CA1151466A - Low-fat, butter-flavored spread and process - Google Patents
Low-fat, butter-flavored spread and processInfo
- Publication number
- CA1151466A CA1151466A CA000365992A CA365992A CA1151466A CA 1151466 A CA1151466 A CA 1151466A CA 000365992 A CA000365992 A CA 000365992A CA 365992 A CA365992 A CA 365992A CA 1151466 A CA1151466 A CA 1151466A
- Authority
- CA
- Canada
- Prior art keywords
- fat
- butter
- low
- emulsion
- flavored
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
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Classifications
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
- A23D7/00—Edible oil or fat compositions containing an aqueous phase, e.g. margarines
- A23D7/01—Other fatty acid esters, e.g. phosphatides
- A23D7/011—Compositions other than spreads
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
- A23D7/00—Edible oil or fat compositions containing an aqueous phase, e.g. margarines
- A23D7/005—Edible oil or fat compositions containing an aqueous phase, e.g. margarines characterised by ingredients other than fatty acid triglycerides
- A23D7/0053—Compositions other than spreads
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
- A23D7/00—Edible oil or fat compositions containing an aqueous phase, e.g. margarines
- A23D7/015—Reducing calorie content; Reducing fat content, e.g. "halvarines"
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Polymers & Plastics (AREA)
- Edible Oils And Fats (AREA)
- Coloring Foods And Improving Nutritive Qualities (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A low-fat, butter-flavored spread comprises: a dispersed phase comprising from 5 to 40% fat, based on the weight of the spread; a continuous aqueous phase including a stabilizer; and an emulsifier system comprising a combination of a lipophilic emulsifier and a hydrophilic emulsifier; the relative and total amounts of the emulsifiers and the stabilizer being effective to provide a stable emulsion and a product which is solid at 40°F. A process for preparing the spread is also disclosed.
The product realistically simulates the flavor, texture, mouth-feel, appearance, and stability of butter, yet reduces the calo-ric density by from 50 to 90%.
A low-fat, butter-flavored spread comprises: a dispersed phase comprising from 5 to 40% fat, based on the weight of the spread; a continuous aqueous phase including a stabilizer; and an emulsifier system comprising a combination of a lipophilic emulsifier and a hydrophilic emulsifier; the relative and total amounts of the emulsifiers and the stabilizer being effective to provide a stable emulsion and a product which is solid at 40°F. A process for preparing the spread is also disclosed.
The product realistically simulates the flavor, texture, mouth-feel, appearance, and stability of butter, yet reduces the calo-ric density by from 50 to 90%.
Description
l~S146~
The present invention relates to low-fat content, butter-flavored spreads which simulate the flavor, texture, mouthfeel, appearance, and stability of butter and margarine. More particu-larly, the present invention relates to diet products of this type having a reduction in caloric density of from 50 to 90%, and to processes for preparing them.
The art is replete with prior art attemptS to provide low-fat butter or margarine substitutes. Among these is U.S.
3,457,086 to Josefowicz, et al. which teaches the production of a protein-free spread which can contain as low as 35% fat.
The patent states that observance of specified conditions is necessary to maintain the emulsion in the water-in-oil form.
Unfortunately, products of this type tend to have a watery flavor because of their high water contents and the absence of milk proteins which help impart the desirable butter-like taste of margarine or butter, but which cannot be tolerated in the product because of their emulsion de-stabilizing effect. Moreover, the high water contents tend to make emulsions of this type rapidly break down on hot foods, tending to make foods like toast become soggy and unappetizing. Also, while some consumers have found it convenient to buy large quantities of margarine or butter at sale prices and then freeze them, low-fat spreads based on water-in-oil emulsions cannot tolerate freezing. Upon thawing, the emulsion breaks down with consequential release of its water phase.
Some recent patents suggest that water-in-oil emulsions can be formed with fat contents as low as 25 or 30% to success-fully simulate butter or margarine. This has always presented~
severe problems because the external fat phase tends to become -stretched out and the aqueous phase becomes more predominant.
A ~
SlSl~i~i For example, U.S. 4,103,037, to Bodor et al. discloses a processfor preparing a proteinaceous low-fat spread which is stabilized by a gelling agent, such as gelatin, having ~ melting point sufficiently high to withstand room temperature yet low enough to allow it to melt in the mouth. This gelling agent ties up all available water into minute solid particles which are dispersed throughout a continuous fat phase. These meltable particles contain the water soluble flavors and salt, and further diminish the flavor impact of these components which are already diminished due to the nature of the water-in-oil emulsion.
The adverse effect of water-in-oil emulsions on flavor impact is so pronounced that this is the problem which was dealt with by Moran in U.S. 4,115,598. Therein, flavor impact for a low-fat spread comprising 35 to 65% by weight of a continuous fat phase and dispersed aqueous phase is said to be improved by specially formulating the water-in-oil emulsion to destabilize in the mouth to release the water-soluble flavors.
Further representative of the state of the art of low-fat spreads is U.S. 4,071,634 to Wilton et al. This patent states that low-fat spreads are generally emulsions of the water-in-oil type and cap have fat contents reduced to as low as 30%, as compared to 80% for margarine~ It is indicated that problems related to inferior organoleptic properties or emulsion stability are often encountered in these types of products. Apparently, products of this type which are sufficiently stable, have flavor release problems; while those with good flavor release, are in-sufficiently stable to keep the aqueous phase adequately dis-persed under storage conditions. To remedy this problem, Wilton et al. propose a complex emulsion wherein a discontinuous aqueous li5~gSlI
phase contains phosphatides and a discontinous, second fatty phase dispersed therein.
Among other attempts to provide low-fat spreads is the approach described by Nijhoff in U.S. 3,418,133. Therein, edible spreads are described wherein a portion of a fat content is replaced by an aqueous solution of carboxyme~hyl-ceLlulose.
In Example 2, a margarine substitute is described which is pre-pared from a 50/50 mixture of margarine and aqueous solution.
This product presumably has a fat content of about 40% (i.e., one half that of margarine~; however, the type of emulsion is not identified and the emulsions do not remain stable and solid at room temperature.
U.S. 3,809,764 to Gabby et al. discloses essentially fat-free products which are characterized as "emulsions" of poly-glycerol fatty est,ers with an aqueous hydrophilic colloid. Among the products, are those which are said to simulate margarine yet contain fat contents of less then 5%. These products, while fairly flavorful and fat mimetic, are significantly different in overall flavor, texture, mouthfeel, and appearance from either margarine or butter.
Richardson, in U.S. 4,156,021, also discloses low-fat compositions said to simulate margarine. Example III of this patent employs about 7% corn oil. The emulsions are said to be of the oil-in-water type but obtain much of their body from high levels of cellulose fiber, which also adds its characte-ristic impact on mouthfeel which is significantly different from that of fat.
Other workers have disclosed stable emulsified products containing oil-in-water emulsions, wherein sugars where employed;
however, the necessity for sugar made them sweet and clearly 115~,46d distinct from butter or margarine. Among these is U.S. 3,958,033 to Sims et al. which relates to shelf-stable, clear, liquid emul-sions. The sugar was essential in these formulations to supply the desired sweetness, adjust the refractive index of the aqueous phase to improve product clarity, and enhance shelf stability.
Similarly, in U.S. 4,146 652, Xahn et al. describe stable oil-in-water emulsions containing high sugar levels to obtain micro-biological stability. In U.S. 4,107,343 to Petricca the sugar was required for sweetness demanded of the whipped products invol-ved. Thus, despite the disclosure by these patents of stableoil-in-water emulsions with fat contents in the 10 to 30% range, and the disclosure by Sims et al. in Example XXII of a maple-flavored spread, and a confectionary butter cream in Example I of Kahn et al., there is no solution afforded the skilled worker in the low-fat margarine or butter substitute art seeking a pro-duct which can successfully reproduce the flavor, texture, mouth-feel, stability and appearance of butter or margarine at a calo-ric density of 10-45 colories per 14 gram serving, as compared to the 50 or more calories per similar serving for the best low-fat, butter-flavored spreads commercially available to date.
It is an object of the present invention to provide an improved low-fat, butter-flavored spread and a process for preparing it.
According to an aspect of the present invention there is provided a low-fat, butter-flavored spread comprising, a dis-persed phase comprising from 5 to 40% fat, based on the weight of the spread, a continuous aqueous phase including a stabilizer, and an emulsifier system comprising a combination of a lipophilic emulsifier and a hydrophilic emulsifier, the relative and total amounts of the emulsifiers and the stabilizer being effective llS14~;~
to provide a stable emulsion and a product which is solid at 40F.
According to a further aspect of the present invention there is provided a process for preparing a low-fat, butter-flavored spread, which comprises, preparing an oil-in-water emul-sion comprising a dispersed phase comprising from 5 to 40~ fat, based on the weight of the emulsion, a continuous aqueous phase including a stabilizer, and an emulsifier system comprising a combination of a lipophilic emulsifier, and a hydrophilic emulsi-fier, the relative and total amounts of the emulsifiers and thestabilizer being effective to provide a stable emulsion and a product which is solid at 40F, and cooling the emulsion under conditions effective to solidify it to form a product which is solid at 40F.
Embodiments of the invention will now be described by way of example with reference to the accompanying drawings in which:
Figure 1 is a photomicrograph, taken at 225 times magni-fication, of an emulsion sample as described herein after solidi-fication;
Figure 2 is a photomicrograph of the sample of Figure1, taken at 500 times magnification; and Figure 3 is a flow diagram showing a preferred process scheme according to the invention.
The products described herein, which are prepared by the process described herein, effectively simulate natural butter and good quality margarine in flavor, texture, appearance, mouth-feel and stability, yet have caloric densities of less than 50, and preferably about 10 to 35, colories per 14 gram serving com-pared to about 100 for margarine and butter. The spreads are .' ~`
~151~*0 solid at refrigerator temperature and remain so even after stand-ing for at least 2, and preferably 5, hours at a room temperature of 70F. The spreads, which are based on stable oil-in-water emulsions, remain spreadable at normal refrigerator temperature, and melt quickly in the mouth to release flavor without imparting a waxy texture or mouthfeel.
The term "butter-flavored" is meant to include composi-tions flavored to simulate butter by both naturally-derived and simulated butter flavors. This term is used in its literal sense and is not meant to be otherwise restricted. A composition is considered "butter-flavored" when an expert panel trained to evaluate flavors of this type characterizes the product as "buttery" or "butter-like" in flavor.
The term "stable emulsion" identifies those emulsions which do not undergo any noticeable change in stability, due to water or fat separation or otherwise, during storage in mois-tureproof containers at a temperature of 40F or below for 6 months, and which will also remain stable when stored at a room temperature of 70F for a period of at least one day. Preferably, the emu~sions described herein remain stable after melting, even at elevated temperatures of 180F or more.
The term "solid" is used in its normal sense, to mean the product does not flow under its own weight. Included within the scope of this term are plastic, spreadable compositions which, while not susceptible to flow under their own weight in small quantities, are easily spread with a knife. The more realistic-appearing products described herein will exhibit penetrometer readings at 40F within the range of about 60 to 250 units, using a standard penetrometer cone, having a 2.5 inch diameter and a 45 angle, with 47.5 grams added weight at a S-second interval.
: -~S~.466 Preferably, the penetrometer readings will be within the rangeof from 100 to 200 units.
The products described herein can be aerated if desired;
however, it is an advantage that the products do not have to contain any significant quantity of air or inert gas to stiffen their structures and provide a firmer consistency. Thus, unlike many prior art products, the product itself, probably due to its unique microstructure, provides the solid consistency and there is no dependence upon the use of a gas to distend the emul-sion structure to effect stiffening or solidification. To provide the best overall texture, the degree of gas incorporation is preferably kept to less than 40%, and more preferably less than 20~, by volume.
Similarly, in distinction with some of the prior art compositions, those described herein do not depend upon the pre-sence of protein to obtain the solid texture or the superior mouthfeel; however, they can contain proteins if aesired.
Figures 1 and 2 are photomicrographs taken of a repre-sentative emulsion prepared in Example 1. Figure 1 was made 20 at 225 times magnification and Figure 2 was made at 500 times.
Both show the unique microstructure of the product. It is believed that the chains of small bead-like oil droplets entangle, or coalesce or fuse at points, to form small interstices wherein the aqueous phase is physically trapped as well as being bound to some extent by the attraction for the oil due to the presence of the emulsifiers and stabilizers. The thickened state of the aqueous phase contributed by the stabilizers is also believed to aid in maintaining the unique solid structure of the products described herein, even though the degree of thickening would not itself be sufficient to prevent it from flowing were it not r~
~lS14~i6 for the other effects of the composition described herein. These products are so stable that the emulsions do not separate even after standing for 24 hours or more at room temperature.
The ingredients which are essential to the formation of the product are: (1) fat which is suitably selected to have a Solids Fat Index (SFI~ which enables the formation of solid product at 40F, ~2~ a water-soluble emulsion stabilizer, and (3) an effective emulsifier system comprising both lipophilic and hydrophilic emulsifiers.
The fat can be present in amounts within the range of from 5 to 40 percent based on the weight of the spread, but is preferably present in an amount of from 10 to 30 percent by weight of the spread.
The term "fat" as used herein is intended to include all edible, fatty acid triglycerides regardless of origin or whether they are solid or liquid at room temperature. Thus, the term "fat" includes normally liquid and normally solid vege-table oils and animal fats. Typical of the vegetable oils which are included are the usual vegetable oils such as soybean oil, corn oil, coconut oil, cottonseed oil, peanu$ oil, safflower oil, palm kernel oil, sunflower oil, palm oil, and rapeseed oil.
The preferred fats for use herein will comprise partially hydro-genated vegetable oils, and will most preferably be selected from the group consisting of soybean oil, corn oil, coconut oil, cottonseed oil, peanut oil, palm oil, palm kernel oil, safflower oil, sunflower oil, rapeseed oil, and mixtures of these. Pre-ferred among these are thosepartially-hydrogenated vegetable oils which have an SFI profile within the following ranges.
'~
11S~466 .
Temp. BroadPreferred 50F 40-80% 50-70~
70F 25-50% 30-40%
92F <10~ ~5~
Particular, suitable fats are 92F Wiley melting point partially-hydrogenated coconut oils sold under the trade marks PURECO 92 by Capitol City Products; HYDROL 92 by SCM Corporation;
VICTORY 92 by Humko Div. Kraft Inc.; and COBEE 92 by PVO Inter-national, Inc.
The fat will preferably be selected to provide a solid product at 70F, but will substantially completely melt in the mouth. Where necessary to increase the solids content at 40F
or 70F, an amount of a fat having a higher solids content can be added. Fats like hard stock stearin and cottonseed or soybean flakes have this ability, however, they remain solid and impart a waxy mouthfeel at eating temperature. Thus, while they can be employed to provide a desirable effect on texture, they should not be employed in large amounts.
The use of water-soluble emulsion stabilizers is essen-tial to provide the necessary stability. These can be any of , those known to the art for this purpose and will preferably behydrophilic colloids, and can be selected from the group consis-ting of microcrystalline cellulose, carageenin,. guar gum, algi-nate, xanthan gum, methyl cellulose, carboxy-methyl cellulose, ethyl cellulose, hydroxypropolymethyl cellulose, dextrins, starch, gelatin, locust bean gum, soy protein isolate, pectin and the like, and mixtures of these. Commercial stabilizers available from Polak's Frutal Works, Inc. and identified by the manufac-turer under the trade marks FRIMULSION Q8 and FRIMULSION 10 have been found effective, especially when used in combination. The g _ 11514~
Q8 product is a blend of modified food starch, locust bean gum, guar gum, gelatin and pectin, and is preferably employed at a weight ratio within the range of from about 1:1 to 3:1 to the FRIMULSION 10 which is a blend of locust bean gum and guar gum.
The stabilizer can be employed in any amount effective under the conditions of processing and with the particular ingre-dients. It has been found, however, that levels of abou-t 0.1 to 3.0 percent, based on the total weight of the cbmposition, are particularly effective. In addition to their emulsion sta-bilizing function, these materials also,have a viscosity-increasing effect on the emulsion. However, this effect is not sufficient in and of itself to con~rol the large amounts of water present in these emulsions. Thus, the compositions described herein, unlike the approach taken by Bodor et al. in U.S.
4,103,037, do not depend upon a gelling agent to solidify the aqueous phase.
The compositions described herein further comprise an emulsifier system employing both lipophilic and hydrophilic emulsifiers. The relative and total amounts of the emulsifiers are selected to be effective to provide a stable emulsion and a product which is solid at 40F. Typical of effective levels will be levels of from 0.3% to 4.0~, based on the weight of the total composition of the total emulsifier system which employs each of the hydrophilic and lipophilic emulsifiers at levels of at least 0.05%, on the same basis. The lipophilic emulsifier will typically have an HLB (hydrophile-lipophile balance), of less than 7, and the hydrophilic emulsifier will typically have an HLB of from 10 to 20, preferably from 11 to 17.
The emulsifier system is preferably present at a level of from 0.5% to 2~, and the lipophilic and hydrophilic emulsifiers Al i llS1466 are preferably each present at levels of at least 0.10%, all percentages on a formula weight basis.
The hydrophilic emulsifier will preferably comprise a member selected from the group consisting of polyoxyethylene (20) sorbitan monostearate, polyoxyethylene (20) sorbitan monoo-leate, and mixtures of these.
These emulsifiers, commonly known as polysorbate 60 and polysorbate 80, respectively, are preferred, however, it is believed that other hydrophilic emulsifiers with an HLB of between 10 and 20, preferably between 11 and 17, and most prefer-ably 13 and 16, will be operable. Among other suitable emulsi-fiers are the polyglycerol esters of fatty acids, such as octa-glycerol monooleate. Also suitable are other polysorbates, such as polysorbate 65 which is otherwise known as polyoxyethylene (20) sorbitan tristearate. Various factors such as off-flavor, off-color and generally less desirable qualities of these other materials for use in foods make the aforementioned hydrophilic emulsifiers the most desirable choice. Polysorbate 60 and 80 are the most preferred because they provide a stiffness and spreading quality, especially a cold fracture quality, most like butter and margarine.
Polysorbate 60, polyoxyethylene (20) sorbitan mono-stearate, is a mixture of stearate and palmitate partial esters of sorbitol and sorbitol anhydrides condensed with approximately 20 moles of ethylene oxide (C2H4O) for each mole of sorbitol and its mono- and dianhydrides. It is a lemon to orange colored, oily liquid or semi-gell having a faint characteristic odor and a warm, somewhat bitter taste. It is soluble in water, aniline, ethyl acetate, toluene, and is soluble at low levels in mineral and vegetable oils. Polysorbate 60 is commercially available li5146~
under the trade marks TWEEN 60 from ICI-Atlas, SVS-18 from Hodag, Inc., DREWPONE 60 from PVO International Inc., DURFAX 60 from SCM Corporation, and GYSPS-20 from Glyco, Inc.
Polysorbate 80, polyoxyethylene (20) sorbitan mono-oleate, is a mixture of oleate partial esters of sorbitol and sorbitol anhydrides condensed with approximately 20 moles of ethylene oxide (C2H4O) for each mole of sorbitol and its mono-and dianhydrides. It is a yellow to orange colored, oily liquid having a faint, characteristic odor and a warm, somewhat bitter taste. It is very soluble in water, producing an odorless, nearly colorless solution, and is soluble in ethanol, fixed oils, ethyl acetate and toluene. Polysorbate 80 is commercially available under the trade marks TWEEN 80 from ICI-Atlas, SVO-9 from Hodag, Inc., DREWPONE 80 from PVO Internatlonal Inc., DURFAX 80 from SCM Corporation and GYSPO-20 from Glyco, Inc.
Polysorbate 65, polyoxyethylene (20) sorbitan tristear-ate, is not as preferred as polysorbate 60 or polysorbate 80, but still provides an acceptable product. It is a mixture of steareate and palmitate partial esters of sorbitol and its anhy-drides condensed with approximately 20 moles of ethylene oxide (C2H4OI for each mole of sorbitol and its mono- and dianhydr~ides.
It is a tan, waxy solid having a faint, characteristic odor and a waxy, somewhat bitter taste. It is soluble at low levels in mineral and vegetable oils; at higher levels in mineral spirits, acetone, ether, dioxane and methanol; and is dispersible in water and carbon tetrachloride. Polysorbate 65 is commercially avail-able under the trade marks TWEEN 65 from ICI-Atlas, DREWPONE
65 from PVO International, Inc., DURFAX 65 from SCM Corporation, and GYSPTS-20 from Glycol, Inc.
The lipophilic emulsifier of the emulsifier system ~1 lS14fi6 will preferably comprise a member selected from the group consist-ing of mixed fatty acid monoglycerides; mixed fatty acid digly-cerides; mixtures of fatty acid mono- and diglycerides; lipo-philic polyglycerol esters; glycerol esters, such as glyceryl monooleate, glyceryl dioleate, glyceryl monostearate, glyceryl distearate, glyceryl monopalmitate and glyceryl dipalmitate;
lactylated esters such as glyceryl-lacto esters of fatty acids;
propylene glycol esters such as propylene glycol monopalmitate, propylene glycol monostearate and propylene glycol monooleate;
sorbitan esters such as sorbitan monostearate, sorbitan trioleate, sorbitan tripalmitate, sorbtian tristearate and sorbitan sesqui-oleate; fatty acids or their soaps such as stearic acid, palmitic acid and oleic acid; and mixtures thereof. Here, as in the case of the hydrophilic emulsifier, there is no known criticality in the use of any particular lipophilic emulsifier. Thus, it is fully intended that other equivalent materials can be employed with statisfactory results. However, those specifically identi-fied above, especially those selected from the group consisting of lipophilic polyglycerol esters, mono- and diglycerides, propy-lene glycol esters, lactylated esters, and mixtures of these,are preferred from the stand point of taste and effectiveness.
The products described herein will most closely simulate butter and margarine when they are suitably colored and flavored with those materials known to the art for these purposes. Exam-pleas of coloring agents are beta carotene, annatto, turmeric, paprika and FD~C dyes. Typically, the colors will be dissolved or dispersed in oil or the water phase to expedite blending.
Representative of the flavors and/or flavorenhancers will be sodium chloride; lactones; lipolyzed butter oils and starter distillates; diacetyl, 2-octanone, and other ketones; butyric ~ 13 -~1 11514~fi acid; hexanoic acid and other free fatty acids; esters of butyric acid; delta-hydroxy acids and their glycerol esters; and mixtures of any of these with other known dairy, buttery, or like flavors or flavor notes. It is an advantage of the products described herein that flavors have a very pronounced impact as compared to prior art water-in-oii compositions.
In addition to emulsion stability, the products describ-ed herein are preferably stable against microbiological and oxi-dative deterioration. To control mold and yeast growth, the products preferably contain one or more preservatives such as benzoic acid, sorbic acid, phosphoric acid, lactic acid and the soluble salts of these and other like materials. Preferred as antimicrobiais are potassium sorbate, sodium sorbate, potassium benzoate, sodium benzoate and phosphoric acid. The pH of the aqueous phase is preferably maintained at a value below 6.0, and more preferably within the range of 5.0 to 5.9, to provide effective microbial control and good flavor with the lowest neces-sary levels of preservatives. Addtional stability against oxida-tive deterioration at higher temperatures may be obtained by the use of the usual antioxidants, typical among which are normal propyl gallate, the several tocopherols, butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), nordihydroguaiaretic acid (NDGA), tertiary-butylhydroquinon (TBHQ) and citric acid.
While the products described herein do not require proteins to obtain the proper texture or mouthfeel, they are sometimes desired for nutritional reasons as well as their posi-tive contribution to the flavor and physical properties of the product. Additionally, protein can enhance freeze/thaw stability.
Among the suitable protein materials are any of those known to the art for similar uses in margarine and margarine substitutes.
These can include those derived from vegetable as well as animal ~l " 115~46~
-sources. Thus, vegetable protein isolates such as ~hose derived from soy, peanut, cottonseed, alfalfa, pea and the like; milk-protein containing materials such as non-fat dry milk, whey, caseinates, casein and delactosed whey; and other proteins, can be employed in desired amounts. One suitable type of protein is that sold under the MELOTEIN MP-14P trade mark by Dairyland, Inc. These products are spray dried blends of milk proteins such assweet dairy whey and caseinates. Typically, they are added in amounts of up to 10~ based on the total weight of the spread. Preferred levels will be from 1 to 8~ on this basis.
Also added can be any of the vitamins and minerals desired. Preferred among these are vitamins A and D which are normally associated with butter or margarine products. If desir-ed, these can be added in amounts approximating those in butter or margarine.
Also where desired, a chelating agent such as ethylene-diaminetetraacetic acid (EDTA), its salts, such as calcium diso-dium EDTA or the like can be employed to tie up metal ions which may otherwise detrimentally interact with one or more of the ingre-dients.
All of the above ingredients can be formed into the low-fat, butter-flavored spread described herein by following the preferred processscheme set out in Figure 3, or otherwise preparing an oil-in-water emulsion comprising the essential ingre-dients, and then cooling the emulsion under conditions effective to solidify it and forma spread which is solid at 40F, prefera-bly at 70F, and most preferably at 75F.
The flow diagram of Figure 3 shows the separate prepa-ration of fat and aqueous phases prior to blending and emulsi-fying them. The water and water-soluble ingredients, such as ,~1 11514~6 milk protein solids, salt and preservatives, are added to mixing vessel 10 by lines 12 and 14, respectively. The vessel may be equipped with a suitable heater 16 which can be an electrical resistance heater, a water or steam jacket or the like. Alter-natively, the water from line 12 can be supplied hot. Typically, the water will be heated to a temperature of about 190F to assure complete hydration of the water soluble materials added.
Agitation is supplied by mixing device 17. Where the stabilizers, which are water soluble, are mixed with the water at this stage ln processing, the shear supplied by the mixing must be intense enough to overcome the normal tendency of these materials to clump together and prevent complete hydration and dispersion.
It is preferred, however, to predisperse the stabilizers in a portion of the fat phase prior to contact with water. This can be accomplished by blending with mixing device 18 in vessel 19, and then passing to vessel 10 by line 20.
The fat phase is prepared in a separate vessel 21 which can also be equipped with a suitable heating device 22 and mixing device 24. The fat-soluble materials such as the color, flavor, vitamins and emulsifiers, if desired, are added at 26 to the fat which is added at 28. The hydrophilic emulsifier will prefer-ably be added to the water phase instead of the fat phase. The fat is maintained at a temperature high enough to assure its liquid character. Temperatures of from about 120 to 190F, pre-ferably about 130 to 150F, are effective to provide good solubi-lity of additives and a suitably low viscosity.
The fat phase can be drawn from mixing vessel 21 by line 30 and then passed to vessel 35 wherein it i3 mixed with the water phase which is supplied by line 36 and may have been cooled to approximately the same temperature as the fat phase by means of heat exchanger 38. Adequate mixing is provided by device 40 which supplies sufficient shear to begin the emulsifi-cation of the fat lnto the water. At the completion of mixing, an emulsion will have been formed which uniformly disperses the fat into droplets within the aqueous phase; however, the droplets are not broken down finely enough to permit emulsion stability.
The rough emulsion prepared in vessel 35 is then passed via line 42 to homogenizer 44 wherein the final emulsion is form ed. The emulsion will, at this point, still be at a temperature sufficiently high to maintain the fat in the liquid state. Homo-genization will typically be accomplished at a pressure of from 100 to 500, and preferably about 250, atmospheres. Any of the typical homogenizers or colloid mills effective for dairy purposes can be employed in this process. Thus, the Manton-Gaulin 2-stage homogenizer or the Cherry Burrell 2-stage homogenizer can be employed effectively.
From the homogenizer 44, the homogenized emulsion is passed via line 46 to a suitable heat exchanger 48 where it is cooled. The heat exchanger 48 will preferably be of a kind capa-ble of rapidly cooling the emulsion. Typical of the suitable devices are scraped-wall heat exchangers ("A" units), such as those sold under the VOTATOR trade mark. Typically, the heat exchange~ coolant will be maintained at a temperature of about -20F to cool the emulsion rapidly from about 140 to 160F to below about 70F, and preferably below about 40F.
The cooled emulsion is then preferably passed from the heat exchanger 48 via line 50 to a mixing chamber 52 wherein gentle agitation is maintained internally by a suitable rotating mixing device 54 for a period of time effective to initiate crys-tallization of the fat and the propagation of the unique physical A
" ~lSi46i~
structure of the product described herein. The agitation promotes crystalli~ation and enhances solidification. According to the most preferred mode of operation, a series, preferably about three, "A" units cool the emulsion, and a blender ~"B" unit) is positioned at the end of the series, or between two of the "A" units in the series, to aid in promoting crystallation.
The spreads described herein can be printed into sticks, formed into pats or filled into tubs. Thus, these spreads, des-pite their low fat contents and high water contents, have the physical appearance, as well as other characteristics, of high quality margarine or butter.
The following examples are presented for the purpose of further illustrating and explaining the present invention and are not to be taken as limiting in any regard. ~nless other-wise indicated, all parts and percentages will be by weight.
Example I
This example describes the preparation of a preferred spread as described above and details the procedure for obtaining the microphotographs shown in Figures 1 and 2.
The spread was made from the following materials which were employed in the amounts listed:
A~
~1S146~;
Amount Ingredients Iparts by wt.) Coconut oil, 92F Wiley melting point l9.0000 Mono- and diglycerides(a) 0.5000 Polyso~bate 60(b) 0-5000 Beta carotene (30% in oil) and vitamins 0.0050 Salt 1.6500 Butter flavor 0.0200 Stabilizer(C) 1.0000 Stabilizer(d) 0~4000 Water 76.6743 Potassium sorbate 0.1300 Sodium Benzoate 0.1000 Phosphoric acid 0.0150 Calcium disodium EDTA 0.0057 (a) DUREN 114 (b) DURFAX 60 (c) FRIMULSION Q8 (d) FRIMULSION 10 An aqueous phase was prepared by heating the water to 190F and adding the dry ingredients, and the FRIMULSION
Q8 and 10 stabilizers predispersed in a portion of the melted fat, to it with agitation. Mixing was continued until the stabi-lizers were uniformly dispersed and hydrated.
A separate fat phase was prepared by melting the remain-ing portion of the fat and the emulsifiers at a temperature of about 150F. The color and flavor were then admixed with the melt to obtain a uniform blend.
The aqueous and fat phases were then blended at about * A trade mark - 19 -i~S1466 ;
160F to provide an emulsion. The emulsion was then homogenized in a Gaulin Laboratory homogenizer, Model 15M, set at 150 atm.
first stage and 100 atm. second stage.
The emulsion was then cooled to 40F in about 15 min-utes by slowly agitating with a Hobart Modei N50 mixer fitted with a wire whip and a jacketed (water/alcohol coolant at appro-ximately -20F) 5-quart mixing bowl. The resulting product was transferred to a tub and refrigerated for 24 hours. The result-ing solidified spread exhibited a penetrometer reading of 130 10 units when measured by a Krebs Penetrometer with a standard pene-trometer cone having a 2.5 inch diameter and a 45 angle, with 47.5 grams added weight at a 5-second interval. ~Penetrometer procedures according to ANS/ASTM D217-68).
The spread was prepared for microphotography by placing a very small amount of product on a glass slide and carefully covering with a cover glass. Photographs at 225 and 500 times magnification were prepared and are reproduced in Figures 1 and
The present invention relates to low-fat content, butter-flavored spreads which simulate the flavor, texture, mouthfeel, appearance, and stability of butter and margarine. More particu-larly, the present invention relates to diet products of this type having a reduction in caloric density of from 50 to 90%, and to processes for preparing them.
The art is replete with prior art attemptS to provide low-fat butter or margarine substitutes. Among these is U.S.
3,457,086 to Josefowicz, et al. which teaches the production of a protein-free spread which can contain as low as 35% fat.
The patent states that observance of specified conditions is necessary to maintain the emulsion in the water-in-oil form.
Unfortunately, products of this type tend to have a watery flavor because of their high water contents and the absence of milk proteins which help impart the desirable butter-like taste of margarine or butter, but which cannot be tolerated in the product because of their emulsion de-stabilizing effect. Moreover, the high water contents tend to make emulsions of this type rapidly break down on hot foods, tending to make foods like toast become soggy and unappetizing. Also, while some consumers have found it convenient to buy large quantities of margarine or butter at sale prices and then freeze them, low-fat spreads based on water-in-oil emulsions cannot tolerate freezing. Upon thawing, the emulsion breaks down with consequential release of its water phase.
Some recent patents suggest that water-in-oil emulsions can be formed with fat contents as low as 25 or 30% to success-fully simulate butter or margarine. This has always presented~
severe problems because the external fat phase tends to become -stretched out and the aqueous phase becomes more predominant.
A ~
SlSl~i~i For example, U.S. 4,103,037, to Bodor et al. discloses a processfor preparing a proteinaceous low-fat spread which is stabilized by a gelling agent, such as gelatin, having ~ melting point sufficiently high to withstand room temperature yet low enough to allow it to melt in the mouth. This gelling agent ties up all available water into minute solid particles which are dispersed throughout a continuous fat phase. These meltable particles contain the water soluble flavors and salt, and further diminish the flavor impact of these components which are already diminished due to the nature of the water-in-oil emulsion.
The adverse effect of water-in-oil emulsions on flavor impact is so pronounced that this is the problem which was dealt with by Moran in U.S. 4,115,598. Therein, flavor impact for a low-fat spread comprising 35 to 65% by weight of a continuous fat phase and dispersed aqueous phase is said to be improved by specially formulating the water-in-oil emulsion to destabilize in the mouth to release the water-soluble flavors.
Further representative of the state of the art of low-fat spreads is U.S. 4,071,634 to Wilton et al. This patent states that low-fat spreads are generally emulsions of the water-in-oil type and cap have fat contents reduced to as low as 30%, as compared to 80% for margarine~ It is indicated that problems related to inferior organoleptic properties or emulsion stability are often encountered in these types of products. Apparently, products of this type which are sufficiently stable, have flavor release problems; while those with good flavor release, are in-sufficiently stable to keep the aqueous phase adequately dis-persed under storage conditions. To remedy this problem, Wilton et al. propose a complex emulsion wherein a discontinuous aqueous li5~gSlI
phase contains phosphatides and a discontinous, second fatty phase dispersed therein.
Among other attempts to provide low-fat spreads is the approach described by Nijhoff in U.S. 3,418,133. Therein, edible spreads are described wherein a portion of a fat content is replaced by an aqueous solution of carboxyme~hyl-ceLlulose.
In Example 2, a margarine substitute is described which is pre-pared from a 50/50 mixture of margarine and aqueous solution.
This product presumably has a fat content of about 40% (i.e., one half that of margarine~; however, the type of emulsion is not identified and the emulsions do not remain stable and solid at room temperature.
U.S. 3,809,764 to Gabby et al. discloses essentially fat-free products which are characterized as "emulsions" of poly-glycerol fatty est,ers with an aqueous hydrophilic colloid. Among the products, are those which are said to simulate margarine yet contain fat contents of less then 5%. These products, while fairly flavorful and fat mimetic, are significantly different in overall flavor, texture, mouthfeel, and appearance from either margarine or butter.
Richardson, in U.S. 4,156,021, also discloses low-fat compositions said to simulate margarine. Example III of this patent employs about 7% corn oil. The emulsions are said to be of the oil-in-water type but obtain much of their body from high levels of cellulose fiber, which also adds its characte-ristic impact on mouthfeel which is significantly different from that of fat.
Other workers have disclosed stable emulsified products containing oil-in-water emulsions, wherein sugars where employed;
however, the necessity for sugar made them sweet and clearly 115~,46d distinct from butter or margarine. Among these is U.S. 3,958,033 to Sims et al. which relates to shelf-stable, clear, liquid emul-sions. The sugar was essential in these formulations to supply the desired sweetness, adjust the refractive index of the aqueous phase to improve product clarity, and enhance shelf stability.
Similarly, in U.S. 4,146 652, Xahn et al. describe stable oil-in-water emulsions containing high sugar levels to obtain micro-biological stability. In U.S. 4,107,343 to Petricca the sugar was required for sweetness demanded of the whipped products invol-ved. Thus, despite the disclosure by these patents of stableoil-in-water emulsions with fat contents in the 10 to 30% range, and the disclosure by Sims et al. in Example XXII of a maple-flavored spread, and a confectionary butter cream in Example I of Kahn et al., there is no solution afforded the skilled worker in the low-fat margarine or butter substitute art seeking a pro-duct which can successfully reproduce the flavor, texture, mouth-feel, stability and appearance of butter or margarine at a calo-ric density of 10-45 colories per 14 gram serving, as compared to the 50 or more calories per similar serving for the best low-fat, butter-flavored spreads commercially available to date.
It is an object of the present invention to provide an improved low-fat, butter-flavored spread and a process for preparing it.
According to an aspect of the present invention there is provided a low-fat, butter-flavored spread comprising, a dis-persed phase comprising from 5 to 40% fat, based on the weight of the spread, a continuous aqueous phase including a stabilizer, and an emulsifier system comprising a combination of a lipophilic emulsifier and a hydrophilic emulsifier, the relative and total amounts of the emulsifiers and the stabilizer being effective llS14~;~
to provide a stable emulsion and a product which is solid at 40F.
According to a further aspect of the present invention there is provided a process for preparing a low-fat, butter-flavored spread, which comprises, preparing an oil-in-water emul-sion comprising a dispersed phase comprising from 5 to 40~ fat, based on the weight of the emulsion, a continuous aqueous phase including a stabilizer, and an emulsifier system comprising a combination of a lipophilic emulsifier, and a hydrophilic emulsi-fier, the relative and total amounts of the emulsifiers and thestabilizer being effective to provide a stable emulsion and a product which is solid at 40F, and cooling the emulsion under conditions effective to solidify it to form a product which is solid at 40F.
Embodiments of the invention will now be described by way of example with reference to the accompanying drawings in which:
Figure 1 is a photomicrograph, taken at 225 times magni-fication, of an emulsion sample as described herein after solidi-fication;
Figure 2 is a photomicrograph of the sample of Figure1, taken at 500 times magnification; and Figure 3 is a flow diagram showing a preferred process scheme according to the invention.
The products described herein, which are prepared by the process described herein, effectively simulate natural butter and good quality margarine in flavor, texture, appearance, mouth-feel and stability, yet have caloric densities of less than 50, and preferably about 10 to 35, colories per 14 gram serving com-pared to about 100 for margarine and butter. The spreads are .' ~`
~151~*0 solid at refrigerator temperature and remain so even after stand-ing for at least 2, and preferably 5, hours at a room temperature of 70F. The spreads, which are based on stable oil-in-water emulsions, remain spreadable at normal refrigerator temperature, and melt quickly in the mouth to release flavor without imparting a waxy texture or mouthfeel.
The term "butter-flavored" is meant to include composi-tions flavored to simulate butter by both naturally-derived and simulated butter flavors. This term is used in its literal sense and is not meant to be otherwise restricted. A composition is considered "butter-flavored" when an expert panel trained to evaluate flavors of this type characterizes the product as "buttery" or "butter-like" in flavor.
The term "stable emulsion" identifies those emulsions which do not undergo any noticeable change in stability, due to water or fat separation or otherwise, during storage in mois-tureproof containers at a temperature of 40F or below for 6 months, and which will also remain stable when stored at a room temperature of 70F for a period of at least one day. Preferably, the emu~sions described herein remain stable after melting, even at elevated temperatures of 180F or more.
The term "solid" is used in its normal sense, to mean the product does not flow under its own weight. Included within the scope of this term are plastic, spreadable compositions which, while not susceptible to flow under their own weight in small quantities, are easily spread with a knife. The more realistic-appearing products described herein will exhibit penetrometer readings at 40F within the range of about 60 to 250 units, using a standard penetrometer cone, having a 2.5 inch diameter and a 45 angle, with 47.5 grams added weight at a S-second interval.
: -~S~.466 Preferably, the penetrometer readings will be within the rangeof from 100 to 200 units.
The products described herein can be aerated if desired;
however, it is an advantage that the products do not have to contain any significant quantity of air or inert gas to stiffen their structures and provide a firmer consistency. Thus, unlike many prior art products, the product itself, probably due to its unique microstructure, provides the solid consistency and there is no dependence upon the use of a gas to distend the emul-sion structure to effect stiffening or solidification. To provide the best overall texture, the degree of gas incorporation is preferably kept to less than 40%, and more preferably less than 20~, by volume.
Similarly, in distinction with some of the prior art compositions, those described herein do not depend upon the pre-sence of protein to obtain the solid texture or the superior mouthfeel; however, they can contain proteins if aesired.
Figures 1 and 2 are photomicrographs taken of a repre-sentative emulsion prepared in Example 1. Figure 1 was made 20 at 225 times magnification and Figure 2 was made at 500 times.
Both show the unique microstructure of the product. It is believed that the chains of small bead-like oil droplets entangle, or coalesce or fuse at points, to form small interstices wherein the aqueous phase is physically trapped as well as being bound to some extent by the attraction for the oil due to the presence of the emulsifiers and stabilizers. The thickened state of the aqueous phase contributed by the stabilizers is also believed to aid in maintaining the unique solid structure of the products described herein, even though the degree of thickening would not itself be sufficient to prevent it from flowing were it not r~
~lS14~i6 for the other effects of the composition described herein. These products are so stable that the emulsions do not separate even after standing for 24 hours or more at room temperature.
The ingredients which are essential to the formation of the product are: (1) fat which is suitably selected to have a Solids Fat Index (SFI~ which enables the formation of solid product at 40F, ~2~ a water-soluble emulsion stabilizer, and (3) an effective emulsifier system comprising both lipophilic and hydrophilic emulsifiers.
The fat can be present in amounts within the range of from 5 to 40 percent based on the weight of the spread, but is preferably present in an amount of from 10 to 30 percent by weight of the spread.
The term "fat" as used herein is intended to include all edible, fatty acid triglycerides regardless of origin or whether they are solid or liquid at room temperature. Thus, the term "fat" includes normally liquid and normally solid vege-table oils and animal fats. Typical of the vegetable oils which are included are the usual vegetable oils such as soybean oil, corn oil, coconut oil, cottonseed oil, peanu$ oil, safflower oil, palm kernel oil, sunflower oil, palm oil, and rapeseed oil.
The preferred fats for use herein will comprise partially hydro-genated vegetable oils, and will most preferably be selected from the group consisting of soybean oil, corn oil, coconut oil, cottonseed oil, peanut oil, palm oil, palm kernel oil, safflower oil, sunflower oil, rapeseed oil, and mixtures of these. Pre-ferred among these are thosepartially-hydrogenated vegetable oils which have an SFI profile within the following ranges.
'~
11S~466 .
Temp. BroadPreferred 50F 40-80% 50-70~
70F 25-50% 30-40%
92F <10~ ~5~
Particular, suitable fats are 92F Wiley melting point partially-hydrogenated coconut oils sold under the trade marks PURECO 92 by Capitol City Products; HYDROL 92 by SCM Corporation;
VICTORY 92 by Humko Div. Kraft Inc.; and COBEE 92 by PVO Inter-national, Inc.
The fat will preferably be selected to provide a solid product at 70F, but will substantially completely melt in the mouth. Where necessary to increase the solids content at 40F
or 70F, an amount of a fat having a higher solids content can be added. Fats like hard stock stearin and cottonseed or soybean flakes have this ability, however, they remain solid and impart a waxy mouthfeel at eating temperature. Thus, while they can be employed to provide a desirable effect on texture, they should not be employed in large amounts.
The use of water-soluble emulsion stabilizers is essen-tial to provide the necessary stability. These can be any of , those known to the art for this purpose and will preferably behydrophilic colloids, and can be selected from the group consis-ting of microcrystalline cellulose, carageenin,. guar gum, algi-nate, xanthan gum, methyl cellulose, carboxy-methyl cellulose, ethyl cellulose, hydroxypropolymethyl cellulose, dextrins, starch, gelatin, locust bean gum, soy protein isolate, pectin and the like, and mixtures of these. Commercial stabilizers available from Polak's Frutal Works, Inc. and identified by the manufac-turer under the trade marks FRIMULSION Q8 and FRIMULSION 10 have been found effective, especially when used in combination. The g _ 11514~
Q8 product is a blend of modified food starch, locust bean gum, guar gum, gelatin and pectin, and is preferably employed at a weight ratio within the range of from about 1:1 to 3:1 to the FRIMULSION 10 which is a blend of locust bean gum and guar gum.
The stabilizer can be employed in any amount effective under the conditions of processing and with the particular ingre-dients. It has been found, however, that levels of abou-t 0.1 to 3.0 percent, based on the total weight of the cbmposition, are particularly effective. In addition to their emulsion sta-bilizing function, these materials also,have a viscosity-increasing effect on the emulsion. However, this effect is not sufficient in and of itself to con~rol the large amounts of water present in these emulsions. Thus, the compositions described herein, unlike the approach taken by Bodor et al. in U.S.
4,103,037, do not depend upon a gelling agent to solidify the aqueous phase.
The compositions described herein further comprise an emulsifier system employing both lipophilic and hydrophilic emulsifiers. The relative and total amounts of the emulsifiers are selected to be effective to provide a stable emulsion and a product which is solid at 40F. Typical of effective levels will be levels of from 0.3% to 4.0~, based on the weight of the total composition of the total emulsifier system which employs each of the hydrophilic and lipophilic emulsifiers at levels of at least 0.05%, on the same basis. The lipophilic emulsifier will typically have an HLB (hydrophile-lipophile balance), of less than 7, and the hydrophilic emulsifier will typically have an HLB of from 10 to 20, preferably from 11 to 17.
The emulsifier system is preferably present at a level of from 0.5% to 2~, and the lipophilic and hydrophilic emulsifiers Al i llS1466 are preferably each present at levels of at least 0.10%, all percentages on a formula weight basis.
The hydrophilic emulsifier will preferably comprise a member selected from the group consisting of polyoxyethylene (20) sorbitan monostearate, polyoxyethylene (20) sorbitan monoo-leate, and mixtures of these.
These emulsifiers, commonly known as polysorbate 60 and polysorbate 80, respectively, are preferred, however, it is believed that other hydrophilic emulsifiers with an HLB of between 10 and 20, preferably between 11 and 17, and most prefer-ably 13 and 16, will be operable. Among other suitable emulsi-fiers are the polyglycerol esters of fatty acids, such as octa-glycerol monooleate. Also suitable are other polysorbates, such as polysorbate 65 which is otherwise known as polyoxyethylene (20) sorbitan tristearate. Various factors such as off-flavor, off-color and generally less desirable qualities of these other materials for use in foods make the aforementioned hydrophilic emulsifiers the most desirable choice. Polysorbate 60 and 80 are the most preferred because they provide a stiffness and spreading quality, especially a cold fracture quality, most like butter and margarine.
Polysorbate 60, polyoxyethylene (20) sorbitan mono-stearate, is a mixture of stearate and palmitate partial esters of sorbitol and sorbitol anhydrides condensed with approximately 20 moles of ethylene oxide (C2H4O) for each mole of sorbitol and its mono- and dianhydrides. It is a lemon to orange colored, oily liquid or semi-gell having a faint characteristic odor and a warm, somewhat bitter taste. It is soluble in water, aniline, ethyl acetate, toluene, and is soluble at low levels in mineral and vegetable oils. Polysorbate 60 is commercially available li5146~
under the trade marks TWEEN 60 from ICI-Atlas, SVS-18 from Hodag, Inc., DREWPONE 60 from PVO International Inc., DURFAX 60 from SCM Corporation, and GYSPS-20 from Glyco, Inc.
Polysorbate 80, polyoxyethylene (20) sorbitan mono-oleate, is a mixture of oleate partial esters of sorbitol and sorbitol anhydrides condensed with approximately 20 moles of ethylene oxide (C2H4O) for each mole of sorbitol and its mono-and dianhydrides. It is a yellow to orange colored, oily liquid having a faint, characteristic odor and a warm, somewhat bitter taste. It is very soluble in water, producing an odorless, nearly colorless solution, and is soluble in ethanol, fixed oils, ethyl acetate and toluene. Polysorbate 80 is commercially available under the trade marks TWEEN 80 from ICI-Atlas, SVO-9 from Hodag, Inc., DREWPONE 80 from PVO Internatlonal Inc., DURFAX 80 from SCM Corporation and GYSPO-20 from Glyco, Inc.
Polysorbate 65, polyoxyethylene (20) sorbitan tristear-ate, is not as preferred as polysorbate 60 or polysorbate 80, but still provides an acceptable product. It is a mixture of steareate and palmitate partial esters of sorbitol and its anhy-drides condensed with approximately 20 moles of ethylene oxide (C2H4OI for each mole of sorbitol and its mono- and dianhydr~ides.
It is a tan, waxy solid having a faint, characteristic odor and a waxy, somewhat bitter taste. It is soluble at low levels in mineral and vegetable oils; at higher levels in mineral spirits, acetone, ether, dioxane and methanol; and is dispersible in water and carbon tetrachloride. Polysorbate 65 is commercially avail-able under the trade marks TWEEN 65 from ICI-Atlas, DREWPONE
65 from PVO International, Inc., DURFAX 65 from SCM Corporation, and GYSPTS-20 from Glycol, Inc.
The lipophilic emulsifier of the emulsifier system ~1 lS14fi6 will preferably comprise a member selected from the group consist-ing of mixed fatty acid monoglycerides; mixed fatty acid digly-cerides; mixtures of fatty acid mono- and diglycerides; lipo-philic polyglycerol esters; glycerol esters, such as glyceryl monooleate, glyceryl dioleate, glyceryl monostearate, glyceryl distearate, glyceryl monopalmitate and glyceryl dipalmitate;
lactylated esters such as glyceryl-lacto esters of fatty acids;
propylene glycol esters such as propylene glycol monopalmitate, propylene glycol monostearate and propylene glycol monooleate;
sorbitan esters such as sorbitan monostearate, sorbitan trioleate, sorbitan tripalmitate, sorbtian tristearate and sorbitan sesqui-oleate; fatty acids or their soaps such as stearic acid, palmitic acid and oleic acid; and mixtures thereof. Here, as in the case of the hydrophilic emulsifier, there is no known criticality in the use of any particular lipophilic emulsifier. Thus, it is fully intended that other equivalent materials can be employed with statisfactory results. However, those specifically identi-fied above, especially those selected from the group consisting of lipophilic polyglycerol esters, mono- and diglycerides, propy-lene glycol esters, lactylated esters, and mixtures of these,are preferred from the stand point of taste and effectiveness.
The products described herein will most closely simulate butter and margarine when they are suitably colored and flavored with those materials known to the art for these purposes. Exam-pleas of coloring agents are beta carotene, annatto, turmeric, paprika and FD~C dyes. Typically, the colors will be dissolved or dispersed in oil or the water phase to expedite blending.
Representative of the flavors and/or flavorenhancers will be sodium chloride; lactones; lipolyzed butter oils and starter distillates; diacetyl, 2-octanone, and other ketones; butyric ~ 13 -~1 11514~fi acid; hexanoic acid and other free fatty acids; esters of butyric acid; delta-hydroxy acids and their glycerol esters; and mixtures of any of these with other known dairy, buttery, or like flavors or flavor notes. It is an advantage of the products described herein that flavors have a very pronounced impact as compared to prior art water-in-oii compositions.
In addition to emulsion stability, the products describ-ed herein are preferably stable against microbiological and oxi-dative deterioration. To control mold and yeast growth, the products preferably contain one or more preservatives such as benzoic acid, sorbic acid, phosphoric acid, lactic acid and the soluble salts of these and other like materials. Preferred as antimicrobiais are potassium sorbate, sodium sorbate, potassium benzoate, sodium benzoate and phosphoric acid. The pH of the aqueous phase is preferably maintained at a value below 6.0, and more preferably within the range of 5.0 to 5.9, to provide effective microbial control and good flavor with the lowest neces-sary levels of preservatives. Addtional stability against oxida-tive deterioration at higher temperatures may be obtained by the use of the usual antioxidants, typical among which are normal propyl gallate, the several tocopherols, butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), nordihydroguaiaretic acid (NDGA), tertiary-butylhydroquinon (TBHQ) and citric acid.
While the products described herein do not require proteins to obtain the proper texture or mouthfeel, they are sometimes desired for nutritional reasons as well as their posi-tive contribution to the flavor and physical properties of the product. Additionally, protein can enhance freeze/thaw stability.
Among the suitable protein materials are any of those known to the art for similar uses in margarine and margarine substitutes.
These can include those derived from vegetable as well as animal ~l " 115~46~
-sources. Thus, vegetable protein isolates such as ~hose derived from soy, peanut, cottonseed, alfalfa, pea and the like; milk-protein containing materials such as non-fat dry milk, whey, caseinates, casein and delactosed whey; and other proteins, can be employed in desired amounts. One suitable type of protein is that sold under the MELOTEIN MP-14P trade mark by Dairyland, Inc. These products are spray dried blends of milk proteins such assweet dairy whey and caseinates. Typically, they are added in amounts of up to 10~ based on the total weight of the spread. Preferred levels will be from 1 to 8~ on this basis.
Also added can be any of the vitamins and minerals desired. Preferred among these are vitamins A and D which are normally associated with butter or margarine products. If desir-ed, these can be added in amounts approximating those in butter or margarine.
Also where desired, a chelating agent such as ethylene-diaminetetraacetic acid (EDTA), its salts, such as calcium diso-dium EDTA or the like can be employed to tie up metal ions which may otherwise detrimentally interact with one or more of the ingre-dients.
All of the above ingredients can be formed into the low-fat, butter-flavored spread described herein by following the preferred processscheme set out in Figure 3, or otherwise preparing an oil-in-water emulsion comprising the essential ingre-dients, and then cooling the emulsion under conditions effective to solidify it and forma spread which is solid at 40F, prefera-bly at 70F, and most preferably at 75F.
The flow diagram of Figure 3 shows the separate prepa-ration of fat and aqueous phases prior to blending and emulsi-fying them. The water and water-soluble ingredients, such as ,~1 11514~6 milk protein solids, salt and preservatives, are added to mixing vessel 10 by lines 12 and 14, respectively. The vessel may be equipped with a suitable heater 16 which can be an electrical resistance heater, a water or steam jacket or the like. Alter-natively, the water from line 12 can be supplied hot. Typically, the water will be heated to a temperature of about 190F to assure complete hydration of the water soluble materials added.
Agitation is supplied by mixing device 17. Where the stabilizers, which are water soluble, are mixed with the water at this stage ln processing, the shear supplied by the mixing must be intense enough to overcome the normal tendency of these materials to clump together and prevent complete hydration and dispersion.
It is preferred, however, to predisperse the stabilizers in a portion of the fat phase prior to contact with water. This can be accomplished by blending with mixing device 18 in vessel 19, and then passing to vessel 10 by line 20.
The fat phase is prepared in a separate vessel 21 which can also be equipped with a suitable heating device 22 and mixing device 24. The fat-soluble materials such as the color, flavor, vitamins and emulsifiers, if desired, are added at 26 to the fat which is added at 28. The hydrophilic emulsifier will prefer-ably be added to the water phase instead of the fat phase. The fat is maintained at a temperature high enough to assure its liquid character. Temperatures of from about 120 to 190F, pre-ferably about 130 to 150F, are effective to provide good solubi-lity of additives and a suitably low viscosity.
The fat phase can be drawn from mixing vessel 21 by line 30 and then passed to vessel 35 wherein it i3 mixed with the water phase which is supplied by line 36 and may have been cooled to approximately the same temperature as the fat phase by means of heat exchanger 38. Adequate mixing is provided by device 40 which supplies sufficient shear to begin the emulsifi-cation of the fat lnto the water. At the completion of mixing, an emulsion will have been formed which uniformly disperses the fat into droplets within the aqueous phase; however, the droplets are not broken down finely enough to permit emulsion stability.
The rough emulsion prepared in vessel 35 is then passed via line 42 to homogenizer 44 wherein the final emulsion is form ed. The emulsion will, at this point, still be at a temperature sufficiently high to maintain the fat in the liquid state. Homo-genization will typically be accomplished at a pressure of from 100 to 500, and preferably about 250, atmospheres. Any of the typical homogenizers or colloid mills effective for dairy purposes can be employed in this process. Thus, the Manton-Gaulin 2-stage homogenizer or the Cherry Burrell 2-stage homogenizer can be employed effectively.
From the homogenizer 44, the homogenized emulsion is passed via line 46 to a suitable heat exchanger 48 where it is cooled. The heat exchanger 48 will preferably be of a kind capa-ble of rapidly cooling the emulsion. Typical of the suitable devices are scraped-wall heat exchangers ("A" units), such as those sold under the VOTATOR trade mark. Typically, the heat exchange~ coolant will be maintained at a temperature of about -20F to cool the emulsion rapidly from about 140 to 160F to below about 70F, and preferably below about 40F.
The cooled emulsion is then preferably passed from the heat exchanger 48 via line 50 to a mixing chamber 52 wherein gentle agitation is maintained internally by a suitable rotating mixing device 54 for a period of time effective to initiate crys-tallization of the fat and the propagation of the unique physical A
" ~lSi46i~
structure of the product described herein. The agitation promotes crystalli~ation and enhances solidification. According to the most preferred mode of operation, a series, preferably about three, "A" units cool the emulsion, and a blender ~"B" unit) is positioned at the end of the series, or between two of the "A" units in the series, to aid in promoting crystallation.
The spreads described herein can be printed into sticks, formed into pats or filled into tubs. Thus, these spreads, des-pite their low fat contents and high water contents, have the physical appearance, as well as other characteristics, of high quality margarine or butter.
The following examples are presented for the purpose of further illustrating and explaining the present invention and are not to be taken as limiting in any regard. ~nless other-wise indicated, all parts and percentages will be by weight.
Example I
This example describes the preparation of a preferred spread as described above and details the procedure for obtaining the microphotographs shown in Figures 1 and 2.
The spread was made from the following materials which were employed in the amounts listed:
A~
~1S146~;
Amount Ingredients Iparts by wt.) Coconut oil, 92F Wiley melting point l9.0000 Mono- and diglycerides(a) 0.5000 Polyso~bate 60(b) 0-5000 Beta carotene (30% in oil) and vitamins 0.0050 Salt 1.6500 Butter flavor 0.0200 Stabilizer(C) 1.0000 Stabilizer(d) 0~4000 Water 76.6743 Potassium sorbate 0.1300 Sodium Benzoate 0.1000 Phosphoric acid 0.0150 Calcium disodium EDTA 0.0057 (a) DUREN 114 (b) DURFAX 60 (c) FRIMULSION Q8 (d) FRIMULSION 10 An aqueous phase was prepared by heating the water to 190F and adding the dry ingredients, and the FRIMULSION
Q8 and 10 stabilizers predispersed in a portion of the melted fat, to it with agitation. Mixing was continued until the stabi-lizers were uniformly dispersed and hydrated.
A separate fat phase was prepared by melting the remain-ing portion of the fat and the emulsifiers at a temperature of about 150F. The color and flavor were then admixed with the melt to obtain a uniform blend.
The aqueous and fat phases were then blended at about * A trade mark - 19 -i~S1466 ;
160F to provide an emulsion. The emulsion was then homogenized in a Gaulin Laboratory homogenizer, Model 15M, set at 150 atm.
first stage and 100 atm. second stage.
The emulsion was then cooled to 40F in about 15 min-utes by slowly agitating with a Hobart Modei N50 mixer fitted with a wire whip and a jacketed (water/alcohol coolant at appro-ximately -20F) 5-quart mixing bowl. The resulting product was transferred to a tub and refrigerated for 24 hours. The result-ing solidified spread exhibited a penetrometer reading of 130 10 units when measured by a Krebs Penetrometer with a standard pene-trometer cone having a 2.5 inch diameter and a 45 angle, with 47.5 grams added weight at a 5-second interval. ~Penetrometer procedures according to ANS/ASTM D217-68).
The spread was prepared for microphotography by placing a very small amount of product on a glass slide and carefully covering with a cover glass. Photographs at 225 and 500 times magnification were prepared and are reproduced in Figures 1 and
2.
The final product was then heated to determine the 20 stability and viscosity of the emulsion at various temperatures.
Using a Brookfield RVT Viscometer fitted with a number 1 spindle, the emulsion exhibited the following viscosities at 10 rpm:
100F - 880 centipoises 150F - 500 centipoises 200F - 310 centipoises The emulsion was stable at all of these temperatures.
The product was tested to determine the type of emul-sion by microscopic and colorimetric analysis. Under the micro-scopic test, a small amount of the product was placed on a micro-30 scope slide. A drop of water was then placed near the outer ~15146~
, edge of the product. The interface between the product and thewater was then observed. If the emulsion was diluted, i.e., water from the droplet entered the emulsion, the emulsion was of the oil-in-water type, with the water being the continuous phase. Under the colorimetric test, an intensely colored fruit juice, such as grape, elderberry, raspberry or the like, was drop-ped on the surface of the product. If the color was absorbed by the product, the emulsion was of the oil-in-water type. If no color was absorbed, the emulsion was of the water-in-oil type.
Under both tests, the emulsion of this example was found to be oil-in-water.
Example II
This example describes the preparation of another spread. The details of the procedure were the same as in Example I. The only difference was that dairy solids were added and the proportions of the other ingredients were adjusted according-ly .
The spread was made from the following materials which were employed in the amounts listed.
~1 1~514~;
Amount Ingredient ~parts by wt.) Coconut oil, 92F Wiley melting point18.5000 Mono- and diglycerides(a) 0.5000 Polysorbate 60 (b) 0.5000 Beta carotene (3096 in oil) and vitamins 0.0050 Salt 1.6500 Butter flavor 0.0200 Stabilizer(C) 1.0000 Stabilizer(d) 0,4000 Water 73.6743 Potassium sorbate 0.1300 Sodium benzoate 0.1000 Phosphoric acid 0.0150 Whey/caseinate blend(e) 3.5000 Calcium disodium EDTA 0.0057 _ (a), (b), (c) and (d): see Example I.
(e) MELOTEIN MP-14P.
The solidified spread exhibited a penetrometer reading of 175 units when measured as in Example I.
Example III
This example describes the preparation of another spread, but this time containing about 30% fat. The procedure was the same as in Example I. The spread was made from the fol-lowing materials which were employed in the amounts listed:
* A trade mark ;
:11514~6 Amount Ingredient (parts by wt.) Coconut oil, 92F Wiley melting point 29.0000 Mono- and diglycerides(a) 0.5000 Polysorbate 60(b) 0.5000 Beta carotene (30% in oil) and vitamins 0.0050 Salt 1.6500 Butter flavor 0.0200 Stabilizer(C) 1.0000 Stabilizer(d) 0.4000 Water 66.6743 Potassium sorbate 0.1300 Sodium bensoate 0.1000 Phosphoric acid 0.0150 Calcium disodium EDTA 0.0057 (a), (b), (c) and (d): see Example I.
The resulting solidified spread exhibited a penetrometer reading of 166 units when measured as in Example I.
Exam~ e IV
This example describes the preparation of yet another spread, again employing the procedure of Example I, but this time utilizing only 10% fat. The spread was made from the follow-ing materials which were employed in the amounts listed:
~\
il51~
Amount Ingredient (parts by wt.) Coconut oil,, 92F Wiley melting point 9.0000 Mono- and diglycerides(a) 0.5000 Polysorbate 60(b) . 0.5000 Beta carotene (30% in oil) 0.0050 Salt 1.6500 Butter flavor 0.0200 Stabilizer (c) 1.0000 Stabilizer~d) 0.4000 Water 86.6791 Potassium sorbate , 0.1300 Sodium benzoate 0.1000 Phosphoric acid 0.0150 Calcium disodium EDTA 0.0057 (a), (b), (c) and (d): see Example I
The penetrometer reading for the final product was 227 when measured as in Example I.
Example V
This example describes the preparation of another spread, but this time utilizing different stabilizers. The spread was made from the following materials which were employed in the amounts listed:
~ !
~ 1514~6 :`
Amount Ingredient (parts by wt.) Coconut oil 92F Wiley melting point 20.0000 Mono- and diglycerides(a) 0.5000 Polysorbate 60(b) . 0.5000 Beta carotene (30% in oil) and vitamins 0.0035 Salt 1.6500 Butter flavor 0.0320 Stabilizer (89% micro-crystalline2.1000 cellulose and 11% sodium carboxy-methyl cellulose)(f) Water 74.9613 Potassium sorbate 0.1300 Sodium benzoate 0.1000 Phosphoric acid 0.0250 ~-_ (a) and (b): see Example I
(f) AVICEL 581, FMC, Inc.
The procedure was essentially the same as that of Example I, but differing in that: the water was heated to only 160F; and the oil was heated to only 130F.
The penetrometer reading for the final product was 82 units when measured as in Example I.
Example VI
This example describes the preparation of another spread, but this time employing a different emulsifier system.
Except for the change in formulation, the process was the same as in Example I. The spread was made from the following mate-rials which were employed in the amounts listed:
* A trade mark , 1~51q~
Amount Ingredient (parts by wt.) Coconut oil, 92F Wiley melting point 17.5000 Glyceryl-lacto esters of fatty 0.5000 acid, lipophilic emulsifier(g~
Octaglycerol monooleate, hydro- - . 2.0000 philic emulsifier (HLB=13.0) Beta carotene (30% in oil) 0.0050 Salt 1.6500 Butter flavor . 0.0200 Stabilizer (c) 1.0000 Stabilizer(d) 0.4000 Water 76.6743 Potassium sorbate 0.1300 Sodium benzoate 0.1000 Phosphoric acid 0.0150 Calcium disodium EDTA 0.0057 (c) and (d): see Example I
(g) DURLAC 100 WK
20 The resulting solidified spread exhibited a penetrometer reading of 117 units when measured as in Example I.
* A trade mark - 26 -~ ' ~ ', li514~i6 Example VII
This example describes the preparation of anotherspread, but this time employing soybean oil and employing a lower level of polysorbate 60 than in Example I. The process was the same as in Example I. The spread was made from the following materials which were employed in the amounts listed:
Amount Ingredient (parts by wt.) Soybean oil, partially hydrogenated(h) 19.2500 Mono- and diglycerides(a~ 0.5000 Polysorbate 80(b) 0.2500 Beta carotene (30% in oil) and vitamins 0.0050 Salt 1.6500 Butter flavor 0.0200 Stabilizer(C) 1.0000 Stabilizer(d) 0.4000 Water 76.6743 Potassium sorbate 0.1300 Sodium benzoate 0.1000 Phosphoric acid 0.0150 : Calcium disodium EDTA 0.0057 _ (a), (b), (c) and (d): see Example I
(h) TEM-Plus 95, Swift, Inc.
The resulting spread exhibited a penetrometer reading of 199 units when measured as described in Example I.
* A trade mark 27 _ ~15146ff Exam~le VIII
This example describes the preparation of another spread, but this time employin~ polysorbate 80 in place of the low level of polysorbate 60 in Example VII. The process was the same as in Example VII. The spread was made from the follow-ing materials which were employed in the amounts listed:
Amount Ingredient (parts by wt.) Coconut oil, 92F Wiley melting point 19.2500 Mono- and diglycerides( ) 0.5000 Polysorbate 80(i) 0.2500 Beta carotene (30% in oil) and vitamins 0.0050 Salt 1.6500 Butter flavor 0.0200 Stabilizer(C) 1.0000 Stabilizer~d) 0.4000 Water 76.6743 Potassium sorbate 0.1300 Sodium benzoate 0.1000 Phosphoric acid 0.0150 Calcium disodium EDTA 0.0057 _ (a), (c) and (d): see Example I
(i) DURFAX 80 The resulting spread exhibited a penetrometer reading of 182 units when measured as in Example I.
* A trade mark _ 28 _ l~S146~¢
Example IX
A comparison was made between the product prepared according to Example I, conventional margarine products (both soft and stick) and a commercial diet margarine substitute.
Margarine will typically contain:
Amount Inqredient Iparts by wt.) Partially Hydrogenated Vegetable Oil 80.000 Lecithin 0.100 Mono- & Diglycerides 0.150 Color, Flavor, Vitamins 0.020 Dairy Solids 1.600 Salt 2.000 Water 16.130 To prepare the margarine it will typically be processed by blending oil (130F) and water (50F) phases either in-line or in an emulsion tank. The emulsion ls pumped through a series of coollng scraped surface heat exchangers (usually 3). A blend-er ("B" unit) is usually positioned between the second and third heat exchanger or after the third heat exchanger, to aid in pro-moting crystallization. The product is normally filled ln the 40-50F range.
The margarines made in this manner are available in two general types - soft, which is sold in small plastic dishes called tubs; and stick, which is sold in sticks like butter.
A diet margarine substitute will typically contain:
~1 -- . ...
115146:~;
Amount Ingredient (parts by wt.) Partially hydrogenated vegetable oil 39.40 Monoglycerides 0.50 Lecithin 0.10 Vitamin, Color and Flavor Mix 0.01 Water 57.78 Salt 2.00 Preservatives 0.21 To prepare the diet margarine substitute a water-in-oil emulsion is prepared by blending the oil phase (120F) with the water phase (95F~ in an emulsion tank. The emulsion is pumped through a series of cooling, scraped-surface heat exchang-ers (usually 3). A blender ("B" unit) is usually positioned between the second and third heat exchanger or after the third heat exchanger, to aid in promoting crystalliæation. The product is normally filled in the 70 - 75F range. Diet products proces-sed in this manner are normally available only in the soft form, which is sold in small plastic dishes called tubs. Taking the product produced in Example I, a commercial soft margarine, a commercial stick margarine and a commercial diet margarine sub-stitute, the penetrometer readings were taken as discussed in Example I.
Penetrometer Data (40F) Ran~e Average Example I 117-143 130 Soft Margarine 103-174 131 Stick Margarine 80-133 113 Diet Margarine substitute 135-180 155
The final product was then heated to determine the 20 stability and viscosity of the emulsion at various temperatures.
Using a Brookfield RVT Viscometer fitted with a number 1 spindle, the emulsion exhibited the following viscosities at 10 rpm:
100F - 880 centipoises 150F - 500 centipoises 200F - 310 centipoises The emulsion was stable at all of these temperatures.
The product was tested to determine the type of emul-sion by microscopic and colorimetric analysis. Under the micro-scopic test, a small amount of the product was placed on a micro-30 scope slide. A drop of water was then placed near the outer ~15146~
, edge of the product. The interface between the product and thewater was then observed. If the emulsion was diluted, i.e., water from the droplet entered the emulsion, the emulsion was of the oil-in-water type, with the water being the continuous phase. Under the colorimetric test, an intensely colored fruit juice, such as grape, elderberry, raspberry or the like, was drop-ped on the surface of the product. If the color was absorbed by the product, the emulsion was of the oil-in-water type. If no color was absorbed, the emulsion was of the water-in-oil type.
Under both tests, the emulsion of this example was found to be oil-in-water.
Example II
This example describes the preparation of another spread. The details of the procedure were the same as in Example I. The only difference was that dairy solids were added and the proportions of the other ingredients were adjusted according-ly .
The spread was made from the following materials which were employed in the amounts listed.
~1 1~514~;
Amount Ingredient ~parts by wt.) Coconut oil, 92F Wiley melting point18.5000 Mono- and diglycerides(a) 0.5000 Polysorbate 60 (b) 0.5000 Beta carotene (3096 in oil) and vitamins 0.0050 Salt 1.6500 Butter flavor 0.0200 Stabilizer(C) 1.0000 Stabilizer(d) 0,4000 Water 73.6743 Potassium sorbate 0.1300 Sodium benzoate 0.1000 Phosphoric acid 0.0150 Whey/caseinate blend(e) 3.5000 Calcium disodium EDTA 0.0057 _ (a), (b), (c) and (d): see Example I.
(e) MELOTEIN MP-14P.
The solidified spread exhibited a penetrometer reading of 175 units when measured as in Example I.
Example III
This example describes the preparation of another spread, but this time containing about 30% fat. The procedure was the same as in Example I. The spread was made from the fol-lowing materials which were employed in the amounts listed:
* A trade mark ;
:11514~6 Amount Ingredient (parts by wt.) Coconut oil, 92F Wiley melting point 29.0000 Mono- and diglycerides(a) 0.5000 Polysorbate 60(b) 0.5000 Beta carotene (30% in oil) and vitamins 0.0050 Salt 1.6500 Butter flavor 0.0200 Stabilizer(C) 1.0000 Stabilizer(d) 0.4000 Water 66.6743 Potassium sorbate 0.1300 Sodium bensoate 0.1000 Phosphoric acid 0.0150 Calcium disodium EDTA 0.0057 (a), (b), (c) and (d): see Example I.
The resulting solidified spread exhibited a penetrometer reading of 166 units when measured as in Example I.
Exam~ e IV
This example describes the preparation of yet another spread, again employing the procedure of Example I, but this time utilizing only 10% fat. The spread was made from the follow-ing materials which were employed in the amounts listed:
~\
il51~
Amount Ingredient (parts by wt.) Coconut oil,, 92F Wiley melting point 9.0000 Mono- and diglycerides(a) 0.5000 Polysorbate 60(b) . 0.5000 Beta carotene (30% in oil) 0.0050 Salt 1.6500 Butter flavor 0.0200 Stabilizer (c) 1.0000 Stabilizer~d) 0.4000 Water 86.6791 Potassium sorbate , 0.1300 Sodium benzoate 0.1000 Phosphoric acid 0.0150 Calcium disodium EDTA 0.0057 (a), (b), (c) and (d): see Example I
The penetrometer reading for the final product was 227 when measured as in Example I.
Example V
This example describes the preparation of another spread, but this time utilizing different stabilizers. The spread was made from the following materials which were employed in the amounts listed:
~ !
~ 1514~6 :`
Amount Ingredient (parts by wt.) Coconut oil 92F Wiley melting point 20.0000 Mono- and diglycerides(a) 0.5000 Polysorbate 60(b) . 0.5000 Beta carotene (30% in oil) and vitamins 0.0035 Salt 1.6500 Butter flavor 0.0320 Stabilizer (89% micro-crystalline2.1000 cellulose and 11% sodium carboxy-methyl cellulose)(f) Water 74.9613 Potassium sorbate 0.1300 Sodium benzoate 0.1000 Phosphoric acid 0.0250 ~-_ (a) and (b): see Example I
(f) AVICEL 581, FMC, Inc.
The procedure was essentially the same as that of Example I, but differing in that: the water was heated to only 160F; and the oil was heated to only 130F.
The penetrometer reading for the final product was 82 units when measured as in Example I.
Example VI
This example describes the preparation of another spread, but this time employing a different emulsifier system.
Except for the change in formulation, the process was the same as in Example I. The spread was made from the following mate-rials which were employed in the amounts listed:
* A trade mark , 1~51q~
Amount Ingredient (parts by wt.) Coconut oil, 92F Wiley melting point 17.5000 Glyceryl-lacto esters of fatty 0.5000 acid, lipophilic emulsifier(g~
Octaglycerol monooleate, hydro- - . 2.0000 philic emulsifier (HLB=13.0) Beta carotene (30% in oil) 0.0050 Salt 1.6500 Butter flavor . 0.0200 Stabilizer (c) 1.0000 Stabilizer(d) 0.4000 Water 76.6743 Potassium sorbate 0.1300 Sodium benzoate 0.1000 Phosphoric acid 0.0150 Calcium disodium EDTA 0.0057 (c) and (d): see Example I
(g) DURLAC 100 WK
20 The resulting solidified spread exhibited a penetrometer reading of 117 units when measured as in Example I.
* A trade mark - 26 -~ ' ~ ', li514~i6 Example VII
This example describes the preparation of anotherspread, but this time employing soybean oil and employing a lower level of polysorbate 60 than in Example I. The process was the same as in Example I. The spread was made from the following materials which were employed in the amounts listed:
Amount Ingredient (parts by wt.) Soybean oil, partially hydrogenated(h) 19.2500 Mono- and diglycerides(a~ 0.5000 Polysorbate 80(b) 0.2500 Beta carotene (30% in oil) and vitamins 0.0050 Salt 1.6500 Butter flavor 0.0200 Stabilizer(C) 1.0000 Stabilizer(d) 0.4000 Water 76.6743 Potassium sorbate 0.1300 Sodium benzoate 0.1000 Phosphoric acid 0.0150 : Calcium disodium EDTA 0.0057 _ (a), (b), (c) and (d): see Example I
(h) TEM-Plus 95, Swift, Inc.
The resulting spread exhibited a penetrometer reading of 199 units when measured as described in Example I.
* A trade mark 27 _ ~15146ff Exam~le VIII
This example describes the preparation of another spread, but this time employin~ polysorbate 80 in place of the low level of polysorbate 60 in Example VII. The process was the same as in Example VII. The spread was made from the follow-ing materials which were employed in the amounts listed:
Amount Ingredient (parts by wt.) Coconut oil, 92F Wiley melting point 19.2500 Mono- and diglycerides( ) 0.5000 Polysorbate 80(i) 0.2500 Beta carotene (30% in oil) and vitamins 0.0050 Salt 1.6500 Butter flavor 0.0200 Stabilizer(C) 1.0000 Stabilizer~d) 0.4000 Water 76.6743 Potassium sorbate 0.1300 Sodium benzoate 0.1000 Phosphoric acid 0.0150 Calcium disodium EDTA 0.0057 _ (a), (c) and (d): see Example I
(i) DURFAX 80 The resulting spread exhibited a penetrometer reading of 182 units when measured as in Example I.
* A trade mark _ 28 _ l~S146~¢
Example IX
A comparison was made between the product prepared according to Example I, conventional margarine products (both soft and stick) and a commercial diet margarine substitute.
Margarine will typically contain:
Amount Inqredient Iparts by wt.) Partially Hydrogenated Vegetable Oil 80.000 Lecithin 0.100 Mono- & Diglycerides 0.150 Color, Flavor, Vitamins 0.020 Dairy Solids 1.600 Salt 2.000 Water 16.130 To prepare the margarine it will typically be processed by blending oil (130F) and water (50F) phases either in-line or in an emulsion tank. The emulsion ls pumped through a series of coollng scraped surface heat exchangers (usually 3). A blend-er ("B" unit) is usually positioned between the second and third heat exchanger or after the third heat exchanger, to aid in pro-moting crystallization. The product is normally filled ln the 40-50F range.
The margarines made in this manner are available in two general types - soft, which is sold in small plastic dishes called tubs; and stick, which is sold in sticks like butter.
A diet margarine substitute will typically contain:
~1 -- . ...
115146:~;
Amount Ingredient (parts by wt.) Partially hydrogenated vegetable oil 39.40 Monoglycerides 0.50 Lecithin 0.10 Vitamin, Color and Flavor Mix 0.01 Water 57.78 Salt 2.00 Preservatives 0.21 To prepare the diet margarine substitute a water-in-oil emulsion is prepared by blending the oil phase (120F) with the water phase (95F~ in an emulsion tank. The emulsion is pumped through a series of cooling, scraped-surface heat exchang-ers (usually 3). A blender ("B" unit) is usually positioned between the second and third heat exchanger or after the third heat exchanger, to aid in promoting crystalliæation. The product is normally filled in the 70 - 75F range. Diet products proces-sed in this manner are normally available only in the soft form, which is sold in small plastic dishes called tubs. Taking the product produced in Example I, a commercial soft margarine, a commercial stick margarine and a commercial diet margarine sub-stitute, the penetrometer readings were taken as discussed in Example I.
Penetrometer Data (40F) Ran~e Average Example I 117-143 130 Soft Margarine 103-174 131 Stick Margarine 80-133 113 Diet Margarine substitute 135-180 155
Claims (50)
1. A low-fat, butter-flavored spread comprising:
a dispersed phase comprising from 5 to 40% fat, based on the weight of said spread;
a continuous aqueous phase including a stabilizer; and an emulsifier system comprising a combination of a lipophilic emulsifier and a hydrophilic emulsifier;
the relative and total amounts of said emulsifiers and said stabilizer being effective to provide a stable emulsion and a product which is solid at 40°F.
a dispersed phase comprising from 5 to 40% fat, based on the weight of said spread;
a continuous aqueous phase including a stabilizer; and an emulsifier system comprising a combination of a lipophilic emulsifier and a hydrophilic emulsifier;
the relative and total amounts of said emulsifiers and said stabilizer being effective to provide a stable emulsion and a product which is solid at 40°F.
2. A low-fat, butter flavored spread according to claim 1, wherein said fat comprises from 10 to 30% of the total weight of said spread.
3. A low-fat, butter-flavored spread according to claim 1, wherein said fat comprises a partially hydrogenated vegetable oil having a solids profile effective, when employed in the total system, to provide a product which remains solid at 40°F, remains spreadable at normal refrigerator temperature, and melts quickly in the mouth to release flavor without imparting a waxy texture or mouthfeel.
4. A low-fat, butter-flavored spread according to claim 3, wherein said fat comprises a partially-hydrogenated vegetable oil having an SFI profile with the following ranges:
50°F - 40-80%
70°F - 25-50%
92°F - <10%.
50°F - 40-80%
70°F - 25-50%
92°F - <10%.
5. A low-fat, butter-flavored spread according to claim 4, wherein said fat comprises a partially-hydrogenated vegetable oil having an SFI profile with the following ranges:
50°F - 50-70%
70°F - 30-40%
92°F - <5%.
50°F - 50-70%
70°F - 30-40%
92°F - <5%.
6. A low-fat, butter-flavored spread according to claim 1, 3 or 4, wherein said fat is selected from the group consisting of: soybean oil, corn oil, coconut oil, cottonseed oil, peanut oil, palm oil, palm kernel oil, safflower oil, sunflower oil, rapeseed oil and mixtures thereof.
7. A low-fat, butter-flavored spread according to claim 3,4 or 5, wherein said fat is selected from the group consisting of; 92°F Wiley melting point partially-hydrogenated coconut oils identified by the trade marks: PURECO 92, HYDROL 92, VICTORY 92 and COBEE 92.
8. A low-fat, butter-flavored spread according to claim 1, which exhibits a penetrometer reading at 40°F within the range of 60 to 250 units using a standard penetrometer cone, having a 2.5 inch diameter and a 45° angle, with 47.5 grams added weight at a 5-second interval.
9. A low-fat, butter-flavored spread according to claim 8, which exhibits a penetrometer reading within the range of 100 to 200 units under the same conditions.
10. A low-fat, butter-flavored spread according to claim 1, wherein said emulsifier system is present in an amount of from 0.3 to 4.0%, based on the total weight of said spread, and each of said lipophilic and hydrophilic emulsifiers are present at levels of at least 0.05% on the same basis.
11. A low-fat, butter-flavored spread according to claim 1, wherein said emulsifier system is present in an amount of from 0.5 to 2%, based on the total weight of said spread, and each of said lipophilic and hydrophilic emulsifiers are present at levels of at least 0.10% on the same basis.
12. A low-fat, butter-flavored spread according to claim 10, wherein said hydrophilic emulsifier has an HLB of from 11 to 17.
13. A low-fat, butter-flavored spread according to claim 10 or 11, wherein said hydrophilic emulsifier has an HLB
of from 10 to 20.
of from 10 to 20.
14. A low-fat, butter-flavored spread according to claim 11, wherein said hydrophilic emulsifier has an HLB of from 13 to 16.
15. A low-fat, butter-flavored spread according to claim 11, 12 or 14, wherein said hydrophilic emulsifier comprises a member selected from the group consisting of: polyoxyethylene (20) sorbitan monostearate , polyoxyethylene (20) sorbitan monooleate and mixtures thereof.
16. A low-fat, butter-flavored spread according to claim 11, 12 or 14, wherein said hydrophilic emulsifier comprises polyoxyethylene (20) sorbitan tristearate.
17. A low-fat, butter-flavored spread according to claim 11, 12 or 14, wherein said hydrophilic emulsifier comprises octaglycerol monooleate.
18. A low-fat, butter-flavored spread according to claim 1, wherein said lipophilic emulsifier has an HLB of less than 7.
19. A low-fat, butter-flavored spread according to claim 18, wherein said lipophilic emulsifier comprises a member selected from the group consisting of: mixed fatty acid monoglycerides; mixed fatty acid diglycerides; mixtures of fatty acid mono- and diglycerides; lipophilic polyglycerol esters;
glycerol esters including glyceryl monooleate, glyceryl dioleate, glyceryl monostearate, glyceryl distearate, glyceryl monopalmitate and glyceryl dipalmitate; lactylated esters including glyceryl-lacto esters of fatty acids; propylene glycol esters including propylene glycol monopalmitate, propylene glycol monostearate, and propylene glycol monooleate; sorbitan esters including sorbitan monostearate, sorbitan trioleate, sorbitan tripalmi-tate, sorbitan tristearate and sorbitan sesquioleate; fatty-acids and their soaps including stearic acid, palmitic acid and oleic acid; and mixtures thereof.
glycerol esters including glyceryl monooleate, glyceryl dioleate, glyceryl monostearate, glyceryl distearate, glyceryl monopalmitate and glyceryl dipalmitate; lactylated esters including glyceryl-lacto esters of fatty acids; propylene glycol esters including propylene glycol monopalmitate, propylene glycol monostearate, and propylene glycol monooleate; sorbitan esters including sorbitan monostearate, sorbitan trioleate, sorbitan tripalmi-tate, sorbitan tristearate and sorbitan sesquioleate; fatty-acids and their soaps including stearic acid, palmitic acid and oleic acid; and mixtures thereof.
20. A low-fat, butter-flavored spread according to claim 18, wherein said lipophilic emulsifier comprises a member selected from the group concisting of: lipophilic polyglycerol esters, mono- and diglycerides, propylene glycol esters, lactyl-ated esters and mixtures thereof.
21. A low-fat, butter-flavored spread according to claim 1, having less than 40% by volume of gas incorporated therein.
22. A low-fat, butter-flavored spread according to claim 12, 14 or 18, having less than 20% by volume of gas incor-porated therein.
23. A low-fat, butter-flavored spread according to claim 1, wherein said stabilizer is a hydrophilic colloid selected from the group locust bean gum, gelatin, pectin, micro-crystalline cellulose, carageenin, guar gum, alginate, xanthan gum, soy protein isolate, methyl cellulose, carboxymethyl cellulose, ethyl cellulose, hydroxypropylmethyl cellulose, dex-trins, soluble starch and mixtures thereof.
24. A low-fat, butter-flavored spread according to claim 1, wherein said stabilizer comprises from 0.1 to 3.0%
of the total weight of said spread.
of the total weight of said spread.
25. A low-fat, butter-flavored spread according to claim 1, 11 or 24, which is solid at 70°F.
26. A low-fat, butter-flavored spread according to claim 1, wherein said hydrophilic emulsifier comprises a member selected from the group consisting of: polyoxyethylene (20) sorbitan monostearate, polyoxyethylene (20) sorbitan monooleate and mixtures thereof; and said spread is solid at 70°F.
27. A low-fat, butter-flavored spread according to claim 1, wherein the composition further comprises an effective amount of an antimicrobial agent to prevent microbiological spoilage of said spread.
28. A low-fat, butter-flavored spread according to claim 27, wherein the pH of the aqueous phase is below 6.
29. A low-fat, butter-flavored spread according to claim 28, wherein the pH of said aqueous phase is in the range from 5.0 to 5.9.
30. A low-fat, butter-flavored spread according to claim 29, further comprising an additive selected from the group consisting of: a coloring agent, a flavoring agent, a flavor enhancing agent, an antioxidant, a protein, a vitamin, a mineral, a chelating agent and mixtures thereof.
31. A low-fat, butter-flavored spread according to claim 30, wherein said spread has 10 to 35 calories per 14 gram serving and remains solid after standing for 5 hours at 70°F.
32. A low-fat, butter-flavored spread according to claim 31, wherein the emulsion is stable for 6 months when stored in a moistureproof container at a temperature up to 40°F
and is stable for at least one day at a temperature of 70°F.
and is stable for at least one day at a temperature of 70°F.
33. A low-fat, butter-flavored spread according to claim 32, wherein said emulsion is stable, after melting, at a temperature of 130°F.
34. A low-fat, butter-flavored spread according to claim 33, which is solid at 75°F.
35. A process for preparing a low-fat, butter-flavored spread, which comprises:
preparing an oil-in-water emulsion comprising a dispersed phase comprising from 5 to 40% fat, based on the weight of said emulsion, a continuous aqueous phase including a stabil-izer, and an emulsifier system comprising a combination of a lipophilic emulsifier, and a hydrophilic emulsifier, the relative and total amounts of said emulsifiers and said stabilizer being effective to provide a stable emulsion and a product which is solid at 40 F; and cooling said emulsion under conditions effective to solidify it to form a product which is solid at 40°F.
preparing an oil-in-water emulsion comprising a dispersed phase comprising from 5 to 40% fat, based on the weight of said emulsion, a continuous aqueous phase including a stabil-izer, and an emulsifier system comprising a combination of a lipophilic emulsifier, and a hydrophilic emulsifier, the relative and total amounts of said emulsifiers and said stabilizer being effective to provide a stable emulsion and a product which is solid at 40 F; and cooling said emulsion under conditions effective to solidify it to form a product which is solid at 40°F.
36. A process according to claim 35, wherein said lipophilic emulsifier and other fat soluble components are blended with said fat at a temperature effective to provide a uniform blend, prior to preparing said emulsion.
37. A process according to claim 35 or 36, wherein said stabilizer is blended with said fat prior to preparing said emulsion.
38. A process according to claim 35, wherein said stabilizer is blended with water at a temperature and with sufficient agitation to provide a uniform suspension, prior to preparing said emulsion.
39. A process according to claim 35, 36 or 38, wherein said hydrophilic emulsifier is blended with water prior to pre-paring said emulsion.
40. A process according to claim 35 or 36, wherein said hydrophilic emulsifier is blended with said fat prior to preparing said emulsion.
41. A process according to claim 35, 36 or 38, wherein said emulsion is agitated after cooling to promote crystalliza-tion and enhance solidification.
42. A process according to claim 35, wherein all of the ingredients are thoroughly blended, at a temperature suffi-cient to maintain said fat in a liquid state, prior to homogeni-zation.
43. A process according to claim 42, wherein the blended ingredients are homogenized at a temperature of from 120 to 190°F.
44. A process according to claim 43, wherein a temperature of from 130 to 150°F is used.
45. A process according to claim 43 or 44, wherein said blended ingredients are homogenized at a pressure of from 100 to 500 atmospheres.
46. A process according to claim 43 or 44, wherein said blended ingredients are homogenized at a pressure of 250 atmospheres.
47. A process according to claim 43, wherein said emulsion is rapidly cooled to a temperature below 70°F after emulsification.
48. A process according to claim 47, wherein the rapid cooling is effected by a series of 3"A" units.
49. A process according to claim 47, wherein said emulsion is agitated after cooling to a maximum temperature of 50°F.
50. A process according to claim 35, 36 or 42, wherein the emulsion is cooled and then agitated in a "B" unit blender.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/095,644 US4273795A (en) | 1979-11-19 | 1979-11-19 | Low-fat spread and process |
US06/095,626 US4279941A (en) | 1979-11-19 | 1979-11-19 | Low-fat, butter-flavored spread and process |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1151466A true CA1151466A (en) | 1983-08-09 |
Family
ID=26790410
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000365992A Expired CA1151466A (en) | 1979-11-19 | 1980-12-02 | Low-fat, butter-flavored spread and process |
CA000365956A Expired CA1170498A (en) | 1979-11-19 | 1980-12-02 | Low-fat, spread and process |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000365956A Expired CA1170498A (en) | 1979-11-19 | 1980-12-02 | Low-fat, spread and process |
Country Status (13)
Country | Link |
---|---|
AU (1) | AU538723B2 (en) |
CA (2) | CA1151466A (en) |
DE (1) | DE3043655A1 (en) |
DK (1) | DK492780A (en) |
ES (1) | ES8205256A1 (en) |
FI (1) | FI69952C (en) |
FR (1) | FR2469877B1 (en) |
GB (1) | GB2066039B (en) |
IT (1) | IT1134321B (en) |
MX (1) | MX6378E (en) |
NL (1) | NL8006317A (en) |
SE (1) | SE450451B (en) |
WO (1) | WO1981001354A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10610035B2 (en) | 2015-03-20 | 2020-04-07 | Champions Of Butter, Inc. | Spreading device |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0098663B1 (en) * | 1982-07-08 | 1987-03-11 | Unilever N.V. | Process for the production of a reduced fat spread |
CA1237939A (en) * | 1984-06-11 | 1988-06-14 | Daniel W. Parke | Low fat spreads containing emulsion disruptors |
FR2580471B1 (en) * | 1985-04-22 | 1987-10-09 | Agronomique Inst Nat Rech | LOW LIPID SPREADABLE FOOD PRODUCT AND PROCESS FOR OBTAINING SAME |
GB8716111D0 (en) * | 1987-07-08 | 1987-08-12 | Unilever Plc | Edible plastic dispersion |
DE68910299T2 (en) * | 1988-12-23 | 1994-02-24 | Unilever Nv | Spread. |
DE3907676A1 (en) * | 1989-03-09 | 1990-11-22 | Kraft Europ R & D Inc | METHOD FOR PRODUCING A MARGARINE WITH A REDUCED FAT CONTENT |
DK0422713T3 (en) * | 1989-10-09 | 1995-04-10 | Unilever Plc | Edible lubricant |
US5346716A (en) * | 1992-08-28 | 1994-09-13 | Cumberland Packing Corp. | Low calorie low fat butter-like spread |
US5360627A (en) * | 1992-11-30 | 1994-11-01 | Van Den Bergh Foods Co., Division Of Conopco, Inc. | Reduced fat shortening substitute for bakery products |
DE19736429C2 (en) * | 1996-08-29 | 1998-11-19 | Karlheinz Altvater | Spread of cola drinks |
DE19730150C1 (en) * | 1997-07-14 | 1998-10-08 | Claudia Wagner | Food with banana and chocolate and/or nut flavour |
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---|---|---|---|---|
US3117010A (en) * | 1960-08-26 | 1964-01-07 | Atlas Chem Ind | Liquid shortening emulsions |
US3223532A (en) * | 1963-08-06 | 1965-12-14 | Grace W R & Co | Emulsions for food use |
US3350209A (en) * | 1965-04-07 | 1967-10-31 | Germantown Mfg Company | Stabilized topping |
ES336574A1 (en) * | 1966-03-08 | 1968-08-16 | Grace W R & Co | A method of preparing a plastic low-fat content food spread |
US3479190A (en) * | 1966-05-23 | 1969-11-18 | Hercules Inc | Edible compositions and process |
AU411013B2 (en) * | 1970-01-22 | 1971-02-22 | Fuji Oil Company, Limited | Whipping topping anda process for producing thesame |
DE2006418C3 (en) * | 1970-02-12 | 1973-10-25 | Fuji Oil Co. Ltd., Osaka (Japan) | Protein-free base for the production of whipped cream and the use of the base for the production of oil in water emulsions |
GB1335502A (en) * | 1972-01-10 | 1973-10-31 | Top Scor Products | Frozen confection stabilizer systems |
US4115548A (en) * | 1974-01-18 | 1978-09-19 | The Procter & Gamble Company | Detergent compositions comprising modified proteins |
US4089981A (en) * | 1976-06-04 | 1978-05-16 | Maxfibe Foods, Inc. | Fibrous simulated food product with gel structure |
US4107343A (en) * | 1976-11-08 | 1978-08-15 | Scm Corporation | Whippable emulsion stable at room temperature |
US4146652A (en) * | 1977-01-28 | 1979-03-27 | Rich Products Corporation | Intermediate moisture, ready-to-use frozen whippable foods |
US4208444A (en) * | 1977-11-30 | 1980-06-17 | Scm Corporation | Whippable topping mix |
GB2014426B (en) * | 1978-02-17 | 1982-06-03 | Unilever Ltd | Artifical creams |
US4238520A (en) * | 1979-06-28 | 1980-12-09 | Scm Corporation | Low-fat comestible spread substitutes |
-
1980
- 1980-11-14 SE SE8007996A patent/SE450451B/en not_active IP Right Cessation
- 1980-11-14 WO PCT/US1980/001539 patent/WO1981001354A1/en unknown
- 1980-11-17 IT IT26048/80A patent/IT1134321B/en active
- 1980-11-17 FI FI803591A patent/FI69952C/en not_active IP Right Cessation
- 1980-11-17 GB GB8036867A patent/GB2066039B/en not_active Expired
- 1980-11-18 AU AU64486/80A patent/AU538723B2/en not_active Ceased
- 1980-11-19 MX MX809170U patent/MX6378E/en unknown
- 1980-11-19 FR FR8024559A patent/FR2469877B1/en not_active Expired
- 1980-11-19 ES ES496983A patent/ES8205256A1/en not_active Expired
- 1980-11-19 DK DK492780A patent/DK492780A/en not_active Application Discontinuation
- 1980-11-19 NL NL8006317A patent/NL8006317A/en not_active Application Discontinuation
- 1980-11-19 DE DE19803043655 patent/DE3043655A1/en not_active Ceased
- 1980-12-02 CA CA000365992A patent/CA1151466A/en not_active Expired
- 1980-12-02 CA CA000365956A patent/CA1170498A/en not_active Expired
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10610035B2 (en) | 2015-03-20 | 2020-04-07 | Champions Of Butter, Inc. | Spreading device |
Also Published As
Publication number | Publication date |
---|---|
GB2066039A (en) | 1981-07-08 |
IT8026048A0 (en) | 1980-11-17 |
DK492780A (en) | 1981-05-20 |
MX6378E (en) | 1985-05-23 |
AU6448680A (en) | 1981-05-28 |
DE3043655A1 (en) | 1981-05-27 |
CA1170498A (en) | 1984-07-10 |
FI69952B (en) | 1986-01-31 |
ES496983A0 (en) | 1982-06-01 |
IT1134321B (en) | 1986-08-13 |
NL8006317A (en) | 1981-06-16 |
WO1981001354A1 (en) | 1981-05-28 |
AU538723B2 (en) | 1984-08-23 |
FR2469877A1 (en) | 1981-05-29 |
FI803591L (en) | 1981-05-20 |
FR2469877B1 (en) | 1985-07-12 |
GB2066039B (en) | 1984-04-04 |
FI69952C (en) | 1986-09-12 |
SE450451B (en) | 1987-06-29 |
ES8205256A1 (en) | 1982-06-01 |
SE8007996L (en) | 1981-05-20 |
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MKEX | Expiry |