Note: Descriptions are shown in the official language in which they were submitted.
2027279
BACRGROnND OF THE INVENTION
Field Of The Invention
The present invention relates to a parting composition
for use in cooking foodstuffs, more especially to a parting
composition of the type applied to cooking utensils, such as
baking and frying pans and the like, in order to prevent or
reduce the sticking of food to the utensil during cooking.
Related Art
U.S. Patent 4,654,221 to E.R. Purves et al discloses
the addition to cooking fats of alkali and alkaline earth
metal salts of an oxyacid of phosphorus, e.g., sodium,
potassium and calcium phosphate salts, to provide an anti-
sticking composition. The known use of lecithin (a phospho-
lipid) as an anti-sticking additive for cooking fats is de-
scribed, as is the tendency of increased lecithin content to
cause darkening and the development of off-flavors during
cooking. Additives for inhibiting such darkening, including
carbonate or bi-carbonate salts, are described.
The use of flour in parting compositions containing
edible oils and lecithin is known. U.S. Patent 4,211,802 to
W.C. Carey discloses a parting composition comprising clear
flour (a wheat flour obtained from the first milling of the
wheat), soybean flour, hydrogenated vegetable shortening,
vegetable oil and lecithin. U.S. Patent 3,821,007 to W.C.
Carey discloses a method of preparing a spray-type pan ma-
terial comprising vegetable shortening, commercial grades of
wheat and soybean flour, a liquid vegetable salad oil, and
lecithin.
U.S. Patent 4,339,465 to O.L. Strouss discloses a
baking pan release agent comprising a liquid emulsifier
containing mono-glycerides and di-glycerides derived from
animal fat or vegetable oils and a polysorbate compound,
together with a ma~or portion by weight of water. Un-
bleached liquid lecithin may be added to the composition to
aid in its adherence to the walls of baking pans.
*'
,. ~
-2- 2~27279
The use of sodium glyceryl oleate phosphate ("SGOP")
as a pan release agent is disclosed in a technical bulletin
of Witco Chemical Company (Bulletin 268, dated March, 1978),
which discloses an ionic emulsifier surfactant, sold under
the trademark EMPHOS D70-30C, comprised of phosphated mono-
and di-glycerides derived from vegetable oils. The Techni-
cal Bulletin discloses that the functional properties of the
surfactant are similar to those of lecithin and that, since
the EMPHOS D70-30C product does not contain nitrogen deriva-
tives, it is not sub~ect to the degradation of taste andflavor sometimes associated with naturally occurring phos-
pholipids.
S~MMARY OF T~E I~V~~ ON
Generally, the present invention provides a parting
composition for cooking foodstuffs, the composition util-
izing, in lieu of lecithin or other natural phospholipids,
a phosphated derivative of glycerides of edible fatty ma-
terials ("Phosphated Derivative") in combination with a
suitable blocking agent, preferably a refractory blocking
agent. The present invention is predicated on the dis-
coveries that (l) surprisingly good results are attained by
the combination of the aforesaid Phosphated Derivative and a
suitable blocking agent, and (2) that refractory blocking
agents provide not only high temperature resistance to the
parting composition, but superior results when used in
combination with Phosphated Derivative.
Specifically, in accordance ~ith the present inven-
tion, there is provided a parting composition for cooking
foodstuffs comprising the following ingredients. A release
agent comprising one or more phosphated derivatives of
glycerides of edible fatty materials, for example, phos-
phated derivates of mono- and di-glycerides of edible fatty
materials; an edible oil; and a blocking agent comprising an
edible pulverulent material, for example, a material se-
lected from the group consisting of edible clays, such as
food grade or pharmaceutical grade clays, e.g., bentonites
-3_ 2027279
or kaolins, magnesium aluminum silicate, sodium bicarbonate
(baking soda), baking powder, ground limestone, calcium
carbonate, magnesium or calcium stearate, flours and
starches.
One aspect of the invention provides that the release
agent is selected from the group consisting of salts, such
as sodium, potassium, calcium and magnesium salts, of phos-
phate derivatives of edible fatty materials, for example,
the release agent may be a monosodium phosphate derivative.
The parting composition may further include one or
more of suitable additives of the type employed in parting
compositions, especially in those which are combined with
a propellant for dispensing from a pressurized aerosol con-
tainer. Thus, the parting composition may also contain
water, a dispersant such as pyrogenic silica and a foam-
control ingredient such as ethanol.
Another aspect of the invention provides that the
parting composition may comprise from about 2 to 8 parts by
weight of the release agent, from about 77 to 97 parts by
weight of the edible oil, and from about l to 12 parts by
weight of the blocking agent.
Other aspects of the present invention are described
in the following detailed description of the invention and
preferred embodiments thereof.
As used herein and in the claims, the term "edible
fatty materials" means and includes edible fats, edible oils
and edible fat-forming fatty acids; the term is used broadly
to generally encompass all edible oils and fats and fat-
forming fatty acids, whether of vegetable or animal origin.
Reference herein, including the claims, to an in-
gredient of the parting composition being "edible" means
that at least in the quantities used in the composition it
may be ingested without ill effect, it does not necessarily
mean that the edible material has nutritional value, al-
though it may, as in the case of flour, some starches, and
oils. Reference herein, including the claims, to "food-
grade" or "pharmaceutical" with respect to a clay or other
-4- 2027279
material simply means a grade or quality of such material
which is suitable and safe for ingestion, e.g., which may
safely be used in or as a component of a food or medicine,
and is otherwise suitable for such use by reason of its
color, particle size, etc. As used herein including the
claims: "baking soda" has its usual meaning of a synonym
for sodium bicarbonate which may, but need not, contain a
filler of minor amounts of other additives; "baking powder"
has its usual meaning, i.e., a mixture of sodium bicar-
bonate, plus a weak acid or acidic compound and, usually, afiller. A typical baking powder composition is sodium
bicarbonate, tartaric acid or monobasic calcium phosphate,
and cornstarch. "Limestone" has its usual meaning of rock
comprised mostly of calcium carbonate.
Reference herein, including the claims, to a blocking
agent being "refractory" means edible materials which are
significantly more resistant than flours and edible starches
to charring or decomposition at high cooking temperatures;
generally, the term embraces edible non-carbohydrate mate-
rials and includes clays, alkali metal and alkaline earth
metal salts, such as carbonates and stearates, and mixtures
thereof, e.g., ground limestone.
A11 percentages given herein, including those in the
claims, are percentages by weight, based on the total weight
of the formulation, unless explicitly stated otherwise.
DETAILED DESCRIPTION OF THE IN~NllON
I~CLUDING PREFERRED EMBODIMENTS THEREOF
As indicted by some of the related art described
above, a drawback of the use of lecithin or other phospho-
lipids in parting compositions for cooking foodstuffs is
their tendency to darken and provide off-colors and off-
flavors at normal cooking temperatures. Some lecithin
formulas begin to decompose at temperatures as low as 200F
(93.3C) and blacken or darken when exposed to a temperature
of about 350F (176.7C) for twenty minutes. The darkened
decomposition products of lecithin are often transferred to
-5- 2027279
the food being cooked, with adverse effects on appearance
and flavor. The decomposition also destroys the anti-stick
properties of the lecithin, resulting in sticking of the
food to the cooking pan.
In contrast, the parting composition of the present
invention has been found to exhibit excellent anti-stick
characteristics and resistance to darkening and the develop-
ment of off-flavors. These characteristics are maintained
even at the high end of temperatures normally used for cook-
ing, that is, at temperatures of about 400F to about 500F
(204.4 to 260C), for significant time periods. Of course,
if flour or starch is employed as the blocking agent in the
composition, some discoloration will show after being heated
to temperatures of about 400F (204.4C) for appreciable
periods of time. However, when a refractory blocking agent
such as an edible clay, sodium bicarbonate or calcium or
magnesium stearate is used in the compositions of the pres-
ent invention, the compositions show, in addition to excel-
lent release characteristics, even greater resistance to
discoloration at high cooking temperatures. To that extent,
the use of refractory blocking agents is preferred.
The compositions of the present invention include, as
described above in the Summary Of The Invention, a release
agent which comprises one or more phosphated derivatives of
glycerides of edible fatty materials, e.g., of mono- and
di-glycerides of edible fatty materials. Generally, these
compounds may be regarded as phospholipids which, unlike
natural or processed lecithin, are free of nitrogen deriva-
tives. For example, a preferred release agent utilizable in
accordance with the present invention is sodium glyceryl
oleate phosphate ("SGOP") which is identified by the Food
and Drug Administration (Code of Federal Regulations, Title
-21, Part 182.4521) as a monosodium phosphate derivative of
mono- and di-glycerides of edible fats or oils, or edible
fat-forming fatty acids. SGOP is a heat stable material and
is listed by the Food and Drug Administration as generally
recognized as safe (I'GRAS''). SGOP is commercially available
~
, .
2327279
as described in the above-mentioned Technical Bulletin of
Witco Chemical Company describing its EMPHOS~ D70-30C prod-
uct. The CTFA Cosmetic Ingregient Dictionary (published by
The Cosmetic, Toiletry and Fragrance Association, Inc.,
Washington, DC) identifies the EMPHOS~ D70-30C material as
sodium glyceryl oleate phosphate, the sodium salt of a
complex mixture of phosphate esters of glyceryl mono-oleate.
Among the uses described for the EMPHOS~ surfactant in the
afore-mentioned Technical Bulletin are as a mold release
agent for chocolates and a pan release agent for fat-free
frying. The Bulletin notes that the material functions over
a wide temperature range. Although the EMPHOS~ material, an
SGOP, may work well by itself as a pan release agent as
claimed in the Witco Bulletin, the present inventors' at-
tempts to substitute SGOP for lecithin in combination with avegetable oil to provide an aerosol-dispensable parting com-
position were unsuccessful, because the anti-stick charac-
teristics were lacking or insufficient. However, it was
found that when a suitable blocking agent is added to a com-
position including SGOP and an edible oil, the result wasnot only the attainment of anti-sticking or parting charac-
teristics which were superior to those of lecithin-based
products, but a greatly improved resistance to high cooking
temperatures for prolonged periods, without significant
charring or the formation of off-colors or off-flavors.
Especially good high-temperature resistance was attained,
even for prolonged high-temperature cooking, when a re-
fractory blocking agent, for example, a food or pharmaceu-
tical grade clay or magnesium or calcium stearate, or cal-
cium carbonate (ground limestone) was utilized in the com-
position. However, flours and starches are also useful
blocking agents.
- For example, good results were obtained with compo-
sitions using SGOP and flour or starch blocking agents in
oil bases; it is believed that excellent results would also
be attained with other release agents comparable to SGOP.
For example, useful release agents should be provided by
,
_7_ 2027279
appropriate alkali metal or alkaline earth metal phosphate
derivatives, such as potassium, calcium and magnesium phos-
phate derivatives, of glycerides, e.g., mono- and di-glycer-
ides, of edible fatty materials, i.e., of edible fats or
oils, or edible fat-forming fatty acids.
Any appropriate edible oil or mixture of edible oils
may be utilized in the parting composition of the invention.
Vegetable oils, including partially hydrogenated vegetable
oils, such as soybean oil, corn oil and canola oil have
proved to be eminently satisfactory in use. 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.
As noted above, it has been found that a blocking
agent comprised of a suitable edible pulverulent solid ma-
terial such as an edible clay, a bicarbonate or carbonate
such as sodium bicarbonate or calcium carbonate, magnesium
or calcium stearate, flour or starches, must be combined
with the above-described release agent in order to impart
the desired anti-stick or parting characteristics to the
parting composition. The edible clay material may comprise,
for example, one or more of a pharmaceutical grade kaolin,
a food grade bentonite. Similarly, any suitable flour may
be utilized, including ordinary commercial grades of wheat
or other cereal flours or soybean flour, and any suitable
starches such as cornstarch or the like, or mixtures of any
of the foregoing. Without wishing to be bound by any theory
of operation, it appears that the blocking agent acts to re-
tain the other ingredients, the edible oil and the release
agent, at the interface between the food being cooked and
the utensil in which the food is cooked, by preventing,
i.e., blocking, migration of the edible oil and the release
agent into the foodstuff and away from the interface. In
the absence of a blocking agent, the release agent of the
invention, for example, SGOP, proved to be ineffective as a
substitute for lecithin in parting compositions, because the
resultant compositions showed poor release qualities.
.: .
2027279
Generally, the improved parting composition of the
invention may have added to it ingredients and additives of
the type known to be suitable to provide parting composi-
tions tailored for specific uses, such as for being dis-
pensed by conventional aerosol spray pressurized cans. Forexample, ethanol in small amounts may be added to the com-
position in order to control foaming, especially when the
parting composition is packaged for application by means of
a pressurized gas aerosol spray, for which purpose the com-
position may be combined with gaseous hydrocarbon propel-
lants in a manner as known in the art. Water may also be
added to the composition which may be made into an oil and
water emulsion of the type used in pressurized aerosol-
dispensed parting compositions. Any suitable suspending
agent such as fumed silica may also be employed in the com-
position as a suspending agent for water and oil emulsions.
The parting compositions of the invention, as will be
demonstrated by some of the Examples set forth below, show
good high-temperature resistance, especially when a re-
fractory blocking agent is used. That is, the compositionsof the present invention show no, or very little, blackening
or development of off-colors or off-flavors, and the reten-
tion of superior anti-stick properties even when used for
cooking at high temperatures up to about 500F (260C). The
parting compositions of the present invention are utilize-
able in both frying and baking for a variety of foodstuffs.
Generally, the efficacy of the present invention is
demonstrated by the following Examples which disclose, among
other things, specific preferred embodiments of the inven-
tion.
Example l lists a number of parting compositions pro-
viding a series of embodiments of the present invention,
which embodiments are adapted for dispersal by an aerosol
spray using hydrocarbon dispersants. A number of compara-
tive formulations are listed in Example 2, which illustratesa number of parting compositions (including some commercial-
ly available products) which lie outside the scope of the
9 20~7279
present invention either because they use lecithin instead
of the release agent of the present invention (a "Phosphated
Derivative" as described above in the Summary Of The Inven-
tion), or because they lack a blocking agent.
E~ample 1
Parts A, B, C and D of Example 1 give formulations
comprising embodiments of the present invention.
A. All Formulas in this Part A contained, in addition
to the below-listed ingredients, 20 percent by weight of
hydrocarbon propellant IP-46 and 1.8 percent by weight of
Cab-O-Sil pyrogenic silica as a dispersent. IP-46 propel-
lant is a standard propellant gas used in consumer aerosol
spray packages. It is a mixture of isobutane and propane
in a proportion to provide a vapor pressure of 46 psig at
70F. The Release Agent is SGOP (that sold under the trade-
mark EMPHOS D70-30C BY Witco Chemical Co.,). The Edible Oil
is a partially hydrogenated canola oil, referred to below as
"PHC".
Ingredients - Percent by Weight of Formula
Edible Oil Release
25Formula PHC Agent Flour
M140D 74.2 2.5 1.5
M140E 67.7 2.5 8.0
M140F 71.7 4.0 2.5
M140G 68.7 6.0 3.5
30 M140H 60.2 6.0 12.0
M140I 54.2 8.0 16.0
M140J 66.2 4.0 8.0
M139A 70.7 2.5 5.0
M139B 65.2 8.0 5.0
B. All Formulas in this Part B contained, in addition
to the below-listed ingredients, 4.0 percent by weight SGOP
-lO- 2027279
as the Release Agent and 1.8 percent by weight Cab-O-Sil
pyrogenic silica as a dispersent, except as otherwise noted
for Formula DllA. The Propellant for all Formulas in Part B
was IP-46. Edible oil SO is soybean oil, PHC is partially
hydrogenated canola oil, CO is corn oil, CA is canola oil;
Blocking Agent FL is flour, CS is cornstarch and BS is
baking soda (sodium bicarbonate). The Release Agent is SGOP
in all cases.
Ingredients - Percent By Weight of Formula
EdibleBlocking
FormulaPropellant Oil Agent Water
D7A 18.0 15.0 SO4.0 FL 57.0
D7C 18.0 15.0 SO4.0 FL 59.0
D8A 30.0 61.2 SO3.0 CS --
D8B 30.0 61.2 SO3.0 BS --
D9A(a)30.0 53.2 SO3.0 FL --
D2A 30.0 61.2 CA3.0 FL --
DllA(b)30.0 61.2 MO3.0 FL --
DllB(C)30.0 57.6 MO3.0 FL ~~
D12A 18.0 30.0 SO4.0 FL 44.0
D12C 18.0 30.0 SO4.0 FL 44.0
D13A 18.0 30.0 SO4.0 BS 42.2
D13B 18.0 30.0 SO4.0 CS 42.2
D14A 30.0 63.2 SO1.0 CS --
D14B 30.0 58.2 SO6.0 CS --
D3A 30.0 61.2 CO3.0 FL --
D4A 30.0 61.2 SO3.0 FL __
D5A 30.0 61.2 CA3.0 FL --
(a) Formula D9A contains, in addition to the listed ingredi-
ents, 8.0 weight percent of 200 proof ethanol.
(b) Formula DllA contains 1.8 weight percent Aerosil pyro-
genic silica as the suspending agent, in place of Cab-O-Sil.
(c) Formula DllB contains 1.8 weight percent Sylox pyrogenic
silica as the suspending agent, in place of Cab-O-Sil.
-11- 2027279
C. All Formulas in this Part C contained PHC as the
edible oil; 30.0 weight percent IP-46 as the propellant in
addition to the other ingredients listed; 1.8 weight percent
Cab-O-Sil as the suspending agent, SGOP as the Release
Agent, and Flour as the Blocking Agent.
Ingredients - Percent by Weight of Formula
PHC SGOP Flour
10Formula Edible OilRelease Agent Blocking Agent
152A 63.70 2.50 2.00
152B 62.70 2.50 3.00
152C 61.70 2.50 4.00
153A 64.20 1.00 3.00
15 153B 63.45 1.75 3.00
D. A11 Formulas in this Part D contained 20.0 weight
percent IP-46 as the propellant; 69.2 weight percent PHC as
the Edible Oil; 5.0 weight percent Flour as the Blocking
Agent and 1.8 weight percent Cab-O-Sil as the suspending
agent, i.e., dispersent. The Release Agent is a combination
of SGOP and a lecithin.
Ingredients - Percent by Weight of Formula
Formula SGOP Lecithin HR2B Lecithin Cent. A
M146A 0.5 3-5 ~~~
M146B 2.0 2.0 ---
M146C 3.5 0.5 ---
30 M145A 0.5 --- 3.5
M145B 2.0 --- 2.0
M145C 3.5 --~ 5
When exposed to higher cooking and baking tempera-
tures, for example, to temperatures of from 400 to 500F,
compositions in accordance with the present invention main-
tain their superior anti-stick characteristics and showed no
-12- 2~2 72 7~
evidence of darkening even when heated to 450F for 20 min-
utes, a test which successful commercial products failed.
Example 2 shows six parting compositions prepared in
accordance with the present invention which include refrac-
tory blocking agents. Refractory blocking agents includeedible clays, such as purified white bentonite, a water-
purified colloidal montmorillonite clay sold under the mark
Polar Gel by American Colloid Company, pharmaceutical grades
of kaolin, such as colloidal kaolin USP sold by Whittaker,
Clark and Daniels, Inc. of South Plainfield, New Jersey,
calcium carbonate (ground limestone) also available from
Whittaker, Clark and Daniels, Inc., sodium bicarbonate,
magnesium aluminum silicate, and the like. Compositions
using such refractory blocking agents show less charring and
darkening when exposed to high temperatures than do other-
wise comparable blocking compositions using non-refractory
blocking agents, e.g., carbohydrate blocking agents such as
flour and starch.
E~ample 2
The Formulas of Example 2 comprise embodiments of the
invention using refractory blocking agents. Each of the
formulas of Example 2 are comprised of 4.0 weight percent
SGOP as the release agent, 66.0 weight percent soybean oil
as the edible oil, and contain 2.0 weight percent Cab-o-Sil
M-5 fumed silica as a dispersant and, together with the re-
fractory blocking agent were formulated in an aerosol con-
tainer with 25.0 percent by weight of IP-46 hydrocarbon gas
propellant. Each of the formulations contained 3.0 weight
percent of a refractory blocking agent, as follows:
Formula Blocking Agent
D-66A Polar Gel purified white bentonite
(American Colloid Company)
D-66C Colloidal kaolin 2457
(Whittaker, Clark & Daniels, Inc.)
-13- 2027279
D-66D Ground limestone, Clavcal 9133
(Whittaker, Clark & Daniels, Inc.)
D-66E Ground limestone, 2933
(Whittaker, Clark & Daniels, Inc.)
D-79C Magnesium stearate
D-79D Calcium stearate
~ample 3 - Comparative For~ulations
Parts A, B and C of Example 3 give comparative formu-
lations which lie outside the scope of the present inven-
tion, either because they employ lecithin in lieu of the
Phosphated Derivative (as defined in the above Summary of
the Invention) or because they do not employ a blocking
agent.
A. All Formulas in this Part A contained 20.0 weight
percent of IP-46 as the Propellant, and PHC (partially
hydrogenated canola oil) as the Edible Oil. Where a Block-
ing Agent is present, it is flour. As to the release
agents, the Phospated Derivative is SGOP, the above-de-
scribed Emphos D70-30C sodium glyceryl oleate phospate;
"Cent. C" is Centrophase C, a lecithin product sold by
Central Soya, Chemurgy Division, Fort Wayne, Indiana; it is
stated by the supplier to contain 52% phospholipids and
47.3% other lipids. Release Agent "3FSB" is available from
the same supplier, Central Soya, and is described as a
natural fluid soybean lecithin. Release Agent "Cent. O" is
"Centrophil", also available from the same supplier, and
described as an oil-free soybean lecithin in selected vege-
table oils (coconut and cottonseed oils) and including
anti-oxidants. "Cent. A" is Centrolene A, a hydroxylated
lecithin sold by Central Soya, a water-dispersible fluid
lecithin which has been modified by hydroxylation. Release
Agent "HR2B" is Centrophase HR-2B, also sold by Central
~r
~.^ ~,...
-14- 2 0 2 72 7 9
Soya, described as a food grade, medium viscosity, highly
filtered, refined fluid lecithin. None of these composi-
tions contains both SGOP and a blocking agent; some contain
neither.
Ingredients - Percent By Weight of Formula
Flour
PHC Release Agent Blocking
FormulaEdible Oil SGOP HR2BCent. A Agent
M147A 69.2 -- 2.0 2.0 5.
M147B 76.0 -- 2.0 2.0 --
M147C 76.0 -- 4.o -- __
M147D 76.0 -- -- 4.0 --
M140A(a)80.0 -- -- ~~ ~~
M140B(a)73.2 -- -- -- 5.0
M140C(a)71.2 4.0 -- -- --
M138D 72.0 8.0 -- -- __
(a)These formulas contain, in addition to the listed ingre-
dients, 1.8 weight percent Cab-O-Sil as a Suspending Agent.
B. All Formulas in this Part B contained IP-46 as the
Propellant; Edible Oil SO is soybean oil, Edible Oil PHC is
partially hydrogenated canola oil; the Release Agent is SGOP
in all cases, in the amount of 4.0 weight percent of the
Formula. Where present, the Suspending Agent is Cab-O-Sil
M-5. No blocking agent was used in these compositions.
Ingredients - Percent By Weight of Formula
Edible Suspending Xanthan
FormulaPropellant Oil Agent Gum
DlOB 30.0 61.2 PHC 1.8 3.0
D12B 18.0 30.0 SO --- ___
D12D 18.0 30.0 SO --- ---
D12E 18.0 30.0 SO --- 4.0
.
20 27279
-15-
D13C 18.0 30.0 SO 1.8 ---
D13D 18.0 30.0 SO 1.8 4.0
D16A 30.0 64.2 PHC 1.8 ---
D16B 30.0 64.2 PHC 4.8 ---
C. All Formulas in this Part C contained IP-46 as the
Propellant in the amount of 20.0 percent by weight of the
Formula except as otherwise noted with respect to Formula
154A; Edible Oil SO is soybean oil, PHC is partially hydro-
genated canola oil, CO is corn oil; and CA is canola oil
(rapeseed oil). None contains a blocking agent.
Ingredients - Percent By Weight of Formula
Release Agent
Formula Edible Oil SGOP Cent. C 3FSB Cent. O
142A 76.0 PHC 0.5 --- 3.5 ---
142B 76.0 PHC 2.0 --- 2.0 ---
142C 76.0 PHC 3.5 --- 0.5 ---
143A 76.0 PHC 0. 5 --- 3.5 ---
143B 76.0 PHC 2.0 --- 2.0 ---
Xc(b) 77.5 SO ___ 1.0 --- ---
XB(b) 75.0 CO --- --- ___ ___
Ml50A(b) 77.5 PHC 2.5 -__ ___ ___
Ml50B 77.5 PHC 2.5 -__ ___ ___
Ml37E( ) 77.5 PHC --- ___ 2.5 ---
(b)Formulas XC, XB and Ml50A each contain silicone DC 200 as
a dispersant in the following amounts, expressed as percent
by weight of the Formula; XC has 0.025 percent; XB has 0.001
percent and M150B has 0.025 percent.
(C)Formula M137E contains, in addition to the listed ingre-
dients, 6.o weight percent of 188 proof ethanol.
Each of the formulations of Examples 1 and 2, com-
prising specific embodiments of the present invention, and
each of the formulations of Example 3, comprising compara-
2027279
-16-
tive formulations, were tested and the results obtained are
set forth in the following Example 4. The comparative com-
positions identified as "Brands" are popular brands of
aerosol-dispensed food-release sprays readily available in
supermarkets and grocery stores.
Example 4
Each of the compositions of Examples l, 2 and 3 were
tested in a cake release test, as follows. Two cupcake pans
were used in the test; one was an aluminum muffin pan having
twelve individual cupcake cavities measuring two inches in
diameter at the top, one and one quarter inches in diameter
at the bottom and three quarters of an inch deep. The se-
cond pan was a steel pan having twelve cavities measuring
two and seven eighths inches in diameter at the top, two
inches in diameter at the bottom, and one and three sixteen-
ths inches deep.
Jiffy Brand White Cake Mix was used in the test. This
is a high sugar cake mix and the cake batter was prepared in
accordance with the package directions by adding whole eggs
and water to the mix and stirring to make the batter. After
making the batter, a group of three cupcake cavities were
sprayed with one test formulation product while the nine
other cavities were covered with a cardboard sheet; then
another test formulation was applied in the next three adja-
cent cavities, and so on. This procedure was continued
until all of the cavities were sprayed or otherwise coated
with a test formulation, giving four products tested in
three different cavities of each pan.
Approximately the same amount of the Jiffy White Brand
Cake batter was then spooned into each cavity and the filled
pans were then put into a pre-heated gas-fired oven and
baked at 350F for twenty minutes. The pans were then re-
moved and allowed to cool at ambient room temperature for
five minutes. The pan was inverted to an upside-down posi-
tion to see if any of the cupcakes fell out, and the results
noted. While inverted, the pan was shaken once to see if
-17- 2027279
additional cupcakes fell out and the results were noted.
The shakes were repeated one at a time until the upside-down
pan was subjected to ten shakes and the number of cakes that
fell out in each shake was recorded. At the end of ten
shakes it was noted how many cupcakes, if any, were not re-
moved by the ten shakes procedure.
Table I of this Example 4 tabulates the results at-
tained by testing the compositions of Example 1, which com-
prise different embodiments of the present invention. Table
II of this Example 4 tabulates the results attained by test-
ing the comparative compositions of Example 2, each of which
lie outside the scope of the present invention. The results
attained are quantified by assessing "points" according to
the total number of shakes required for de-panning of the
cupcakes, as follows. For each cupcake which fell out of
its cavity upon the pan being tipped over, without necessity
of shaking the pan, zero points is charged; if one or more
shakes of the upside-down pan are required to de-pan the
cupcake, one point is assessed for each shake required; if
zo the cupcake was not de-panned after 10 shakes, 15 points are
assessed against that cavity. In the tabulation of Tables I
and II the "Individual Scores, Points" shows the points
assessed to each cavity tested with a particular spray and
the "Average Score" is attained by dividing the sum of in-
dividual points by the number of cavities tested with agiven spray formulation. With this system, a perfect score
with respect to release of the cupcakes is zero, and the
worst possible score is an average of 15 points, which means
that none of the cupcakes was de-panned with ten shakes of
the upside-down pan. Most formulations were tested in three
cavities, some in six and a few in nine; the number of cav-
ities in which a given formulation was tested is indicated
by the number of individual scores reported for that formu-
lation.
202 72 79
-18-
Table I
Results of Release Tests of Compositions of Example 1
Individual Scores,Average Score,
Formula Points Points Per Cavity
M146A 2, 3, 15 6.67
M146B 0, 0, 0; 0, 0, 1 0.17
M146C 0, 0, 0; 1, 1, 1 0.50
M140D 2, 3, 4 3.00
M140E 0, 0, 1 0.33
M140F 0, 1, 1 0.67
M140H 1, 1, 1 1.00
M140H 0, 1, 1 0.67
M140I 0, 0, 1 0.33
M140J 0 0 0 0
M139A 0, 0, 1; 0, 1, 1; 1, 1, 1 0.67
M139B 0, 0, 1 0.33
D7C 3, 3, 3 3.00
D8A 0, 0, 1 0.33
M145B 1, 1, 3 1.67
D3A 0, 0, 0; 0, 0, 1 0.17
D4A 0, 0, 0; 0, 0, 1 0.17
D5A 0, 0, O; 0, 0, 0 -0-
M152A 0, 1, 2 1.00
M152B 0, 1, 1 0.67
M152C 1, 1, 1 1.00
M153A 1, 1, 1 1.00
M153B 1, 1, 1 1.00
M154B 1, 2, 6 3.00
M143C 4, 6, 8 6.00
D8B 0, 1, 1 0.67
D9A 0, 1, 1 0.67
D2A 0, 1, 1; 0, 0, 0; 0, 1, 1 0.44
DllA 0, 0, 0; 0, 0, 0; 1, 2, 15 2.00
DllB 0, 0, 0; 0, 0, 1 0.17
D13B 1, 1, 3 1.33
D14A 1, 1, 1; 1, 5, 15 4.00
--19--
2~2 72 79
Results of Release Tests of Compositions of Example 2
(Refractory Release Agents)
Part B
D-66A 1, 1, 1; 1, 1, 1 1.00
D-66C 1, 1, 1; 1, 1, 2 1.16
D-66D 1, 1, 1; 1, 2, 2 1.33
D-66E 0, 0, 1; 1, 1, 0;
1, 1, 0; 0, 0, 1 0.50
D-79C 0, 0, 0; 0, 0, 0;
O, O, O; O, O, 0 0.00
D-79D 0, 1, 0; 0, 0, 0
0, 0, 0; 0, 1, 0 0.17
Summary of Results of Table I
Compositions
Allof Example 2
Total Points: 192 29
Total Cavities: 189 54
Overall Average Points: 192 = 1.0229 = 0.54
189 54
Table II
Results of Release Tests of Comparative Compositions of
Example 3
Individual Scores,Average Score,
Formulation Points Points Per Cavity
M150A 7, 15, 15 12.33
M150B 2, 3, 3; 5, 6, 15 5.67
M137E 1, 1, 2; 3, 3, 6 2.67
D16A 1, 2, 3; 3, 3, 7 3.17
D16B 2, 3, 3; 8, 10, 15 6.83
M154A 1, 1, 2 1.33
M142A 15, 15, 15 15.00
M142B 15, 15, 15 15.00
~r
-20- 2027279
M142C 15, 15, 15 15.00
M143A 15, 15, 15 15.00
M143B 1, 6, 15 7.33
DlOB 1, 2, 2 1.67
D12B 0, O, 15 5.00
D12D 9, 15, 15 13.00
D12E 1, 5, 15 7.00
D13C 1, 7, 15 7.67
D13D 3, 8, 15 8.67
M147A 15, 15, 15 15.00
Ml47B 8, 15, 15 12.67
M147C 7, 9, 15 10.33
M147D 15, 15, 15 15.00
M140B 4, 15, 15 11.33
M140C 15, 15, 15 15.00
M138D 15, 15, 15 15.00
Brand K 9, 15, 15 13.00
Brand L 9, 15, 15 13.00
Brand H 3, 6, 10 6.33
Brand A 15, 15, 15 15.00
Brand D 0, O, l; 1, 2, 3 2.33
Flour 15, 15, 15; 15, 15, 15 15.00
Vegetable Oil 15, 15, 15; 15, 15, 15 15.00
Unlubricated,
clean cavities 15, 15, 15; 15, 15, 15 15.00
.,~ ~
-21- 2027279
Summary of Results of Table II
All (X)
Total Points: 1779 1509
Total Cavities: 123 105
Overall Average Points: 1779 = 14.46 1509 = 14.37
123 105
(X) = Omitted from these figures are the results of the
tests conducted with cavities coated with flour, with
vegetable oil, and unlubricated cavities.
The results provided by the popular brand food-release
sprays, Brands K, L, H, A and D, are summarized as follows:
Total Points: 149
Total Cavities: 18
Overall Average Points: 149 = 8.28
18
The above tabulated results show that the food-release
compositions of Table I, each of which is an embodiment of
the present invention, were on average dramatically more
effective than those of Table II, each of which is a compar-
ative composition not in accordance with the present inven-
tion. The compositions of Table I show an average point
value of 1.02 points whereas the compositions of Table II
show, even after eliminating the worst results (attained
using only a flour as a release composition, only vegetable
oil as a release composition, and no release composition) an
average of 14.37 points. Even the commercially available
popular brands showed an average point score of 8.28, more
than eight times greater than the average of 1.02 for compo-
sitions (Example 2) in accordance with the present inven-
tion. Compositions in accordance with the present invention
using the refractory blocking agents (clay, limestone, cal-
-
,.. .
-22- 2027279
cium stearate or magnesium stearate) of the D-66 and D-79
series of formulas showed even better results than the other
compositions of the invention, with an excellent average
point score of only 0.54, less than one-fifteenth of the
8.28 average point score of popular brand, commercially
available spray release compositions. The results clearly
show that SGOP when used in combination with a vegetable oil
but without a blocking agent (e.g., Formulas in Parts B and
C of Example 3) does not provide a parting composition which
exhibits satisfactory anti-stick or parting characteristics
as compared to those provided by the compositions of the
present invention. The anti-stick characteristics become
radically more effective only when a release agent in accor-
dance with the present invention, e.g., SGOP, is combined
with a suitable blocking agent in a composition containing
the edible oil. Similarly, the utilization of flour in com-
bination with oil and lecithin but lacking SGOP (Formula
Ml47A of Part A of Example 3) shows only fair to poor anti-
stick characteristics. On the other hand, the combination
of a release agent plus a blocking agent in accordance with
the present invention, and an edible oil, exhibits-superior
anti-stick characteristics as compared to the prior art
compositions.
Example 5
Parting compositions made in accordance with the pres-
ent invention were tested against commercially available,
nationally known food-release compositions, the ingredients
of which, as printed on their labels, are as follows.
Brand A contains two or more of the following vege-
table oils: soybean, coconut, corn, safflower or sunflower;
plus lecithin, beta-carotene, artificial butter flavors, and
propellant.
Brand B contains two or more of the following vege-
table oils: soybean, corn or cottonseed with mineral oil;
plus lecithin, imitation butter flavor, and propellant.
23 2 0 2 7 2 7 9
Brand C contains partially hydrogenated and winterized
soybean oil, coconut oil, lecithin, artificial butter
flavor, beta-carotene, dimethylpolysiloxane (anti-foaming
agent), with propellant.
Brand D contains soybean oil, propellant (isobutane),
hydroxylated lecithin, lecithin, enriched flour, (niacin,
iron, thiamine mononitrate, riboflavin), silicon dioxide,
and tbhq (to insure freshness).
Brand E contains corn oil, lecithin, alcohol, methyl
silicone (for better pan coverage), citric acid (to protect
freshness), and propellant.
Brand F contains vegetable oil, lecithin, concentrated
natural butter flavor, salt, beta-carotene and propellant.
Brand G contains corn oil, grain alcohol, natural
lecithin, and propellant.
Brand H contains corn oil, lecithin, artificial butter
flavor, dimethylpolysiloxane, beta-carotene and propellant.
Brand I contains a blend of two or more of the follow-
ing vegetable oils: soybean, coconut, corn or safflower oilwith lecithin, beta-carotene, imitation butter flavor and
propellant.
Brand J contains a blend of two or more of the follow-
ing vegetable oils: soybean, corn, cottonseed with mineraloil, lecithin, artificial flavor, and propellant.
The propellant in each of the above compositions is
believed to be a hydrocarbon propellant similar or identical
to those used in the Examples of compositions in accordance
with the present invention.
A typical institutional pancake batter, Belgian Waffle
24- 2027279
Base by Superior Coffee and Foods Company, Bensenville,
Illinois, was used for this test. Two skillets were used in
the test; one was heavy aluminum and the other was high
quality stainless steel. Both skillets performed about the
same. Before each test the pans were scoured with Brillo
brand soaped steel wool pads to remove evidence of any
coating, and then the pans were scoured a second time with
A~ax brand scouring powder, rinsed and dried. Little if any
difference in the release characteristics was noted between
spraying the skillets while at room temperature, or while
hot. The skillets were sprayed lightly to just wet the
total cooking surface with the product under test. Batter
was poured in the center of the pan and the pancake was
allowed to fry until the batter surface appeared bubbly. At
this point the pan was tilted and shaken to see if the pan-
cake would slide on the bottom of the pan. If it slid, then
the pan was tossed to flip-turn the pancake. This, obvious-
ly, indicated the desired release characteristics. When the
pancake was done on the flip side, it was slide-transferred
to a plate and additional batter was placed in the pan for
another pancake. No additional spray was applied. This was
continued until either a pancake stuck and could not be
flip-turned, or severe black charring was noted on the pan
cooking surface. If fifteen pancakes were consecutively
flipped without additional spraying or evidence of sticking,
the test was discontinued. The number of pancakes that
could be fried before sticking commenced was noted, as well
as the condition of the pan and the difficulty in cleaning
the used pan. A surface thermometer indicated the pan sur-
face temperature at over 450F but less than 500F during
cooking. This temperature is considered appropriate for
institutional or commercial cooking of pancakes, parti-
cularly when time is a factor.
Test #1: No Lubricant. Batter was added to a hot,
clean, dry skillet with no spray applied. The pancake
immediately stuck tight and was difficult to remove
even with a metal spatula.
-25- 2027279
Test #2: Margarine Lubricant. Batter was added to
a skillet containing a patty of butter flavored mar-
garine. The first two pancakes were removed satis-
factorily, but the third pancake stuck.
Test #3: Comparative Formulations.
Brand A food-release spray: The first two pancakes
were satisfactorily removed, but the third pancake
stuck to the skillet, which darkened and was diffi-
cult to clean.
Brand B food-release spray: Satisfactorily flip-
turned fifteen pancakes, and the skillet stayed
fairly clean and was not too difficult to clean
back to bare metal.
Brand C food-release spray: The first pancake was
satisfactorily removed, but the second pancake
stuck to the skillet.
Brand D food-release spray: Dispensed foam that
splattered when being applied to the skillet. When
hot, the foam turned dark brown around edges of the
pancake. The first three pancakes were satisfactor-
ily removed, and the fourth pancake slightly stuck
on the flip side. The fifth pancake did not stick
tight, but could not be flip-turned and left some
burnt spots on skillet.
Brand E food-release spray: Flip-turned nine pan-
cakes satisfactorily, but the tenth pancake stuck.
The skillet remained clean while frying.
Brand F food-release spray: Satisfactorily flip-
turned twelve pancakes. The skillet appeared fairly
clean, but was very difficult to clean back to bare
metal after use.
-26- 2027279
Brand G food-release spray: Sprayed satisfactorily
onto the skillet. The first pancake was a little
brown around the edges, but release from the skillet
was good. Flip turned fifteen pancakes. Noted
black charred ring on cooking surface of the skil-
let, which was somewhat difficult to clean, although
not as bad as some of the other products tested.
Brand H food-release spray: The first pancake stuck
and the skillet was very hard to clean.
Brand I food-release spray: The first two pancakes
were satisfactorily removed but the third pancake
stuck to the skillet, which stayed fairly clean.
The first pancake cooked very brown.
Brand J food-release spray: Satisfactorily flip-
turned fifteen pancakes. The skillet appeared
fairly clean but was very hard to clean back to bare
metal.
Test #4: Formulation In Accordance With An Embodiment
Of The Present Invention Employing A Non-Refractory
Blocking Agent (Flour).
Formula D2A (Part B of Example l). Sprayed satis-
factorily with some foam on the surface of the
skillet, but no splattering. Satisfactorily flip-
turned fifteen pancakes. The skillet was not brown
or discolored, and was easy to clean back to bare
metal.
Some of the commercially available, well-known prod-
ucts performed quite well, while others left a great deal to
be desired with respect to the anti-stick characteristics
and ease of cleaning after use. Formula D2A in accordance
with the present invention provided excellent anti-stick
characteristics, easy clean-up, and lack of discoloration,
~r
-27- 2027279
performing as well as any, and better than most, of the com-
mercially available sprays.
Test #5: Formulations in accordance with an embodi-
ment of the present invention employing refractory
blocking agents.
Formulas D-66A, D-66C, D-66D and D-66E (Example 2)
were employed in both pancake frying tests as described
above and in waffle-baking tests employing the Superior
Belgian Waffle Base Mix to prepare waffles in a waffle-
baking iron in accordance with the package direction, and in
an egg-frying test. Generally, the formulations of the
present invention utilizing the refractory blocking agents
performed as well as, and, in some cases, significantly
better than the commercially available spray-release compo-
sitions when used in identical tests for pancake frying, egg
frying and waffle baking. For example, in the waffle baking
test Formula D-66A, with a single application, enabled the
cooking and easy removal of two waffles with the third waf-
fle sticking only slightly. The same results were achieved
with Formula D-66C and, with Formula D-66D, the first five
waffles were removed entirely without sticking with a single
application of the Formula. The sixth waffle stuck slight-
ly. Formula D-66E provided good, non-sticking release
through the seventh waffle with a single application of the
Formula. Each of the four Formulas D-66A, C, D, and E per-
formed well in the egg-frying test, the first egg fried
being able to be flipped-turned without a spatula by flip-
ping the frying pan, with a second egg being easily turned
with use of a spatula. All four of the tested Formulas
utilizing the refractory blocking agent cleaned up very
easily, generally better than the commercially available
cooking sprays, enabling cleaning of the cooking utensil
back to the bare metal with a minimum of effort. The
Formula D-66E provided notably easy clean-up.
Formulas D-79C and D-79D (Example 2) were also tested
for use in egg-frying. In a clean, metal frying pan onto
-28- 2027279
which Formula D-79C was sprayed, the first egg fried could
be flipped-turned, i.e., flipped over, in the frying pan. A
second egg fried without re-spraying the pan could not be
flip-turned but was easily removed and turned by use of a
spatula. The results were obtained in an egg-frying test
using Formula D-79D.
Typical pressurized aerosol spray formulas in accor-
dance with the present invention, which includes an aerosol
propellant and provide performance characteristics better
than most commercial aerosol food-release products, include
the compositions A-O of the following Example 6.
Example 6
Formulation
Ingredient A B C
SGOP 1.5% 4.0% 7.0%
Pillsbury XXXX Flour 2.0% 3.0% 9.0%
Cab-o-Sil 0.9% 1.8% 2.3%
Soybean Oil 75.6% 69.2% 53.7%
Hydrocarbon Propellant 20.0% 22.0% 28.0%
1 00 . 0% 1 0 0 . O % 1 00 . O %
Formulation
Ingredient D E F
SGOP 1.5% 4.0% 7.0%
Magnesium or Calcium2.0% 3.0% 9.0%
Stearate
Cab-o-Sil 0.9% 1.8% 2.3%
Soybean Oil 75.6% 69.2% 53.7%
Hydrocarbon Propellant 20.0% 22.0% 28.0%
100 . 0% 100 . 0% 100 . 0%
-29- 2027279
Formulation
Ingredient G H
SGOP 1.5% 4.0% 7.0%
Corn Starch 2.0% 3.0% 9.0%
Cab-o-Sil 0.9% 1.8% 2.3%
Soybean Oil 75.6% 69.2% 53.7%
Hydrocarbon Propellant 20.0% 22.0% 28.0%
100 . 0% 100 . 0% 100 . 0%
Formulation
Ingredient J K L
SGOP 1.5% 4.0% 7.0%
Pillsbury XXXX Flour 3.0% 3.0% 3.0%
Cab-o-Sil 0.9% 1.8% 2.3%
Soybean Oil 18.0% 30.0% 42.0%
Hydrocarbon Propellant 20.0% 22.0% 22.0%
Water 56.6% 39.2% 23.7%
100.0% 100.0% 100.0%
Formulation
Ingredient M N O
SGOP 1.5% 4.0% 7.0%
Pillsbury XXXX Flour 2.0% 3.0% 9.0%
Cab-o-Sil 0.9% 1.8% 2.3%
Soybean Oil 67.6% 61.2% 45.7%
Hydrocarbon Propellant 20.0% 22.0% 28.0%
Ethanol 8.0% 8.0% 8.0%
100 . 0% 100 . 0% 100 . 0%
The aerosol Formulas of this Example 6 exhibit no
foaming when sprayed according to directions for use, al-
though some foaming may occur when excessive amounts are
sprayed onto the surface of the cooking utensil. If foaming
presents a problem, the addition of alcohol (ethanol) to the
-30- 2~27279
Formulas will radically reduce their foaming characteris-
tics. Ethanol should be added in an amount of from about
2.0% to about 14.0%. The performance of the product will
not be altered by addition of ethanol in these amounts.
The combination of SGOP and flour can be packaged for
marketing as a liquid for application by cloth, brush,
sponge of the like, as a pump spray, aerosol spray or for
use in any dispensing mechanism that will provide a thin
film of the Formula on the surface of the utensil, e.g.,
baking or frying pan. An oil based concentrate formula
could be prepared as follows:
Example 7
SGOP from about 2% to about 8%
Flour from about 1% to about 12%
Suspending Agent from about o.8% to about 2.5%
Vegetable Oil from about 77.5% to about 96.2%
A formulation intended for use as an aerosol spray
product would include the concentrate of Example 5 plus from
about 12% to about 35% of a suitable propellant. The pro-
pellent would consist of one of, or an appropriate blend of,
propane, isobutane or n-butane, to provide a pressure of
about 20-50 psig at 70F. Soluble, non-liquifiable propel-
lants such as nitrous oxide or carbon dioxide could be used
to pressurize the container to about 100 psig at 70F.
Water-based emulsion formulations could be prepared as
follows:
E~ample 8
SGOP from about 2% to about 8%
Flour from about 1% to about 12%
Vegetable Oil from about 12% to about 50%
Water from about 27.5% to about 60%
Suspending Agent from about 0.8% to about 2.5%
-31- 2027279
Preparation of the formulation of Example 7 as an aer-
osol spray product would call for the addition of a propel-
lent as described above.
As indicated by the above formulation, the composi-
tions of the invention may include other usual and desirable
additives, in particular, the addition of a suspending agent
such as a micronized or fumed amorphous silica or similar or
comparable suspending agents is useful, especially when com-
positions in accordance with the present invention are for-
mulated as emulsion products with water and oil.
While the invention has been described in detail with
respect to specific preferred embodiments thereof, it will
be understood that upon a reading of the foregoing descrip-
tion, variations to the specific embodiments disclosed may
occur to those skilled in the art and it is intended to in-
clude such variations within the scope of the appended
claims.
