NON-STICK COATING SYSTEM WITH PTFE OF DIFFERENT MELT VISCOSITIES FOR CONCENTRATION GRADIENT

Abstract: Improved non-stick coating systems can be applied to untreated smooth substrate with a primer of a first polytetrafluoroethylene having a melt viscosity over 10<5> Pa Sec plus a second polytetrafluoroethylene having a melt viscosity in the range of 10<2> to 10<7> Pa Sec, with the melt viscosity of the first being at least 10<2> Pa Sec higher than that of the second to give a concentration gradient.

Description: TITLE NON-STICK COATING SYSTEM WITH PTFE OF DIFFERENT MELT VISCOSITIES FOR CONCENTRATION GRADIENT BACKGROUND OF THE INVENTION 5 This invention relates to coatings systems, such as for cookware, which πύiώnize sticking. More particularly, it relates to multilayer coating systems that can be used directly on smooth, untreated substrates and which provide concentration gradients within the coating. Generally in the art a metal or glass substrate is roughened by 0 some means before the first layer of coating is applied so that mechanical bonding will assist chemical adhesive means in holding the coating onto the substrate. Typical roughening means include acid etching, sand-blasting, grit-blasting, and baking a rough layer of glass, ceramic or enamel frit onto the substrate. The problem of adhesion of non-stick coatings to substrates is 5 exacerbated by the nature of the coatings. If the coating is optimized for release to prevent food particles from sticking to it, for easy clean-up after cooking or durability, or to facilitate low friction sliding contact, almost by definition there will be difficulties in making it adhere well to the substrate. The substrate can be metal, often aluminum or stainless steel 0 used for cookware or industrial applications. It can be glass or ceramic. It might even be plastic for microwave oven cookware, or it could be an industrial article such as a saw made of carbon steel. Whatever the substrate or the application, if it is necessary to roughen the substrate to make the coating adhere, that at least adds cost and can cause other difficulties 5 including creating a rough profile which can protrude or telegraph through the coating. This is especially undesirable when smoothness is sought, such as for saws, steam irons and copier rolls. The environmental cost of disposing of etchant materials can be significant. Sometimes, especially for glass and ceramic substrates, it also can cause unacceptable weakness or o brittleness of the substrate- Means of enhancing adhesion of non-stick coatings to a substrate are illustrated by the following patents. U.S. 4,049,863 - Vassiliou (1977) teache a primer containing fluoropolymer, such as polytetrafluoroethylene (PTFE), colloidal silica and a polyamide imide (PAI), along with other constituents, applied by various techniques to a substrate that is preferably pretreated by grit blasting, flame spraying of metals or metal oxides or frit coating, or to phosphated and chromated metals. The PTFE:PAI ratio can be 1:9. The primer coat is ordinarily applied to a dry film thickness (DFT) of about 2-15 microns (μ m). After air drying, the primer is topcoated with a conventional fhioropolymer enamel and baked. (Parts, percentages and proportions herein are by weight except where indicated otherwise.) U.S. 4,087,394 - Concannon (1987) discloses aqueous concentration gradient coatings of fhioropolymer which is 20-80% of a homopolymer or a copolymer of fluorinated ethylene-propylene (FEP) made of 5-100% tetrafluoroethylene (TFE) with 95-0% hexafluoropropylene (HFP), with 80-20% of a film forming polymer which can be PAI. The coating is applied by spraying onto aluminum sheet, or a variety of substrates. Other application techniques are mentioned. Nothing is said about substrate preparation. Although PTFE and FEP are treated as a continuum, there are no suggestions to use a blend such as 50% PTFE, 50% FEP. U.S. 3,928,675 and 3,857,852, both to Tieszen, teach the use of high viscosity (> 10^) and low viscosity (10^" poise) (10^ and 10^ Pa Sec) PTFE along with polyaiylene sulfide such as polyphenylene sulfide (PPS) in coatings. SUMMARY OF THE INVENTION The present invention, in certain of its embodiments, provides a coating composition comprising perfluorocarbon resin and at least one of polyamide imide and polyether sulfone resins, wherein the perfluorocarbon resin comprises at least two different polytetrafluoroethylene resins, the first f - having a melt viscosity of at least 10 poises (10^ Pa Sec), and the second * -_ Q having a melt viscosity in the range of 10 to 10 poises (10^ to 10^ Pa Sec), with the melt viscosity of the first being at least 10^ poises (Pa Sec) higher than that of the second. The invention also comprises multi-layer coating systems on substrates with the defined coating composition in the primer or in the topcoat. DETAILED DESCRIPTION The present invention permits not only lower cost by avoiding the roughening of the substrate but also smoother coated surfaces which can be advantageous for release on cookware, and for the gliding effect on steam iron sole plates. Also it can allow ehmination of costly polishing of coated copier roll surfaces and application of dispersion PTFE coatings by coil 5 coating and roller coating techniques. Various embodiments of the invention involve using at least two PTFE resins having different melt viscosities in a primer or a topcoat. One pair of resins has relatively high and low melt viscosity resins. Another has relatively low and lower still melt viscosity resin. o The adhesion of high melt viscosity fhioropolymer coatings to all types of metal substrates, particularly to smooth metal, can be significantly improved through chemically induced stratification or formation of a concentration gradient in the primer. Addition of perfluorocarbon polymer having a low melt 5 viscosity (MV) in the range of 10 -10 poise (10^ - 10? Pa Sec), to a primer system composed of PTFE with a high MV of 10 poise (lO 1 ^ Pa Sec) and a polymeric binder such as polyamide-imide or polyphenylene sulfide, imparts a synergistic effect in which the fluor opolymer stratifies away from the substrate interface allowing the polymeric binder to obtain a higher ° concentration and degree of cure at the substrate interface resulting in improved adhesion. The required cure temperature to achieve this stratification can be modified by the choice of fluoropolymer. Melt viscosity of perfluoropolymers can be determined by know technique such as that in U.S. Patent 4,636,549 - Gangal et al (1987). 5 See Col. 4, lines 25 - 63. With use of the coatings of the invention on smooth substrates, treated only by washing to remove grease and any other contaminants which might interfere with adhesion, coating systems of the invention give good food release and good resistance to usual durability tests ° such as the "tiger paw" abuse cooking tests involving a weighted holder with multiple ball point pen shafts rotating around the inside of a frying pan during cooking tests. The tests are generally described in U.S. patent 4,252,859, ~ Concannon and Vary (1981) col. 2, lines 14-24. Typical prior art preparation of surfaces to enhance adhesion of a release coating has involved etching or sand or grit blasting to develop a surface profile. The profile is measured in average microinches using a model RT 60 surface roughness tester made by Alpa Co. of Milan, Italy. The profile on typical rolled aluminum after washing to remove grease and contaminants is 16-24 microinches (.6 - 0.96 μm). The profile on steel varies more widely but is typically less than 50 microinches (2 μm). On both steel and aluminum, before a release coating is applied the profile typically is increased to over 100 micro inches (4 μ m), preferably for aluminum for some uses to 180-220 micro inches (7.2 - 8.8 μ m). Thus, the present invention is particularly useful with steel or aluminum substrates having a profile of less than 100, preferably less than 50 micro inches (less than 4μm, preferably less than 2μm). Similar effects can be achieved using a low MV (at least 10^ 10 5 Pa Sec) PTFE with a lower still MV (10 3 to 10 5 poise or 10 2 to 10 4 M Pa Sec)PTFE. To obtain stratification, it is desirable to have a difference of at least 10^ poise in melt viscosities of the two PTFE's. The primers of the invention can also be used on substrates roughened in various ways known in the art to make coating systems even better than without such undercoats. This can combine improved chemical adhesion with mechanical effects to produce products that may be superior. In the following examples, the polyamide imide, colloidal silica and dispersions are known in the art and preferably are those of U.S. Patent 4,049,863 - Vassiliou (1977); and the ultramarine blue is that of U.S. Patent 4,425,448 - Concannon and Rummel (1984). The following examples and test data demonstrate this improved adhesion when used as a primer for fluoropolymer topcoats. The fluor opolymers are provided as 60% dispersions in water. As usual, the solids content of dispersions is indicated in the tables. The compositions were blended by techniques normal in the art and them applied to a smooth, degreased aluminum substrate by spraying. EXAMPLE 1: Polymerization and Concentration of Lower MV PTFE A cylindrical, horizontally disposed, water jacketed, stirred, stainless steel reactor having a length to diameter ratio of about 1:5, a 4-bladed cage-type agitator running the length of the reactor, and a water capacity of about 80 parts was charged with 46 parts of demineralized water and 0.022 parts of ammonium perfluorocaprylate dispersing agent. The reactor was pressure tested at 2.8 MPa and 90° C while stirring the reactor contents at 46 rpm. The reactor was then cooled to reduce the temperature of its contents below 30° C. The reactor was then evacuated and purged three times with tetrafluoroethylene (TFE) monomer, leaving a reduced pressure on the reactor after the final evacuation. A valve was then opened to slowly release ethane into the reactor until the pressure was raised by 0.06 MPa. The valve was then closed and the reactor temperature was raised to 90° C with the agitator running at 46 rpm. After the temperature reached 90° C, the reactor was pressurized with TFE to a pressure of 2.6 MPa. A freshly prepared solution of 1.1 parts of a solution of (0.1%) ammonium persulfate (APS) and (1.5%) disuccinic acid peroxide (DSP) in demineralized water was pumped into the reactor at a rate of 0.11 parts/minute to initiate polymerization. After polymerization began (0.07 MPa drop in reactor pressure), additional TFE was added to the reactor at a rate so as to maintain the pressure at 2.6 MPa. After 3 parts of TFE had been added to the reactor after kickoff, 2.2 parts of a 2.4% solution of ammonium perfluorocaprylate in demineralized water was pumped into the reactor at a rate of 0.2 parts/minute. After 15 parts TFE addition, 0.66 parts of a solution of APS (0.05%), DSP (0.5%), and methanol (0.5%) in demineralized water were pumped into the reactor at a rate of 0.11 parts/minute. When 22 parts of TFE had been added to the reactor, the TFE feed was stopped but the reaction was continued until the reactor pressure dropped to 1.3 MPa. The reactor was then vented and the product dispersion was removed. The dispersion contained about 34% polymer by weight. A small amount of the dispersion was coagulated by the application of vigorous stirring and the resulting powder was then dried in a 120° C oven. The melt viscosity of the dried resin was measured at 372° C by the procedure described in ASTM D-1238-52T modified by (1) using a cylinder, orifice, and piston tip made of a corrosion-resistant alloy, Haynes Stellite 19, (2) charging a 5.0 g sample to the 9.53 mm ID cylinder, and (3) five minutes after charging, the sample is extruded through a 2.10 mm diameter, 8.00 mm long square-edged orifice under a load of 5000 g. The melt viscosity in poise was calculated as 36,910 divided by the observed extrusion rate expressed in grams per minute. The melt viscosity of this dried powder was 5.6 x 10 poise (5.6 x 10^ Pa Sec). The remaining as-polymerized dispersion was heated to 80° C while gently stirring. When the temperature reached 40-45° C, a weight of Triton X-100 non-ionic surfactant of octyl phenol polyether alcohol sold by Rohm and Haas Co. equivalent to 8% of the weight of polymer was added to the dispersion. Citric Acid (0.02% based on polymer) and then 19% aqueous ammonium carbonate solution (0.7% based on polymer) were then added. When the temperature reached 80° C, the agitation and heat were stopped. Upon cooling, the dispersion separated into two layers with nearly all of the polymer being concentrated in the lower layer. This lower layer was removed and analyzed for % solids and % Triton X-100. The respective levels were found to be 53.6% solids and 3.7% Triton X-100. Adjustments were made with water and Triton X-100 additions so that the final levels were 46.7% and 8.9% respectively. EXAMPLE 2: Polymerization and Concentration of Higher MV PTFE A batch was polymerized in a similar manner to that described in Example 1 except for the following; (1) the precharge included 1.3 lbs. of paraffin wax, and (2) chloroform (0.026 parts) was added to the reactor in place of ethane. All other respects of the polymerization were identical to that described in Example 1. The product dispersion contained 34% (by weight) polymer. A small amount of the dispersion was coagulated and dried. The melt viscosity of the dried powder was measured as above except that the 5000 g weight was replaced by a 15,000 g weight. The melt viscosity was then calculated by dividing 110,250 by the observed melt flow in grams per minute. The value obtained was 7.3 x 10^ poise. The remaining dispersion was concentrated in an identical manner to that described above except that the ammonium carbonate solution was replaced by an equivalent amount of 28% ammonium carbonate solution. The final solids level was 60.2% and the Triton X-100 level was 5.9%. Low MV PTFE for the invention can be provided in the form of as- polymerized micropowder made in accordance with this example or in the form of irradiated and comminuted micropowder made by techniques such as taught by the above-identified Brown et al and Derbyshire patents. EXAMPLE 3: Low MV PTFE /Regular PTFE - Multiple Coat System Composition: Table 1 Application: This system is comprised of a primer of the invention which is applied at 5-10 μm dry film thickness (DFT) to a metal surface which has been washed to remove oil and dirt contamination, air dried, and topcoated with a single (15-17.5 μm. DFT) or multiple topcoats in thicknesses of 12.5-17.5 μm DFT each and having compositions similar to those shown in the Table 1. The films are baked 10 minutes at 150° C followed by a high temperature bake for a minimum of 3 minutes over 415° C. Two different proportions of resins were used as a primer with a topcoat on smooth aluminum cookware which was subjected to tiger paw testing, described above. The number of standard cooking cycles to a rating of 5, determined by coating deterioration, was recorded and presented below along with the percentages of the comparable value for a commercial coating on a grit-blasted substrate run as a control. The results are better than many good commercial products. Testing: Table 2 Low MV PTFE for the invention can be provided in the form of as-polymerized micropowder made in accordance with Example 1 or in the form of irradiated and comminuted or ground micropowder made by known techniques. A preferred topcoat is that of Example 1 of U.S. Patent 4,118,537. Alternatively, the coats above the undercoat and primer (topcoat and optional intermediate coats) can be those of U.S. Patent 4,252,854; 4,351,882; and 4,425,448, and combinations thereof. EXAMPLE 4: Single Coat Unique Coating Characteristics: This coating is unique in that one can obtain excellent adhesion to smooth metal at fluoropolymer to binder ratios of up to 10:1. It produces a high gloss appearance and a silky feel in a one-coat. The two types of PTFE were made in accordance with Examples 1 and 2. Composition: Table 1 Low MV PTFE Single Coat Weight Percent 2.080 "Afflair 153" titania coated mica from 5 EM Industries 1.984 Channel black pigment 0.992 Aluminum silicate 14.664 PTFE MV = 7.3 x 10 6 poise (7.3 x 10 5 Pa Sec) 3.489 "Ludox AM" colloidal silica from Du Pont l ° 11.742 PTFE MV = 5.6 x 10 4 poise (5.6 x 10 3 Pa Sec) 3.394 AI-10 polyamide imide resin from Amoco 0.138 Sodium polynaphthalene sulfonate 53.352 Deionized water 1.784 "Triton X-100" octyl phenol polyether alcohol 1 non-ionic surfactant from Rohm and Haas 0.479 DiethyleΛanolamine 0.958 Triethylamine 2.607 Furfuryl alcohol 2.263 N-methyl pyrolidone - ° 0.074 Triethanol amine 100.00 TOTAL Application: Applied at 17.5-20 μm dry film thickness (DFT) to degreased metal and cured for 10 minutes at 150° C followed by 3 minutes at 427° C. 5 Testing: This coating passes fingernail adhesion and Crosshatch testing both prior to and after boiling in water for 15 minutes. Low MV PTFE for the invention can be provided in the form of as-polymerized micropowder made in accordance with Example 1 or in 0 the form of irradiated and comminuted micropowder. If, instead of using the coatings of the invention as a single coat, it is desired to use them as primers, then a preferred topcoat is that of Example 1 of U.S. Patent 4,118,537. Alternatively, the coats above the 5 undercoat and primer (topcoat and optional intermediate coats) can be those of U.S. Patent 4,252,854; 4,351,882; and 4,425,448, and combinations thereof. EXAMPLE 5: Topcoat Table 2 INGREDIENT TOPCOAT 1 TOPCOAT 2 T-30" PTFE from Du Pont 280.74 196.52 PTFE MV=5.6 x 10 4 poises (5.6 x 10 3 Pa Sec) 16.85 101.07 from Example 1 0.42 0.42 (ditto Topcoat 1) 50.01 50.01 Acrylic Latex of 39 parts by weight terpolymer of methyl me thacrylate/57 parts ethyl acrylate/4 parts methacrylic acid, dispersion at 40% solids in water, 0.2 μm average particle size Carbon black mill base Ultramarine blue mill base Application: This system is comprised of a primer of PTFE, FEP and polyamide imide of Example 1 which is applied at 5-10 μm dry film thickness (DFT) to a metal surface which has been washed to remove oil and dirt contamination, air dried, and topcoated with a single (15-17.5 μm DFT) or multiple topcoats of this example in thicknesses 12.5-17.5 μm DFT each and having compositions similar to those shown in Table 2. The films are baked 10 minutes at 150° C followed by a high temperature bake for a minimum of 3 minutes over 415° C. EXAMPLE 6: Testing Smooth aluminum bakeware with cupcake-shaped depressions were coated with primer of Example 4 and topcoat of Example 5. A variety of types of baked goods were baked, then the bakeware was turned upside down. If the baked goods fell out easily, leaving no residue, the coating was rated best. Increasing amounts of residue sticking to the coating, and the need to hit the back of the bakeware or even to dig the baked goods out with a tool, gave progressively lower ratings. Trials were made on bakeware with and without cooking grease applied between bakes. The results without grease were equivalent to commercial coatings, and with grease were superior to commercial coatings. For use with the topcoats of the invention, primers can be applied direct to smooth, degreased substrates, or the substrates can be grit- blasted or etched to provide a greater profile, or frits can be applied first to the substrates.

Claims: CLAIMS 1. An aqueous coating composition comprising perfluorocarbon resin and at least one of polyamide imide and polyether sulfone resins, wherein the perfluorocarbon resin comprises at least two different polytetrafluoroethylene resins, the first having a melt viscosity of at least 10 5 Pa Sec and the second having a melt viscosity in the range of 102 to 10 Pa Sec, with the melt viscosity of the first being at least 10^ Pa Sec higher than that of the second. 2. The coating composition of claim 1 wherein the melt viscosity of said first resin is at least 10 10 Pa Sec and of said second resin is in the range of 10 3 -10 5 Pa Sec. 3. The coating composition of claim 1 wherein the melt viscosity of said first resin is at least 10 M Pa Sec and of said second resin is in the range of 10 2 -104 Pa Sec. 4. The coating composition of Claim 1 wherein the perfluorocarbon resin contains, by weight, about 50-90% of said first resin, and 50-10% of said second resin. 5. The coating composition of Claim 2 consisting essentially of, by weight, about 3-5% colloidal silica, 1-4% surfactant, 15-30% polyamide imide resin, and 25-55% perfluorocarbon resin and the perfluorocarbon resin consists essentially of 60-85% of said first resin, the balance said second resin. 6. A coated substrate wherein the coating comprises a coating composition of Claim 1 and the substrate is free of contaminants that would prevent adhesion of the coating. 7. The coated substrate of claim 6 wherein the coating is a multi-layer non-stick coating comprising a primer, a topcoat and up to one or more intermediate coats between the primer and the topcoat. 8. The coated substrate of claim 7 wherein the primer is said coating composition. 9. The coated substrate of claim 7 wherein the topcoat is said coating composition. 14 10. The coated substrate of Claim 11 wherein the substrate is metal selected from aluminum, stainless steel and carbon steel which, before coating has a surface roughness profile less than 2 - 5μm. 11. The coated substrate of Claim 8 wherein the primer coating resulting from said aqueous dispersion is not uniform in composition throughout its thickness but has a lower concentration of said first polytetrafluoroethylene at the interface with the substrate than at the opposite interface.

Inventors: TANNENBAUM HARVEY PAUL, TANNENBAUM, HARVEY, PAUL
Applicants: DU PONT, E.I. DU PONT DE NEMOURS AND COMPANY
Application year: 1991
Main classification: C09D127
IPC codes: A47J36, A47J37, B32B27, C08L27, C08L79, C08L81, C09D127, C09D171, C09D179, C09D181