CA1136010A - Article coated with improved fluoropolymer finish - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
The apparent scratch resistance of articles coated with a fluoropolymer finish is improved if the article is coated with at least two coats with the topcoat containing mica particles, mica particles coated with a pigment, or metal flake in a smaller amount than is contained in the coat under the topcoat.

Description

:~13~(~10 TITLE
Article Coated With Improved Fluoropolymer Finish BACKGROUND OF I~IE INVENTION
Cookware coated with fluoropolymers, especially polytetrafluoroethylene (PTFE), has come into widespread use in recent years. Many cooks prefer to use such cookware because of its nonstick properties and because it is so easy to clean.
1~ While cookware of this type is quite durable, the fluoropolymer coating tends to become scratched after extended use because it is somewhat softer than the utensils used to stir and turn the food in the ware.
Fluoropolymer compositions which contain mica particles, mica particles coated with pigment, or metal flake, give fluoropolymer finishes of this general type having improved scratch resistance. This improved scratch resistance is actual and can be 20 measured physically with instruments. However, the apparent scratch resistance, that which is perceived by the user of the cookware, may not be as high as the actual scratch resistance because food lodges in the slight scratches which may be present and becomes 25 oxidized. T~ese scratches become highlighted because of the high optical contrast between the finish and the oxidized food, and are therefore much more noticeable than they would ordinarily be.
S UMMARY OF TH E I NVENT I ON
The present invention provides an article bearing a basecoat derived from a composition comprlslng (a) a particulate polymer of monoethylenically unsaturated hydrocarbon monomers completely substituted with fluorine atoms or a combin-ation of fluorine atoms and chlorine atoms;

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1~36(~10 (b) mica particles, mica particles coated with pigment, or metal flake; and (c) a liquid carrier;
overlaid with a topcoat finish derived from a composi-tion comprising (a), (b) and (c), wherein the concentra-tion of (b) is less in the topcoat than in the basecoat.
In a preferred embodiment the topcoat is derived from a composition that additionally contains (d) a polymer of ethylenically unsaturated monomers which depolymerizes and whose depolymerization products vaporize in the tempera-ture range of about 150C below the fusion temperature of(a) to about the decomposition temperature of (a).
The present invention also provides a method for improving the apparent scratch resistance of an article bearing a basecoat derived from a composition comprising:
(a) a polymer of monoethylenically unsaturated hydrocarbon monomers completely substituted with fluorine atoms or a combination of fluorine atoms and chlorine atoms;
(b) mica particles, mica particles coated with pigment, or metal flake;
(c) a liquid carrier; and (d) a polymer of monoethylenically unsaturated monomers which depolymerizes and whose depolymerization products vaporize in the temperature range of about 150C below the fusion temperature of (a) to about the decomposition temperature of (a);
the method comprising topcoating the basecoat with a composition comprising (a), (b), (c) and (d), wherein the concentration of (b) in the topcoat is less than the concentration of (b) in the basecoat, and then fusing the coatings.
DETAILED DESCRIPTION OF THE INVENTION
Representative base coats of articles coated according to this inventlon are described in U. S.

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2a Patents 3,970,627 - Seymus (1976); 4,054,704 - Vassiliou (1977); 4,054,70~ - Vassiliou (1977); 4,064,303 -Vassiliou (1977); 4,070,525 - Vassiliou et al. (1978);
4,120,608 - Vassiliou (1978); 4,123,401 - serghmans et al. (197~). The disclos~res of these patents describe the base coats and how they are obtained.
Coating compositions used in the invention include dispersions of a fluoropolymer in a carrier.
~: The fluoropolymers, carriers and concentrations which can be used are the same as those described in the aforementioned patents. The fluoropolymer is preferably the same one used in each coat, and in the most pre-~;~ ferred case is PTFE. The fluorocarbon polymers used ,' are those of monomers of hydrocarbons or hydrocarbon ethers completely substituted with fluorine atomsor a combination of fluorine and chlorine atoms.
Included in this group are perfluoroolefin polymers such as polytetrafluoroethylene (PTFE) and copolymers of tetrafluoroethylene and hexafluoropropylene in all monomer unit weight ratios, fluorochlorocarbon poly-/ mers such as polymonochlorotribluoroethylene, and copolymers of tetrafluoroethylene and perfluoroalkyl vinyl ethers. Mixtures of these can also be used.

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- ~ , , ~36V10 The amount of total solids in the coating compositions will be governed by the method of application, the curing procedures and like factors.
Ordinarily, the composition will contain about 10-80%
5 of total solids.
The topcoat composition will show improved coalescence on curing if it also contains a polymer additive, which is a polymer of ethylenically unsat-urated monomers which depolymerizes at the curing 10 temperature of the film, as more particularly described in the aforementioned U.S. Patent 4,123,401.
This polymer additive is ordinarily present in the topcoat composition at a concentration of about 5-75~, by weight of the total of fluoropolymer and 15 polymer additive, preferably about 5-15~, the fluoro-polymer being present in a complementary amount to make the total fluoropolymer and polymer additive present equal to 100~.
The preferred polymer additive is an acrylic 20 latex such as of a methyl methacrylate/ethylacrylate/
methacrylic acid 39/57/4 terpolymer. The acrylic particles in the latex preferably have a particle size under 1 micron (~xm), more preferably under 0.5 ~ m, most preferably under 0.3 ~m, and they are present 25 in the latex as a stable aqueous dispersion. Alter-natively, the acrylic could be provided as a solution in suitable solvents.
If the polymer additive is used, it may also be desirable for the topcoat composition to contain 30 a metal compound which will catalyze the depolymeriza-tion of any residue of polymer additive, whose presence might discolor the final finish.
This metal compound can be an oxide or hydroxide of 1136()10 (1) copper gallium cobalt iridium iron rhodium nickel platinum chromium palladium vanadium tin tantalum tungsten cerium lithium thorium sodium manganese potassium bismuth lead cadmium ytterbium molybdenum or silver;
or

(2) a compound of any of the metals listed in (1) which decomposes in the temperature range of about 100-500C to give at least 0.2%, by weight of the metal in the compound, of an oxide or hydroxide.
The metal compound, when it is used, will ordinarily be present in the topcoat composition at a concentration which will provide about 0.005-5 parts of metal per hundred parts of fluoropolymer used.
Preferred metals selected from the list above are:
chromium bismuth cobalt cadmium iron lithium nickel sodium cerium potassium thorium lead manganese or molybdenum.

11360~0 Further preferred, especially for use in food-contact applications, are oxides or hydroxides of lithium, sodium or potassium, and those compounds produced by reaction of a metal from the following 5 list (1) with an acid to form a salt compound of list (2).
(1) Metals:
bismuth manganese cerium lithium cobalt potassium iron sodium (2) Salts:
acetate octoate : caprate oleate caprylate palmitate isodeconoate ricinoleate linoleate soyate naphthenate stearate nitrate tallate Especially preferred oxidation catalyst compounds are:
cobalt octoate bismuth octoate cerium octoate iron octoate manganese octoate 25 Most preferred as an 0xidation catalyst for general purposes of the invention is a combination of cobalt and cerium octoates.
In some cases, it may also be desirable for the topcoat composition to contain an antioxidant to 30 prevent discoloration of the final finish when cookware bearing the finish is subjected to excessive heat over a prolonged period. These antioxidants are, generally speaking, compounds containing phosphorus, sulfur, boron, or combinations of these. Illustrative of such 35 compounds are the ortho-, meta- and pyro acids of these ~1360~0 elements; their neutral and basic salts; their esters;
and their organic- and organo-metallic derivatives.
The preferred antioxidants are phosphoric acid, at least completely neutralized with organic 5 base such as triethanolamine or with ammonia, particularly decomposable phosphate salts containing ammonia or amines, 2-ethylhexyldiphenyl phosphate, magnesium glycerophosphate, calcium glycerophosphate, and iron glycerophosphate. Preferably the acid is 10 sufficiently neutralized so that the coating composition has a pH of at least 8 to prevent coagulation of PTFE
suspended in the composition.
The antioxidants are ordinarily present in the compositions at a concentration of about 0.1-10%, 15 by weight of the total solids in the composition.
The topcoat composition can also contain such conventional additives as flow control agents, surfactants, plasticizers, etc., as are necessary or seem desirable. These additives are added for the 20 usual reasons, in the usual ways and in the usual amounts.
Pigments that can be used in coating compositions of the invention include pigments ordinarily used in fluorocarbon coatings to develop 25 the desired colors and pigments having refractive indices substantially the same as that of the fluoro-polymer used. Representative of the latter type of pigments are alumina, silica, clays and glass spheres.
These pigments are advantageously present in the 30 topcoat composition at a concentration of about 3-30%, by weight of the fluoropolymer to enhance apparent scratch resistance of the topcoat. Colors and opacity can be obtained with such pigments as TiO2 and iron oxide.

The invention involves the use of flake-type pigments of mica particles, mica particles coated with pigment, and metal flake. Mica particles coated with pigment are preferred, especially those described in 5 U.S. Patents 3,087,828 and 3,087,829 to Linton and

3,087,827 to Klenke and Straton. Such flake type pigments are used at least in the topcoat and the coat directly under the topcoat, with the concentration in the topcoat being less than that in the lower coat.
lO When the coated article has 2 coats on it, the lower coat is the primer. When the coating has 3 or more coats, the lower coat is an intermediate coat adjacent to the topcoat. The terms "lower coat" and "basecoat"
are used herein to mean the coat beneath the topcoat, 15 whether it is a primer or an intermediate coat.
The ratio by weight of the flake pigment to the solids content of each coat is such that the topcoat has lO-90~ as high a concentration of flake pigment as does the lower coat. Preferably, the range is from 20 30-70%. The most preferred proportion is 50%.
As a percentage of solids in each of the coats of a 3-layer coating the preferred and most preferred amounts of flake pigment are as follows:
Preferred Most Preferred 25 Topcoat O . 5 - 2 . 0% 1%
Intermediate 1.0 - 4.0% 2~
Primer 0 - 1.0% 0. 2%
The thickness of the three coating layers expressed in ~m are as follows:
Preferred Most Preferred Topcoat and 12.5 - 125 25 - 50 Intermediate Primer 2.4 - 4.0 7.5 - 12.5 The relative thickness of the intermediate and topcoat 35 can vary from 10-90% intermediate and from 90-10%
topcoat. More preferably, the intermediate and topcoat will have about the same thickness.

" 1136010 In the development of the present invention it was found that multi-layer coats with as much or more flake pigment in the topcoat as in the lower coat suffer from an increase in apparent scratching in use S tests. When a fork was used to scratch the surface during cooking tests over an extended period of time, it was found that the larger amount of flake pigment in the topcoat led to more superficial scratches, perhaps caused by disturbing the orientation of the 10 flake pigment.
The next attempt to obtain improved-scratch resistance utilized a 3-layer coating with equal proportions of flake pigment in the primer and inter-mediate coat but no flake pigment in the topcoat. This 15 combination requires close control of the thickness of the topcoat to avoid discoloration upon curing too thick a topcoat and increased apparent scratching with too thin a topcoat. The solution to these problems was found by using a 2- or 3-layer coat with flake pigment 20 in both the topcoat and the coat beneath it, with less flake pigment in the topcoat than in the lower coat.
The multilayer coatings of the invention are most useful for coating metal cookware, especially frypans, but the compositions can also be used to coat 25 other articles requiring scratch resistant fluoropolymer coatings. These other articles can be made of glass, ceramic, plastic or any other material capable of with-standing the baking temperatures used. For example, the compositions can be used to coat bearings, valves, 30 wire, metal foil, boilers, pipes, ship bottoms, oven liners, iron soleplates, 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.

~1360~0 The following examples illustrate the invention. In these examples, all parts and percentages are by weight unless indicated otherwise.
XAMPLE
(A) A polyamide acid amine salt solution was prepared by first charging a vessel with Ingredient Parts Polyamide acid 15 10 (prepared from trimellitic anhydride and bis(4-aminophenyl)methane, having an inherent viscosity of 0.31, measured as a 0.5~ solution in dimethyl-acetamide, and a free acid content of 7.65%, corresponding to 170 milliequivalents of carboxylic acid per 100 grams) Water 50 Diethyl 2-hydroxyethylamine 4 20 Triethylamine 2 Furfuryl alcohol 18 N-methyl pyrrolidone 10 and then stirring the mixture overnight at room tempera-ture.
The resulting clear solution had a Brookfield viscosity (number 2 spindle, 20 revolutions per minute) of 600 centipoises.
(B) The following were added to a vessel in the 30 order given and mixed:
Ingredien~ Parts Polyamide acid amine salt solution124.57 (from Example l(A)) Furfuryl alcohol 12.52 35 Deionized water 280.28 `` il36010 lQ
PTFE dispersion 354,92 (60% solids in water, Teflon~ TFE-fluorocarbon resin aqueous dispersion, T-30, sold by E. I. du Pont de Nemours and Co.~
Ludox AM~ 143.29 (sodiùm stabilized colloidal silica having a pH of about 9 at 25QC and a silica content (calculated at SiQ2~ of 30~, whose particles are suxface modified with aluminum and have a particle diameter of 13-14 milli-microns and a specific surface area of 210-230 square meters per gXam~
Pigment dispersion 106~68 Made by ball-milling a mixture of cobalt oxide 45 parts water 55 parts TiO2 coated mica Q~74 (Afflair* NF-152-D, sold by E. I. du Pont de Nemours and Co,) The resulting primer composition was sp~ayed on a degreased aluminum paneI to a thickness of about 8 microns (dry) and air-dried to ~oxm a pximer-basecoat~
(C~
A topcoat composition was prepared by mixing the following in the order listed.
Ingredi:ent Parts Aqueous PTFE dispersion 772.33 (from Example l(B)) Deionized water 43.9 TiO2 coated mica 4,72 (from Example l(B)) *denotes trade mark A

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:

A mixture of 137.62 butyl carbitol12.51%
toluene 30.72%
cerous octoate4.94%
triethanolamine 37.11%
oleic acid9.67%
Triton* X-1005.05%
(a nonionic surfactant sold by Rohm & Haas Co.) 10 Aqueous 40% solids, of a dispersion of 143.43 methyl methacrylate/ethylacrylate/
methacrylic acid 39/57/4 terpolymer This topcoat composition was applied to a gritblasted aluminum frypan, basecoated as described in Example l(B). The wet thickness of the film was 15 microns.
The 2-layer coating was then air-dried and the pan baked at 425C for 5 minutes.
The resulting finish remained substantially 0 free of apparent scratches after extended use.

A topcoat composition was prepared by mixing the following in the order listed:
Ingredient Parts 25 PTFE dispersion 70-95 (of Example l(B)) Deionized water 3.87 A mixture of 6.19 triethanolamine 25.86%
30 butyl carbitol 15.76%
toluene 46.26%
oleic acid 12.12%
Aqueous dispersion of terpolymer11.90 (of Example l(C)) *denotes trade mark 1136~)10 A mixture of 5.66 deionized water 60.97%
phosphoric acid 85% 6.47~
triethanolamine 32.56%
5 TiO2 coated mica 00-43 (of Example l(B)) This topcoat composition was applied, to a thickness of 15 microns, to a grit-blasted aluminum electric frypan basecoated as described in Example l(B).
lO The 2-layer coating was then air-dried and the pan baked at 425C for 5 minutes.
The resulting finish remained substantially free of apparent scratches and discoloration after extended use.

(A) To make an article of the invention with a 3-layer coating, a grit-blasted aluminum substrate was first coated with a primer, in accordance with the 20 teachings of U.S. Patent 4,070,525 as follows:
The following were then added to a vessel in the order stated and mixed:
Ingredient Parts Polyamide acid amine salt 303.6 of Example l(A) containing 18%
of furfuryl alcohol and lO~ of N-methylpyrrolidone Furfuryl alcohol 30.4 Deionized water 1040.0 30 Pigment dispersion 105.2 (Made by ball-milling a mixture of TiO2 44 Water 48 Triethanolamine oleic 8 acid mixture 2/l) PTFE dispersion of Example l(B)445.0 -` ~3~010 To 200 parts of the resulting mixture were then added, witl~ mixing, 8.86 parts of lithium silicate solution in water (21% solids, sold by E. I. du Pont de Nemours and Co. as "Lithium Polysilicate* 85).
The resulting composition was sprayed as a primer on a grit-blasted aluminum panel to a thickness of 5 microns (dry) and then air-dried.
(B) An intermediate coat was applied on top of the primer and a topcoat was applied on top of the intermediate coat while the intermediate coat was still wet, using the following compositions:
INTERMEDIATE COAT
Ingredient Parts PTFE dispersion of Example l(B) 737.19 Deionized water 66.40 Yellow pigment dispersion 2.81 yellow iron oxide 45%
deionized water 54.5%
sodium polynaphthalene 0.5%
sulfonate Blue pigment dispersion 2.81 cobaltoxide-aluminum 45%
oxide pigment 54.5%
deionized water 54.5%
sodium polynaphthalene 0.5%
sulf~nate Afflair~ TiO2 coated mica of9.78 Example l(B) Solvent-Catalyst 138.73 butyl carbitol 12.42%
toluene30 99% ) UNTIL
cerous octoate (23% 4.83% )DISSOLVED
metal) triethanolamine 36.96%
oleic acid 9.84%
Triton X-100 surfactant 4.96%
Dispersion of Example l(B) 137.22 *denotes trade mark f 13 1136(;~10 TOPCOAT
Ingredient Parts PTFE dispersion of Example l (B) 772 . 33 Deionized water 43 . 90 5 Afflair~ TiO2 coated mica of 4.72 Example l(B) Solvent catalyst 137 . 62 butyl carbitol 12.51% ) MIX
toluene 30.72% )UNTIL
cerous octoate 4.94% )DISSOLVED
(23% metal) triethanolamine 37.11~
oleic acid 9.67%
Triton X-100 surfactant 5.05%
15 Dispersion of Example l(B)- 143.43

Claims (9)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. An article bearing a multi-layer coating comprising a basecoat derived from a composition comprising:
(a) a particulate polymer of monoethylenically unsaturated hydrocarbon monomers completely substituted with fluorine atoms or a combina-tion of fluorine atoms and chlorine atoms;
(b) mica particles, mica particles coated with pigment, or metal flake; and (c) a liquid carrier;
overlaid with a topcoat finish derived from a composition comprising (a), (b), and (c), with the concentration of (b) in the topcoat being from 10% to 90% of the con-centration of (b) in the basecoat.

2. The article of claim 1 wherein the topcoat is derived from a composition comprising:
(a) a polymer of monoethylenically unsaturated monomers completely substituted with fluorine atoms or a combination of fluorine atoms and chlorine atoms;
(b) mica particles, mica particles coated with pigment, or metal flake;
(c) a liquid carrier; and (d) a polymer of ethylenically unsaturated monomers which depolymerizes and whose depolymerization products vaporize in the temperature range of about 150°C below the fusion temperature of (a) to about the decomposition temperature of (a).

3. The article of claim 1 wherein the basecoat is an intermediate coat and there is a primer coat beneath the intermediate coat.

4. The article of either claim 1 or claim 3 wherein the concentration of (b) in the topcoat is from 30 to 70% of the concentration of (b) in the basecoat.

5. The article of claim 1 wherein the polymer in (a) is polytetrafluoroethylene.

6. The article of claim 2 whose topcoat is derived from a composition which additionally contains a catalyst for the depolymerization of the (d) polymer.

7. The article of claim 3 wherein the thickness of the primer coat is 2.5 to 4.0 µm, and the combined thickness of the intermediate and topcoats is 12.5 to 125 µm.

8. The article of claim 3 wherein the thickness of the primer coat is 7.5 to 12.5 µm, and the combined thickness of the intermediate and topcoats is 25 to 50 µm.

9. A method for improving the apparent scratch resistance of an article bearing a basecoat derived from a composition comprising:
(a) a polymer of monoethylenically unsaturated hydrocarbon monomers completely substituted with fluorine atoms or a combination of fluorine atoms and chlorine atoms;
(b) mica particles, mica particles coated with pigment, or metal flake;
(c) a liquid carrier; and (d) a polymer of monoethylenically unsaturated monomers which depolymerizes and whose depolymerization products vaporize in the temperature range of about 150°C below the fusion temperature of (a) to about the decomposition temperature of (a);
the method comprising topcoating the basecoat with a composition comprising (a), (b), (c) and (d), wherein the concentration of (b) in the topcoat is from 10% to 90% of the concentration of (b) in the basecoat, and then fusing the coatings.