-95% by weight, based on the weight of b(i) and b(ii) and b(ii) in an amount of 75-5% by weight, based on the weight of b(i) and b(ii). b(ii) may comprise an alkyl acrylate or alkyl methacrylate wherein the alkyl group contains 1 to 8 carbon atoms, styrene, α-methylstyrene, vinyltoluene, a glycidyl ester of up to 14 carbon atoms copolymerised with acrylic acid, methacrylic acid, fumaric acid, itaconic acid, maleic acid, maleic anhydride; b(ii) is preferably methylmethacrylate / 2-ethylhexyacrylate / methacrylic acid terpolymer, methylmethacrylate/ ethylacrylate/acrylic acid terpolymer, n-butylacrylate or i-butyl acrylate/methylmethacrylate/glycidyl ester/acrylic acid quadripolymer, styrene/methylmethacrylate/glycidyl ester/ acrylic acid quadripolymer wherein said glycidyl ester has the formula wherein R 1 is CH 3 , R 2 and R 3 are alkyl, and R 1 , R 2 , R 3 contain 7 to 9 carbon atoms. (a) may be a polymer of hydrocarbon monomer(s) completely substituted with fluorine atoms or a combination of fluorine and chlorine atoms. (a) may also comprise a siliceous material, preferably derived from colloidal silica sol which has a silica content of 30% by weight and a pH of 9.0 at 25‹C, whose particles have been surface modified with aluminium, have a size of 13 to 14 millimicrons and a specific surface area of 210 to 230 square metres per gramme. (a) which is preferably polytetrafluoroethylene, may comprise 90 to 30% by weight of the fluorocarbon polymer, and 10 to 70 % by weight of the siliceous material. The article is preferably metal cook-ware. In the Examples; (a) is (2) polytetrafluoroethylene, colloidal silica, 'Triton' X-100, toluene, butyl 'Carbitol', silicone (60% solids in xylene), titanium dioxide, channel black; (b) is (1) (2) polyetetrafluoroethylene, methylmethacrylate / ethylacrylate / methacrylic acid terpolymer, triethanolamine, oleic acid, toluene, butyl 'Carbitol', water, channel black, sodium polynaphthalene sulphonate, aluminium silicate. The article is a fritcovered pan, and the layer thickness of (a) is 0.2-0.6 mil and of (b) is 0.8 to 1 mil. (The words 'Triton' and 'Carbitol' are registered Trade Marks).

Description

This invention relates to articles, e.g. of cookware, bearing a cured topcoat comprising a fluorocarbon polymer.
Cookware coated with fluorocarbon polymers of various sorts has come into widespread use in recent years. Almost every housewife prefer to use such cookware in her kitchen because food is less likely to stick to it because it is so easy to clean.
It has now been found, according to this invention, that the fluorocarbon polymer film which coats such cookware can be made denser and less porous,and that this makes the product still easier to clean and improves its appearance by making the finish glossier.
One can get these advantage's by using, instead of the customary fluorocarbon polymer cookware enamel, a composition which contains as its principal ingredients a fluorocarbon polymer, a polymeric adjunct having specific physical properties, and a liquid carrier.
The fluorocarbonpolymers used in this composition are those of ethylenically unsaturated hydrocarbon monomers completely substituted with fluorine atoms or a combination of fluorine atoms and chlorine atoms. Included in this group are polytetraf1uoro-ethylene (PTFE), copolymers of tetraf1uoro-ethylene and hexafluoropropylene in all monomer unit weight ratios (FEP) and f1uoro-chlorocarbon polymers such as polymono-chlorotrifluoroethylene. PTFE is preferred.
The fluorocarbon polymers used are particulate.
The particles should be small enough to pass through the nozzle of a spray gun without clogging it and also small enough to give the resulting film integrity. Preferably, -241763 the particles should be no larger than 0.35 micron in the longest dimension.
Although a dry flour or powder of fluorocarbon polymer can be used, a polymer in the form of an aqueous dispersion is preferred because it is most easily obtained in that form. Dispersions of fluorocarbon polymer in organic liquids miscible with water, such as ethanol, isopropanol, acetone and Cellosolves, can also be used. (the word Cellosolve is a Trade Mark). In either case, the liquid also serves as a carrier for the composition.
The present invention provides an article bearing (a) a primer coating comprising a fluorocarbon polymer overlaid with (b) a cured topcoat obtained from a composition compri sing (i) a fluorocarbon polymer which is a polymer of hydrocarbon monomer(s) completely substituted with fluorine atoms or a combination of fluorine atoms and chlorine atoms, and (ii) a polymer of monoethylenically unsaturated monomer(s) which depolymerizes and whose depolymerization products vaporize in the temperature range of 150°C below the fusion temperature of the fluorocarbon polymer (b) (i) to the decomposition temperature of the fluorocarbon polymer (b) (i), and (iii) a liquid carrier. -341763 Preferably the cured topcoat has been obtained from a composition comprising (i) 25 to 95% by weight of the total of (b) (i) and (ii), Of polymer (b) (i), (ii) 75 to 5%, by weight of the total of (i) and (ii), of a polymer of mono-ethylenically unsaturated monomer units which are or include mono-ethylenically unsaturated acid or acid anhydride monomer units, and (iii) a liquid carrier The primer comprises a fluorocarbon polymer (a) which is preferably a polymer of hydrocarbon monomer units completely substituted with fluorine atoms or a combination of fluorine atoms and chlorine atoms, preferably PTFE.
The primer may also comprise a siliceous material which may be colloidal silica derived from colloidal silica sol having a silica content of 30% by weight and a pH of 9.0 at 25°C, whose particles are surface modified with aluminium, have a size of 13 to 14 millimicrons and a specific surface area of 210 to 230 square meters per gram. The primer preferably comprises 10 to 70% by weight of siliceous material and 90 to 30% by weight of fluorocarbon polymer (a).
The fluorocarbon polymer (b) (i) is usually present in- the composition at a concentration of from 25% to 95% (by weight) of the total of fluorocarbon polymer (b) (i) and polymer (b) (ii) preferably from 85% to 95%, even more preferably 85% to 89% -4417 6 3 The closer the depolymerization and vaporization temperatures associated with polymer (b) (ii) are to the fluorocarbon's fusion temperature, the better.
Depolymerization means degradation of the polymer to the point at which the degradation products are volatile at the temperatures encountered in curing the film. These degradation products can be monomers, dimers or oligomers.
Vaporize means volatilization of the degradation products and their evaporation from the film. Ideally, all of the degradation products pass from the film, but as a practical matter, a small but insignificant amount generally remains.
Representative of the ethylenically unsaturated monomer units which form polymer (b) (ii) are alkyl acrylates and methacrylates having 1-8 carbon atoms in the alkyl group, styrene, alpha-methyl styrene, vinyl toluene and glycidyl esters of up to 14 carbon atoms. Alkyl acrylates and methacrylates are preferred.
Representative of the monoethylenically unsaturated acid or acid anhydride monomer units which form -5417 6 3 polymer (b) (ii) are acrylic acid, methacrylic acid, fumaric acid, itaconic acid and maleic acid (or anhydride). Acrylic acid and methacrylic acid are preferred.
The preferred glycidyl ester unit is one derived from a product sold by the Shell Chemical Co. as Cardura E ester. This is a mixed ester of the general formula H9C-CH-CH9-O-C-C-R9 2 2 ξ 2 R3 where R-] is CHg and R2 and R3 are alkyl groups, R1 R2 and R3 containing a total of 7-9 carbon atoms. The word Cardura is a Trade Mark.
Polymer (b) (ii) is preferably 1. methyl methacrylate/2 - ethylhexylacrylate/ methacrylic acid terpolymers, preferably the 46-50/48-52/1-4 (weight ratio) terpolymers. 2. n or i - butyl acrylate/methyl methacrylate/ Cardura E/acrylic acid quadripolymers, preferably the 23-27/33-37/21-25/15-19 quadripolymers. 3. styrene/methyl methacrylate/Cardura E/acrylic acid quadripolymers, preferably the 28-32/28-32/ 21-25/15-19 quadripolymers. 4. methyl methacrylate/ethyl acrylate/ methacrylic acid terpolymers, preferably the 37-41/55-59/1-6 terpolymers.
Polymer (b) (ii) is usually present in the composition at a concentration of from 5% to 75% (by weight) of the total ^i) ano ^ii) preferably 5% to 15% even more preferably 11% to 15%, Polymer (b) (ii) can be by any of the conventional free-radical techniques familiar to any polymer chemist. The composition can also contain such conventional additives as pigments, fillers, flow control agents, and plasticizers, as seem necessary or desirable.
These additives are added for the usual reasons, in the usual ways and in the usual amounts.
The composition is made by first choosing the fluorocarbon polymer, polymer (b) (ii) and such conventional additives as may be used, and the amounts of these best suited to the purpose. This can be done with no trouble by one skilled in this art. Preparation of the composition is then a simple matter of thoroughly mixing these components.
The composition will be most useful for topcoating metal cookware, especially frypans, but can be used just- as well on other cookware, or other metal articles requiring lubricious surfaces, such as bearings, valves, wire, metal foil, boilers, pipes, ship bottoms, oven liners, iron sol epiates, waffle irons, ice cube trays, snow shovels and plows, chutes, conveyors, dies, tools such as saws, files and drills, hoppers and other industrial containers and molds.
The composition can be applied in any of the usual ways. Spraying, roller-coating, dipping doctor-blading- all are suitable, although spraying is generally the method of choice. The article to be coated is preferably pretreated by grit-blasting, by the flame-spraying of metals or by frit coating. The article may then be primed with a composition of the type disclosed in U.S. Patent 3,694,392.
The composition is usually applied to a thickness of 0.5 to 5 mils (dry) and then baked for from 0.5 to 30 minutes at a temperature of from 370 to 460°C.
Some preferred embodiments in accordance with the present invention will now be described by way of example.
Those skilled in this art will be able to practice this invention more easily by first referring to the following illustrative example. These artisans, will, no doubt, be able to compose numerous variations on the theme disclosed such as changing the amounts of ingredients slightly but insignificantly from those shown, adding innocuous additives, or substituting equivalent or nearly equivalent components for those shown. All these variations are considered to be part of the inventive concept.
Example 1 A representative coating composition of the invention is made as follows (all parts and percentages are by weight): (1) Mix together PTFE dispersion 411 parts aqueous, 60% solids Water 72 parts (2) Separately mix Triethanolamine 12 parts Oleic acid 6 parts Toluene 40.2 parts Butyl Carbitol 7.2 parts (3) Prepare a mill base by mixing and then pebble milling Water 67 parts Channel black 20 parts Sodium polynaphthalene sulfonate 3 parts Aluminum si 1icate 10 parts The word Carbitol is a Trade Mark.
Thoroughly mix (1) and (2). Then add to this mixture, with stirring, 90 parts of an aqueous dispersion, 40% solids, of a methyl methacrylate/ethyl acrylate/methacrylic acid 39/57/4 (weight ratio) terpolymer. Then blend 37.2 par*s of (3) into this mixture, with _ 9 _ 417 63 stirring. Spray the resulting composition to frit-coated aluminum pan,primed with a primer of the type shown in USP 3,694,392, to a thickness of 0.8-1 mil (dry). Then bake the pan for 5 minutes at 430°C. The resulting finish will be glossy and dense.
Example 2 Repeat Example 1, except in place of the primer shown, use one made as follows: (1) Mix together PTFE dispersion 478.76 parts aqueous, 60% solids Deionized water 130.23 parts Colloidal silica sol1 327.18 parts 30% solids in water 15 (2) Separately mix Triton X-100 17.52 parts (ηοη-ionic surfactant sold by Rohm & Haas Co.) Toluene 34.56 parts 20 Butyl Carbitol 13.36 parts Silicone 34.56 parts (Dow-Corning DC-801, 60% solids in xylene) The words Triton, Carbitol and 25 Dow-Corning are Trade Marks.
Add 85.52 parts of (2) to (1) in a small stream over a 2-3 minute period, with stirring. Then add, with stirring, Τ1 Og (45% solids in water) 35.46 parts and Channel black (22% solids in water) 0.85 parts Continue stirring for 10-20 minutes.
Spray this composition on the frit-coated aluminum pan of Example 1 to a thickness of 0.2-0.6 mil (dry) and air dry it. lLudox AM colloidal silica, sold hy E. 1. du Pont de Nemours and Company. (The word Ludox is a Trade Mark Mark).

Claims (16)

1. WHAT WE CLAIM IS:1. An article bearing (a) a primer coating comprising a fluorocarbon polymer overlaid with (b) a cured topcoat obtained from a composition comprising (i) a fluorocarbon polymer which is a polymer of hydrocarbon monomer(s) completely substituted with fluorine atoms or a combination of fluorine atoms and chlorine atoms, and (ii) a polymer of monoethylenically unsaturated monomer(s) which depolymerizes and whose depolymerization products vaporize in the temperature range of 150°C below the fusion temperature of the fluorocarbon polymer (b) (i) to the decomposition temperature of the fluorocarbon polymer (b) (i), and (iii) a liquid carrier.
2. An article according to Claim 1 wherein polymer (b) (i) is PTFE.
3. An article according to Claim 1 or 2 wherein polymer (b) (ii) is a polymer of monoethylenically unsaturated monomer units which are or include monoethylenically unsaturated acid or acid anhydride monomer units.
4. An article according to Claim 1, 2 or 3 bearing (a) a primer coating comprising a fluorocarbon polymer overlaid with (b) a cured topcoat obtained from a composition comprising (i) 25 to 95% by weight of the total of (i) and (ii) of polymer (b) (i), (ii) 75 to.5% by weight of the total of (i) and (ii), of a polymer of monoethyl enical ly unsaturated monomer units which are or include monoethylenically unsaturated acid or acid anhydride monomer units, and (iii) a liquid carrier.
5. An article according to Claim 3 or 4 wherein (b) (ii) is a (co)polymer of one or more of an alkyl acrylate or methacrylate having 1 to 8 carbon atoms in the alkyl group, styrene, alphamethyl styrene, vinyl toluene or a glycidyl ester of up to 14 carbon atoms, and the monoethylenically unsaturated acid or anhydride is acrylic acid, methacrylic acid, fumaric acid, itaconic acid, maleic acid or maleic anhydride.
6. An article according to any one of Claims 1 to 4 wherein (b) (ii) is a methyl methacrylate/2 - ethylhexyl acrylate/methacrylic acid terpolymer.
7. An article according to any one of Claims I to 4 wherein (b) (ii) is an n- or i- butyl acrylate/methyl methacrylate/glycidyl ester/acrylic acid quadripolymer, wherein the glycidyl ester is of the formula hereinbefore set forth.
8. An article according to any one of Claims 1 to 4 wherein (b) (ii) is a styrene/methyl methacrylate/ glycidyl ester/acrylic acid quadripolymer, wherein the glycidyl ester is of the formula hereinbefore set forth.
9. An article according to any one of Claims 1 to 4 wherein (b) (ii) is a methyl methacrylate/ethyl acrylate/methacrylic acid terpolymer.
10. An article according to any one of the preceding Claims wherein the fluorocarbon polymer of the primer is a polymer of hydro-carbon monomer units comDletely substituted with fluorine atoms or a combination of fluorine atoms and chlorine atoms.
11. An article according to Claim 10 wherein the fluorocarbon polymer is PTFE.
12. An article according to any one of the preceding Claims wherein (a) further 5 comprises a si 1iceous material.
13. An article according to Claim 12 wherein the siliceous material is colloidal silica derived from colloidal silica sol having a silica content of 30% by weight and a 10 pH of 9.0 at 25°C, whose particles are surface modified with aluminum, have a size of 13 to 14 millimicrons and a specific surface area of 210 to 230 square meters per gram.
14. An article according to Claim 12 or Claim 13 wherein (a) comprises 10 to 70% by weight of siliceous material and 90 to 30% by weight of fluorocarbon polymer.
15. An article according to any one of Claims 1 to 14 which is an article of metal cookware.
16. An article according to Claim 1 bearing a primer coating overlaid with a cured topcoat substantially as hereinbefore described with reference to Example 1 or Example 2.
IE2100/74A 1973-10-12 1974-10-10 Articles coated with cured fluorocarbon polymer compositios IE41763B1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US40579973A 1973-10-12 1973-10-12

Publications (2)

Publication Number Publication Date
IE41763L IE41763L (en) 1975-04-12
IE41763B1 true IE41763B1 (en) 1980-03-26

Family

ID=23605288

Family Applications (1)

Application Number Title Priority Date Filing Date
IE2100/74A IE41763B1 (en) 1973-10-12 1974-10-10 Articles coated with cured fluorocarbon polymer compositios

Country Status (13)

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JP (1) JPS542657B2 (en)
BE (1) BE820968A (en)
BR (1) BR7408499D0 (en)
CA (1) CA1046359A (en)
DE (1) DE2448634C2 (en)
DK (1) DK160261C (en)
FR (1) FR2247517B1 (en)
GB (1) GB1482652A (en)
IE (1) IE41763B1 (en)
IT (1) IT1022823B (en)
LU (1) LU71086A1 (en)
NL (1) NL179213C (en)
SE (1) SE7412769L (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2449306A (en) * 2007-05-18 2008-11-19 Univ Sheffield Composite particles
FR3083682B1 (en) * 2018-07-12 2020-12-11 Ethera ANTI-ODOR COVER

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2718452A (en) * 1950-06-30 1955-09-20 Du Pont Polytetrafluoroethylene organosols and the formation of shaped articles therefrom
US2825664A (en) * 1954-01-21 1958-03-04 Du Pont Polytetrafluoroethylene coating compositions containing an alkali metal silicate and colloidal silica and articles coated therewith
JPS4851033A (en) * 1971-10-28 1973-07-18

Also Published As

Publication number Publication date
BR7408499D0 (en) 1975-09-16
DK535274A (en) 1975-06-09
FR2247517B1 (en) 1983-08-19
JPS542657B2 (en) 1979-02-10
DK160261B (en) 1991-02-18
CA1046359A (en) 1979-01-16
NL179213B (en) 1986-03-03
IT1022823B (en) 1978-04-20
LU71086A1 (en) 1975-06-24
NL179213C (en) 1986-08-01
DE2448634A1 (en) 1975-04-24
JPS5088128A (en) 1975-07-15
NL7413433A (en) 1975-04-15
IE41763L (en) 1975-04-12
SE7412769L (en) 1975-05-28
GB1482652A (en) 1977-08-10
DE2448634C2 (en) 1983-01-20
AU7417974A (en) 1976-04-15
BE820968A (en) 1975-04-11
FR2247517A1 (en) 1975-05-09
DK160261C (en) 1991-07-22

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