CA2174029C - Cookware release composition - Google Patents

Abstract

Disclosed herein is an oil-based composition containing phosphated derivatives of glycerides of edible fatty materials (such as sodium glyceryl oleate phosphate) as cookware release agents and a viscosity-reducing agent. Such compositions are further suitable for application through aerosol dispensers or pump dispensers.

Description

COOKWARE RELEASE COMPOSITION
Field of the Invention The present invention relates generally to vegetable oil compositions containing phosphated monoglycerides and/or diglycerides which are suitable for use as cookware release agents. Such compositions may further be dispensed from pump-type dispensers or aerosol containers.
Background of the Invention Lecithin, when applied to the surface of a mold, utensil or other cooking implement provides an excellent release coating. Therefore, much effort has been expended in recent years in the development of lecithin-containing compositions and methods of their application.
For instance, a solid stick form of a lecithin cookware lubricant is disclosed in U.S. Patent No.
4,023,912. Lecithin cookware lubricants dispensable in conventional aerosol containers are disclosed in U.S.
Patent Nos. 2,796,363; 3,896,975; 4,073,411 and 4,073,412.
Pump sprayable lecithin-containing cookware lubricants are further disclosed in U.S. Patent Nos. 4,155,770 and 4,163,676.
However, it has been found that under certain conditions, lecithin exhibits the tendency to darken and/or develop off-flavors which may be imparted to the food undergoing preparation. Additives for inhibiting such tendencies have therefore been utilized. For example, U.S.
Patent No. 4,654,221 describes the use of carbonate and bicarbonate salts as inhibitors against darkening of lecithin-containing compositions.

2 T » o2g other alternatives to the use of lecithin have also been described_ For example, Witco Chemical Company has disclosed the use of pure sodium glycerol oleate phosphate as a cooking release agent in Bulletin 268, dated March 1978. i~litco Chemical further markets an ionic emulsifier surfactant comprised of phosphated mono- and di- glycerides derived from vegetable oils under the trademark EMPHOS b70-30C. Due to its lack of nitrogen-based moieties, it is said to not exhibit the tendency to degrade iti color and/or flavor as phospholipids such as lecithin sometimes do.
U.S. Patent No. 4,654,ZZ1 issued to purees et al discloses the addition of alkali and alkaline earth metal salts of an oxyacid of phosphorus to edible oils to yield anti-sticking compositions.
U_s. patent No. 5,156,876 issued to C~.app et al. further discloses cookware release compositions comprising (a) phosphated salts of mono- and di-glycerides of edible fats, oils and fat-forming fatty acids, (b) an edible oil and (e) a particulate blocking agent. Component (a) is said to include the EMPH05 D70-30C product of Witco Chemical described abOve_ The ~B76 patent further requires the use of a particulate blocking agent (component (c)) such as clays, bicarbonates, carbonates magnesium or calcium stearates, flours or starches.
It is stated in Column 4, lines 15-22, that compositions without such blocking agents (i.e. composed of components (a) and (b) alone) "were unsuccessful, because the anti-stick characteristics were lacking or insufficient"_ the patent at Column 4, lines 15-22 further states that an aerosol-dispensable formulation was prepared. However, the identity of the propellant used in such formulation was not disclosed.
Surprisingly, it has been Found that a cookware release composition may be Formulated consisting essentially of components (a) and (b) in combination with a viscosity reducing agent.

Summary of the Invention The present invention relates t:> a cookware release composition consisting essentially of (a) at least one compound selE~cted from the group consisting of phosphated der_~vatives of glycerides of edible fatty materials;
(b) at least one edible oil; and (c) at least one viscosity-reducing agent.
Detailed Description of the Invention The present invention relates to a cookware release composition consisting essentially of (a) at least one compound selected from the group consisting of phosphated derivatives of glycerides of edible fatty materials;
(b) at least one edible oil; and (c) at least one viscos~.ty-reducing agent.
Component (a) used in the practice of the present invention, is one or more phosphated derivatives of glycerides of edible fatty materials. As used herein, the term "edible fatty materials" means and includes edible fats, edible oils and edible fat-forming fatty acid ; the term is used broadly to generally include all edible oily and fats and fat-forming fatty acids, whether of vegetable or animal origin.
Preferred within the class of materials within component (a) is sodium glyceryl oleate phosphate which is identified by the Tood and Drug Administration (21 CFR 182.4521) as a monosodium phosphate derivative of mono- and diglycerides of edible fats or oils, or edible fat-forming fatty, acids. This material is among those listed as generally recognized as safe ("GRAS~') . It is commercially available from Witco CheZnical as EMPHOS"" D70-3oC. This material is fuxther characterized by the CTFA Cosmetic Ingredient Dictionary (published by The Cosmetic, Toiletry and Fragrance Association, Ine. of Washington, D.C.) as sodium glyceryl oleate phosphate, the sodium salt of a complex mixture of phosphate esters of glyceryl mono-oleate_ The use of minor amounts of lecithin in combination with the above described release agent is further within the scope of the present invention. Lecithin may be present in amounts of from O to about a_5 wt. %, based on the total liquid contents of the composition.
Component (a) typically comprises from about 1_0% to about 10.0% by ~,reigt~t of the total weight of the liquid components. Preferably, it comprises from about 3% to about 6% on the same basis. Most preferably, it is present in an amount of about 4% on such basis.
Useful in the practice of the present invention as component (b) are many of the common food grade edible oils.
These include , but are not limited to, vegetable oils, such as soybean oil, olive oil, corn oil, canola oil, sunflower oil and genetically modified oils. As used herein, the term "vegetable oil's refers to those food grade oils of vegetable origin which are liquid at normal use temperatures (65-809F) as distinguished from fully hydrogenated vegetable fats which are solid at such temperatures. I~or example, vegetable oils having a viscosity of about 40 to about 300 centipoise are suitable for use herein. Other oils or shortenings such as animal fats or edible fat-forming fatty acids derived from any suitable source are also useful in the practice of the present invention. In addition, the use of structured lipids, principally medium chain triglycerides such as caprylie/capric triglycerides marketed by Stepan Food Ingredients as Captri_ne, is also within the scope of the present invention. The use of mixtures of such oils is further ~,rithin the scope of the present in~trention. The use of vegetable oil is preferred and the use of canola oil is especially preferred.
The oil component typically comprises from about 20% to about 95% by weight of the total weight of the liquid components. Preferably, it comprises from about 50% to about 85% on the same basis. Most preferably, it is present in an amount of about BO% on such basis.
The viscosity reducing agent (component (c)) useful in the practice of the px-esent invention is sElected from the group consisting of a low molecular weight hydrocarbon gas, a low molecular weight alcohol, and mixtures thereof.
Preferably the viscosity reducing agent is isobutane, isopropane, N--propane, N-butane, ethyl alcohol, ethyl alcohol denatured with a GRAS~classified food grade denaturant as described below or mixtures thereof. Most preferably, the viscosity reducing agent is ethyl alcohol, Ethyl alcohol, for the purposes of the present invention is ethanol of 190Q and zOOQ proof which conforms with United States Pharmacopoeia (U_S.P.) standards for Alcohol and Dehydrated Alcohol, respectively. The 190Q proof to ZOOQ
proof ethanols are staple articles of commerce and are available, for instance, from U.S. Industrial Chemical Co.
Ethanol of 200 U_5. proof at 6oQF has a specific gravity of 0.79365, is loo percent by weight of ethyl alcohol. Ethanol of 190 U_S. proof at 60pF has a specific gravity of 0.81562, is 92.423 present by weight of alcohol and contains 7.577 percent by weight of water. The 7.9oq proof ethanol may be made by mixing 95 parts by volume of ethyl alcohol ~,rith 6.18 parts by volume of water. As used in the present invention, the ethyl alcohol functions as both a 'viscosity-lowering solvent and a clarifying agent.
Also within the scope of the term ethyl alcohol is ethyl alcohol denatured with a GRAS-classified food grade denaturant, as for example S.D.A. 29-3. S.D.A_ 29-3 contains 99% ethyl alcohol and 1% ethyl acetate as a denaturant. Ethyl acetate is a GRAS denaturant thereby allowing the use of S.D.A. z9-3 in a food grade product such as the claimed composition.
As noted above, the viscosity-reducing component (c) may be a liquified, low molecular weight hydrocarbon gas, such as 21 l4 029 isobutane, isopropane, N~propane, N-butane or mixtures thereof_ Many of these materials are of course well-known aerosol propellants. Therefore, in instances where the claimed compositions are to be dispensed by way, of an aerosol dispenser, such materials may serve as both propellant and as a viscosity-reducing agent. When used as such, additional viscosity-reducing agents, such as an alcohol, may also be present.
In cases where the ~riscosity-reducing agent is other than liquified low molecular hydrocarbon gas, the viscosity-reducinq cox~ponent is typically present in amounts of from about 5% to about 25~ by weight of the total weight of the liquid components. Preferably, it comprises from about 5% to about 1'7% on the same basis. Most preferably, it is present in an amount of about l0% on such basis. In cases where liquified hydrocarbon gases are present, other viscosity-reducing agents may be present in the above amounts. However, it is preferable that they be present in reduced quantities relative to those ranges recited diz~ectly above since the liquified hydrocarbon gas will Function as the primary viscosity-reducing agent.
In the embodiment of the present invention wherein the claimed composition is dispensable by way of an aerosol spray, the claimed composition is admixed with a propellant. The selection of propellants is not critical to the practice of the present invention. Propellants such as; liquified hydrocarbon gases (such as lower molecular weight allcanes), and halogenated compounds, or compressed gases such as nitrogen, Carbon dioxide, nitrous oxide may therefore bra used_ It should further be noted that selection of propellants may bring additional benefits. For instance, the use of nitrous oxide may offer the benefit of miniraizing undue degradation of the spray pattern of the claimed composition When discharged from an aerosol dispenser as reported in related U_S_S.N. 08/111,096 identified above. The use of _ 7 _ nitrous oxide may further aid in compliance with legislation enacted in various states limiting the use of volatile organic compounds ( ~~VOC' s~~ ) _ For instance , C.n 1 ifornia has enacted legislation limiting the VOC content of aerosol food release products to no more than 18 wt.%. Also c=ontemplated as within the scope of the present invention is the use of mixtures of the above propellants. Preferred in the practice of the present invention is the use of low molecular weight hydrocarbon propellants such that the formulation comes under the 18 wt. % VOC limit noted above_ The hydrocarbon propellant is to be present in an amount ranging from about 10 to about 50$ by weight, based upon the total weight of the liquid components. Preferably, the propellant is present in an amount ranging from about 15% to about 25% on the same basis_ Most preferably, it is present in an amount of about 17% on such basis.
=n the case where a compressed gas propellant such as nitrogen, nitrous oxide or carbon dioxide is used as a propellant, it may be present in an amount ranging from about 2 to about a _ 5% by ~,reight, ,based upon the total weight of the liquid components. Preferably, the propellant is present in an amount ranging from about 3% to about 5% an the same basis.
Host preferably, it is present in an amount of about 4.5% on such basis.
The claimed formulation consisting of components (a)-(c) is suitable for manual application to cookware through use of a brush applicator, for instance_ The claimed formulation is further suitable for application through the use of a purilp dispenser such as those disclosed in above-mentioned U.S.
Patent Nos_ 4,~.SS,770 and 4,163,676.
The claimed composition may further contain optional ingredients such as preservatives, antioxidants, emulsifying agents, coloring agents and flavoring agents in minor proportions. Useful preservatives include sodium benzoate, calcium propionate, sorbic acid or salts of sorbic acid such -e_ as sodium sorbate and potassium sorbate. Preferred are sodium benzoate in an amount of from about o.05 to about o.1 wt.
percent and calcium propionate in an amount of from about o.l to about o.3 wt. percent. Naturally or synthetically derived antioxidants may be utilized to prevent rancidity.
In preparing the claimed composition, a suitable manufacturing procedure is as follows: Component (a), which raay be preheated to lOOQ-160QF, is mixed with the vegetable oil component stepwise until a uniform solution is obtained.
The viscosity reducing component, as well as other optional components, may be added separately at this point, or previously introduced in one or both of the other components.
Any optional materials which are not soluble in the resultant solution, such as the previously described visual directing aids may be added with agitation continued until a uniform dispersion is obtained. The resulting blend is then filled into the container and a vacuum is drawn to purge air from the container. A suitable aerosol valve is then inserted and the container is charged with a suitable hydrocarbon propellarzt.
Alternatively, a valve is crimped into place creating an air tight pressure seal. A compressed gas propellant such as nitrogen, nitrous oxide or carbon dioxide is then injected into the container.
With regard to the aerosol containers useful in the practice of the present invention, conventional aerosol containers may be used. Also useful in the practice of the present invention are thin-walled aerosol containers such as those disclosed in U.S. Patent No. 5,211,31, the contents of which are hereby incorporated by reference. Conventional valve componerits may be used in the practice of the~present invention.
The claimed compositions can be uniformly and effectively applied to surfaces of molds, frying pans, sauce pans, baking pans or other cooking surfaces whether composed of metal, glass or ceramic materials. The thin coating film better g _ permits the cooking of moisture-containing materials~such as eggs, pancakes, etc. without grease or fat, and after cooking, these materials will come free from the surface without rubbing or scouring. When fatty foods are cooked on a surface so coated, they will come off readily by soaking in hater for several minutes, even when burned crisp or charred. In no case is scrubbing, scouring or the use of brushes, abrasives or scouring powders, snaps or detergents normally required for the cleaning for such utensils. While preferably, the composition should be applied each time the cooking surface is utilized, in many cases the coating will last for several or more cookings without reapplication.
Preferably, the compositions of the preser~t invention possess a clear spray such as is exemplified xn Examples i --21, 23 and 26 - 28. For purposes of this invention, nclear"
is defined as apparent clarity when dispensed from a distance of 810 inches onto a stainless steel surface, eg. , fryir~g skillet. For evaluation purposes of the Examples, additional terms which follow describing the range of observations of spray appearance are employed: "Milky" which denotes an opaque/cloudy appearance; "Foamy'' which denotes the ability of the actuated material to build and sustain a foam for a minimum of ten seconds. It is noted that in Examples 22, 24 and 25, the milky, foamy and foamy appearances, respectively, yield a clear presentation when heated in a skillet.
The composition of the present invention does not darken when thermally stressed (eg. 35oa - 45ooF). In addition, the composition remains clear when thermally stressed. This is directly attributable to the lack of lecithin and solid particulates (i.e., blocking agents as disclosed in U.S.Patent No. 5,156,876 issued to Clapp et al.).
The folXowing Examples are offered for the purpose of illustration only and are not to be construed in any way as a limitation of the invention or its scope.

_ ~o - 217 4 029 examples 1-28 Compositions made up of vegetable oil, ethyl alcohol, sodium glyeeryl vleate phosphate (marketed by Witco Chemical as EMPHOS"" D7o-3oC) and a propellant were formulated according to the procedure set forth below:
1. The formula amount of vegetable oil (Canola Salad oil) was transferred into an appropriate vessel equipped with a variable speed agitator_ Z. The required amount of D7o-3oC (heated to 100 -l6o~F' to facilitate transfer) was then added to the batch vessel under moderate non-aerating agitation.
3_ While maintaining agitation, the required amount of ethyl alcohol was added to the mixture.
4. The batch was allowed to mix ur~til uniform.
Each composit~,on was then charged into a conventional aerosol container. A vacuum was then drawn to purge air from the container. A suitable aerosol valve was then inserted and the container was charged with a suitable hydrocarbon propellant_ Alternatively, a valve was crimped into place creating an air tight pressure seal. These containers were then each charged with a compressed gas propellant.
As used in the examples, the following terms have the following meanings. Canola oil means the canola oil marketed by ADM under the designation Deodorized Liquid Cariola Oil.
Olive oil means the olive oil marketed by Columbus Foods under the designation Ballaster Spanish olive Oil. D70-30C is as noted above. Lecithin means a lecithin product marketed by Central Soya under the designation of 64 CX. A-67 is a propellant mixtu=e consisting of about 6U/4o% mixture of isobutane and N-propane, respectively. Methyl silicone means polydimethylsiloxane marketed by union Carbide corporation under the designation of L-54 polydimethylsiloxane.
Acetylated monos means distilled acetylated monoglycerides m$rketed by Eastman Chemical. Company under the designation of rlyvacet 9-45_ AF NBA means Natural/Artificial Butter Flavor marketed by Alex Fries under the designation of 83-241 Liquid.

- il -Annatto means Annatto Food Color marketed y Rhone-Foulenc, b Ino. under designation of AFC OS 4s0_ the Spray Example ~ Ingredient Percentag e Description 1. canola oil 77.873 clear EtO~I 13 . 17 B

D70-30C 4.792 Nitrous oxide 4.157 2. canola oil 60.98 clear EtOH 14.025 .

D70=30C g.g87 A-67 15.002 3. canola oil 69.062 clear EtoH 11.688 D70--30C 3 . 400 lecithin 0.850 A-67 15.000 4. canola oil 60.987 clear EtOH 14.025 D70i-30C 9.138 lecithin 0.850 A-67 15.000 5. canola oil 58.000 clear EtOH 11.000 D70-30C 6.000 A-67 25.000 6. canola ail 55.000 clear EtOH 13.000 D70-30C 7.000 A-67 25.000 7. canola oil. 54.000 clear EtOFi 13 . O O
O

D70-30C 8.000 A-67 25.000 8. canola oil 53.000 clear EtOH 13.000 D70-30C 9.000 A-67 25.000 9. canola oil 55.750 clear EtOH 13.000 D70=30C 6.000 lecithin o.25D

A-67 25.000 10. canola oil 55.500 cleat EtOH 13.000 D70-30C 6.000 lecitRin 0.500 A-67 25.000 11. clnola oil 55.Z5o clear EtOH 13.000 D70-30C 6.000 lee2thin 0.750 A-6,7 2 5 . 000 12. canola oil 55.000 clear EtOH 13.000 D70r30C 6.000 lecithin 1.000 A-67 25.000 13. canola oil 56_000 clear EtOH 20.000 D70-30C 9_000 A-67 15.000 14. canola oil 57.000 clear EtOH 15_000 D70-30C 8.000 A-67 ZO.000 15. canola oil 60.000 clear EtOH 10.000 D70-30C 10_000 A-67 20.000 15- canals oil 58.000 clear EtOH 13.000 D70-30C 4.000 A-67 25_000 17. canola oil 50.000 clear EtOH 13.000 D70-30C 12_000 A-67 25.000 18. canola oil 76.843 clear EtOH 15.000 D70-30C 4.000 Nitrous oxide 4.157 19. canola oil 59.000 clear EtOH Zo.ooo D7o-3oc s.ooo A-67 15.000 ZO_ canola oil 59.000 cleat EtOH 15.000 D70-30C 6.000 A-67 20.000 21. canola oil 65.000 clear EtOH 5.000 D70-30C 10.000 A-67 20.000 22 - . canola oil 71. o0o milky EtOH O_0o0 D70-30C 4.000 A-67 25.000 23. canola oil 81.843 clear EtOH 10.000 D70-30C 4.000 Nitrous oxide 4.157 24. canola oil 79.000 foamy EtOH 0.000 D70-30C 4_000 A-67 17.000 Z5_ canola oil 59.000 ~oauty Acetylated Monos 10.000 D70-30C 4.000 A-67 17.000 26. canola oil 78.999 clear EtOH 0.000 D70-30C 4.000 methyl silicene 0.001 A-67 17_000 27- olive vil 78.999 clear EtOH 0_000 D70-30C 4.000 methyl silicone O.oOx A-67 17.000 28. canola oil 76.926 clear EtOH O.o00 D70-30C 4.000 methyl silicone O.ool AF N&A 1.997 Annato 0.076 A-67 l7.Opo Examples Z9-31 steps 1 - 3 used in the preparation of the compositions described in Examples 1 - 2B were repeated. The batch was then allowed to mix until uniform. Each composition was then charged into a conventional pump container. A suitable pump valve was inserted_ spray Example ~ ~naredient Percantaae Descri ti p on 29. canola oil 90.999 clear EtOH 5.000 D70-3pC 4.000 methyl silicone 0.001 30- eanola oil 88.499 clear EtOH 7.500 D70-30C 4.000 methyl silicone 0.001 31. canola oil 85.999 clear EtOIi 10.000 D70-30C 4.000 methyl silicone 0.001

Claims (22)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A cookware release composition consisting essentially of (a) at least one compound selected from the group consisting of phosphated derivatives of glycerides of edible fatty materials;

(b) at least one edible oil; and (c) at least one viscosity-reducing agent.

2. The composition of Claim 1 wherein component (a) is present in such composition in amounts ranging from about 1 wt. % to about 10 wt.%, based upon the total weight of the composition.

3. The composition of Claim 1 wherein component (a) comprises sodium glyceryl oleate phosphate.

4. The composition of Claim 3 wherein component (a) is present in such composition in amounts ranging from about 1 wt. % to about 10 wt.%, based upon the total weight of the composition.

5. The composition of Claim 1 wherein the edible oil component comprises vegetable oil.

6. The composition of Claim 5 wherein the vegetable oil is selected from the group consisting of canola oil, olive oil, soybean oil, corn oil and mixtures thereof.

7. The composition of Claim 1 wherein the edible oil component is present in such composition in amounts ranging from about 10 wt.% to about 95 wt.%, based upon the total weight of the composition.

8. The composition of Claim 1 wherein the viscosity-reducing agent is selected from the group consisting of a low molecular weight hydrocarbon gas, ethanol and mixtures thereof.

9. The composition of claim 8 wherein the viscosity-reducing agent is a low molecular weight hydrocarbon gas selected from the group consisting of isobutane, isopropane, H-propane, N-butane and mixtures thereof.

10. The composition of Claim 9 wherein the viscosity-reducing agent is present in such composition in amounts ranging from about 10 wt. % to about 50 wt. %, based upon the total weight of the composition.

11. The composition of Claim 9 wherein the viscosity-reducing agent is present in such composition in amounts ranging from about 15 wt. % to about 25 wt. %, based upon the total weight of the composition.

12. The composition of Claim 1 wherein the viscosity-reducing agent is ethanol.

13. The composition of Claim 12 wherein the viscosity-reducing agent is present in such composition in amounts ranging from about 5 wt. % to about 25 wt. %, based upon the total weight of the composition.

14. The composition of Claim 12 wherein the viscosity-reducing agent is present in such composition in amounts ranging from about 5 wt. % to about 17 wt. % , based upon the total weight of the composition.

15. The composition of Claim 8 wherein the viscosity-reducing agent is a mixture of ethanol and a low molecular weight hydrocarbon gas selected from the group consisting of isobutane, isopropane, N-propane, N-butane and mixtures thereof.

16. The composition of Claim 1 further comprising an aerosol propellant.

17. The composition of Claim 16 wherein the aerosol propellant comprises a compressed gas selected from the group consisting of nitrogen, nitrous oxide, carbon dioxide and mixtures thereof.

18. The composition of Claim 17 wherein the compressed gas is present in amounts ranging from about 2 to about 8.5 % by weight, based upon the total weight of the liquid components of the composition.

19. A pump dispenser containing the composition of Claim 1.

20. An aerosol dispenser containing the composition of Claim 1.

21. An aerosol dispenser containing the composition of Claim 8.

22. An aerosol dispenser containing the composition of Claim 17.