Method of preparing reduced fat spreads
A food composition useful as a table spread and having a reduced level of fat and/or oil is provided. The composition is a macroscopically homogeneous blend of an oil and an aqueous phase associated with a fragmented granular starch hydrolysate. The fragmented granular starch hydrolysate is capable of forming an aqueous dispersion at 20% starch hydrolysate solids having a yield stress of from about 100 to about 1,500 pascals. Also provided is a method of preparing a table spread which comprises making a premix of the granular starch hydrolysate and oil and then homogenizing the premix to fragment the granular starch hydrolysate and form a macroscopically homogeneous blend.
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This invention relates to food formulations in which at least a portion of the fat and/or oil is replaced by a carbohydrate.
BACKGROUND OF THE INVENTIONU.S. Pat. No. 4,510,166 (Lenchin et al.) discloses converted starches having a DE less than 5 and certain paste and gel characteristics which are used as a fat and/or oil replacement in various foods, including ice cream and mayonnaise. The converted starches are described as dextrins, acid-converted starches (fluidity starches), enzyme-converted starches and oxidized starches. It is also disclosed that if the converted starches are not rendered cold-water soluble by the conversion, they are pregelatinized prior to use or cooked during use.
A product bulletin entitled "Paselli SA2; The Natural Alternative to Fats and Oils" (Avebe b.a., Foxhol, Holland, Ref. No. 05.12.31.167 EF) discloses the use of a low-DE-hydrolysate (DE less than 3) made from potato starch as a replacement for fifty percent of the fat with an amount of the low-DE-potato starch hydrolysate plus water (starch hydrolysate at 28% dry solids) equal to the amount of fat replaced.
U.S. Pat, Nos. 3,962,465 (Richter et al.) and 3,986,890 (Richter et al.) disclose the use of thermoreversible gels of a starch hydrolysate (formed by enzymatic hydrolysis) as a substitute for fat in a variety of foods, including cake creams and fillings, mayonnaise and remoulades, cream cheeses and other cheese preparations, bread spreads, pastes, meat and sausage products, and whipped cream.
The preparation of ready-to-spread frostings having reduced levels of calories is disclosed in U.S. Pat. No. 4,761,292 (Augustine et al.). The patent discloses a frosting which contains (a) about 40 to 85 weight percent sugar, at least about 20 weight percent of which comprises fructose; (b) about 1 to 12 weight percent of a granular starch having a cold-water solubility of greater than 50 weight percent and a fat content of less than 0.25 weight percent; (c) about 5 to 30 weight percent fat; and (d) about 10 to 30 weight percent water. The patent also discloses, at column 5, lines 25-38, that the preferred frostings contain 8 to 18 weight percent fat in comparison to conventional frostings which routinely contain about 18 to 30 weight percent fat.
U.S. Pat. No. 4,536,408 (Morehouse) discloses margarine or butter-like spreads of reduced caloric values which involve an edible fat at levels of from about 15 to 35% by weight of the spread and a low D.E. non-gelling starch hydrolysate having a D.E. value of about 4 and not more than 25. The spreads are described as water-in-oil emulsions.
U.S. Pat. No. 4,917,915 (Cain et al.) discloses spreads containing less than 35 wt. % fat comprising 10-35 wt. % continuous fat phase and 90-65 wt. % dispersed aqueous phase. The aqueous phase contains a gel-forming composition having a viscosity of at least 20 mPA.s when measured at 5.degree. C. and at a shear rate of 17090 sec.sup.-1. Gelling agents are stated to include gelling hydrolyzed starch derivatives, for example Paselli SA2, which is described as a gelling maltodextrin.
U.S. Pat. No. 4,591,507 (Bodor et al.) discloses edible water-in-oil emulsion spreads having an aqueous phase dispersed in a continuous fat phase and produced by incorporating, as a component of the dispersed phase of the emulsion, hydrated, non-crystalline, intact, undissolved starch particles. The starch is more particularly described as being swollen by the aqueous phase to a sub-maximal degree, thereby avoiding disintegration and ultimately dissolution in the starch in the aqueous phase. The emulsions are described as containing 20-70% by weight fat in the case of spreads of the reduced-fat type.
U.S. Pat. No. 4,587,131 (Bodor et al.) discloses edible water-in-oil emulsion spreads having an aqueous phase dispersed in a continuous fat phase and produced by incorporating, as a component of the dispersed phase of the emulsion, 1-25 wt. % based on the total emulsion, of discrete granules of agglomerates of native, crystalline starch granules, 80-100% of which have a diameter of less than 25 microns, preferably between 4 and 15 microns. The emulsions are described as containing 20-70% by weight fat in the case of spreads of the reduced-fat type.
SUMMARY OF THE INVENTIONThis invention relates to a composition of matter useful as a table spread comprising a macroscopically homogeneous blend of (i) a partially continuous aqueous phase having dispersed therein a fragmented granular starch hydrolysate comprised of a major amount of cold-water insoluble starch hydrolysate and a minor amount of cold-water soluble hydrolysate, and (ii) an oil phase, wherein the amount of said oil is less than about 40% by weight of the composition and wherein the amount of said fragmented granular starch hydrolysate dispersed in said aqueous phase is sufficient in relation to the amount of said oil to make said composition non-flowable. By "non-flowable" is meant that the blend will not flow to conform to its container, in the manner of a liquid, when at ambient temperature or lower.
It has been found that the compositions are relatively inert to both the "hot-oil" and "hot-water" tests which are commonly applied to table spreads to determine whether the spread is a water-in-oil emulsion (and so breaks when deposited into hot oil) or an oil-in-water emulsion (and so breaks when deposited in hot water). Thus, the term "partially continuous" has been used to describe the aqueous phase to denote that neither the aqueous nor the oil phase are continuous as in oil-in-water or water-in-oil emulsions, respectively.
However, it has also been found that the aqueous phase is apparently continuous in that at least a portion of the aqueous phase has apparently coalesced into thin, but continuous channels which randomly traverse the three dimensional structure of the composition. This has been confirmed by measuring the electrical conductivity of the composition. Thus, while there is some phase continuity, at least with respect to the aqueous phase, the composition can be considered an intimate mixture that is macroscopically homogeneous.
This invention also relates to a method of preparing a composition useful as a table spread comprising:
preparing a premix comprising a granular starch hydrolysate comprised of a major amount of cold-water insoluble starch hydrolysate and a minor amount of cold-water soluble hydrolysate and an oil, wherein the amount of said oil is less than about 40% by weight of the said premix, and
homogenizing said premix under conditions effective to fragment said granular starch hydrolysate and result in the production of a macroscopically homogeneous blend of (i) a partially continuous aqueous phase having dispersed therein a fragmented granular starch hydrolysate comprised of a major amount of cold-water insoluble starch hydrolysate and a minor amount of cold-water soluble hydrolysate, and (ii) an oil phase, wherein the amount of said oil is less than about 40% by weight of the blend and wherein the amount of said fragmented granular starch hydrolysate dispersed in said aqueous phase is sufficient in relation to the amount of said oil to make said blend non-flowable.
It has been found that the method of preparing the table spread wherein the granular starch hydrolysate is fragmented during homogenization of the aqueous phase with the oil results in a blend that is less susceptible to separation of the oil phase (i.e. oiling out) compared to a spread made by first fragmenting the granular starch to form an aqueous gel, followed by homogenization of the gel with an oil to prepare a table spread. Thus, the amount of emulsifier in the spread can be reduced without causing oiling out if this preferred method is employed.
The use of the terms "major" and "minor" in context together in this specification is meant to imply that the major component is present in a greater amount by weight than the minor component, and no more nor less should be inferred therefrom unless expressly noted otherwise in context.
DETAILED DESCRIPTION OF THE INVENTIONThis invention employs a fragmented granular starch hydrolysate. The granular starch hydrolysate will be capable of forming a particle gel upon fragmentation of the granular starch hydrolysate in an aqueous medium. The preparation of fragmented granular starch hydrolysates useful herein is disclosed in PCT Appln. No. PCT/US91/01029, published Sep. 5, 1991, the disclosure of which is incorporated by reference.
The fragmented, granular starch hydrolysate is made by the sequential acid-hydrolysis and fragmentation of a granular starch material, preferably derived from a starch having a major proportion of amylopectin. Starch is generally comprised of a highly-branched glucan having alpha-1,4 and alpha-1,6 linkages, denominated amylopectin, and a substantially linear glucan, having almost exclusively alpha-1,4 linkages, denominated amylose. Methods of determining the amounts of each are referenced in R. L. Whistler et al., Starch: Chemistry and Technology, pp. 25-35 (Academic Press, Inc., New York, N.Y., 1984), the disclosure of which is incorporated by reference. Examples of starches having a major proportion of amylopectin include the common non-mutant starches of cereals and legumes, e.g. corn, wheat, rice, potato and tapioca, and mutant varieties comprised of a major proportion of amylopectin, e.g. waxy maize. Preferred for use herein are common corn starch and waxy maize starch.
As used herein, the term "granular starch" refers to a starch composition in which the native granular structure is retained. Thus, this term, without further limitations, includes common starches and starches isolated from mutant varieties, e.g. waxy maize starch and high amylose corn starch. High amylose corn starch is commercially available in native granular form and having an amylose content within the range of about 50% to about 80%. For example, native granular starches, one with an amylose content of 55% to 60% and the other with about 70%, are available from National Starch and Chemical Corporation, Bridgewater, N.J., HYLON.TM. and Hylon VII, respectively. The starch should be in the native granular form to be useful as a starting material. This form is resistant to hydration and/or gelatinization during the acid-hydrolysis, and thus, fragments of the starch will retain many of the structural features of the native granule, e.g. the lamellae resulting from the growth pattern of the granule. By "gelatinization temperature" is meant the temperature at which a majority (by weight) of the granular starch starting material is "gelatinized" or "pasted". In other words, a product in which the gelatinization occurs with respect to minor amount of the granular starch starting material is within the scope of the granular starch hydrolysate, unless otherwise noted.
Various pretreatments of the native granule starting material can be performed so long as the resistance to gelatinization during acid-hydrolysis is preserved. A particularly useful pretreatment is defatting of the granule, e.g. by an alkaline wash as described in U.S. Pat. No. 4,477,480 (Seidel et al.), the disclosure of which is incorporated herein by reference, and/or a solvent extraction as described in U.S. Pat. Nos. 3,717,475 and 3,586,536 (Germino), the disclosures of which are incorporated by reference. The granular starch from which the hydrolysate is made should generally contain less than about 1.5% fatty acids and proteins. Because the hydrolysis is accomplished in a predominantly aqueous medium and is typically washed with only water, the hydrolysis will not remove any substantial portion of the lipids present in the starch. Further, because a substantial portion of the starch is hydrolyzed to products soluble in the aqueous medium and subsequent wash water, the hydrolysis and washing will remove starch solids and, thus, result in a lipid content on a weight percentage basis that is higher for the hydrolysate than the parent starch.
The acid-hydrolysis of the granular starch is performed to permit mechanical disintegration of the granular starch hydrolysate residue to a degree that will allow the formation of an aqueous dispersion that is salve-like. The hydrolysate will be capable upon mechanical disintegration of forming an aqueous dispersion (at about 20% hydrolysate solids) having a yield stress of from about 100 to about 1,500 pascals (for example, from about 200 to about 800 pascals or from about 200 to about 600 pascals), but more preferably from about 400 to about 1,500 pascals, and most preferably at least about 500 pascals.
The yield stress of an aqueous dispersion of fragmented starch hydrolysate has been found to correlate well with the fat-like consistency of the aqueous dispersion. In other words, if the yield stress is in an appropriate range, the aqueous dispersion will generally exhibit a fat-like consistency. However, yield stress may not correlate well with properties other than consistency. For example, a sample with an appropriate yield stress may exhibit a gritty mouthfeel (i.e. grittiness) due to aggregation of the insoluble hydrolysate particles (e.g. as a result of freeze-thaw of an aqueous dispersion of fragmented starch hydrolysate). Further, the correlation between yield stress and fat-like consistency may not hold in the converse for all fragmented starch hydrolysates described herein. In other words, a particular fragmented starch hydrolysate may exhibit a fat-like consistency under some conditions, but not exhibit an appropriate yield stress. In sum, while yield stress exhibits a useful correlation with fat-like consistency, yield stress is not believed to be a perfect predictor of fat mimicking properties of a fragmented starch hydrolysate.
An aqueous dispersion of fragmented granular starch hydrolysate should exhibit rheological properties characteristic of a particle gel. One measure of these properties is provided by measuring the dynamic elastic modulus (G') over a range of shear strain. A particle gel will exhibit a transition in G' versus shear strain from a substantially constant G' to a decreasing G' as shear strain increases. The transition indicates fracture of the particle network within the particle gel and is typically a sharp transition at a relatively low (compared to a polymer gel) shear strain. The particle gels useful herein will typically exhibit such a transition at less than about 50 millistrain, and preferably less than about 20 millistrain.
In general, the starch hydrolysate will have a peak molecular weight as measured by gel permeation chromatography of from about 2,000 g/mol to about 10,000 g/mol, preferably from about 3,500 g/mol to about 5,000 g/mol and more preferably from about 4,500 g/mol to about 5,000 g/mol.
It has been found that the weight average molecular weight (M.sub.w) as measured by gel permeation chromatography exhibits a better correlation (better than PMW) to the yield stress of an aqueous dispersion of the fragmented starch hydrolysate. The M.sub.w should generally range from about 3,000 to about 12,000, preferably about 4,000 to about 7,500 and more preferably 4,500 to about 6,500. Of course, M.sub.w also correlates to peak molecular weight, but some factors (e.g. the efficiency of washing of the product centrifuge cake which can affect the cold-water solubles content of the product) can affect the degree of correlation between M.sub.w and peak molecular weight from lot to lot of a given production run. Molecular weights of starch hydrolysates can be measured by the procedure described by J. Bouchard et al., "High-Performance Liquid Chromatographic Monitoring of Carbohydrate Fractions in Partially Hydrolyzed Corn Starch", J. Agric. Food Chem., Vol. 36, pp. 1188-1192 (1988), the disclosure of which is incorporated herein by reference.
The Dextrose Equivalent (by Lane-Eynon method DE) of the starch hydrolysate will vary based on the precise degree of hydrolysis and the efficiency of the washing of the starch hydrolysate, but will typically be greater than about 3, more typically greater than about 5, e.g. from about 5.0 to 7.0.
With an amylopectin based material, the fragmented granular starch hydrolysate will exhibit a bimaximal profile of oligomers of varying degree of polymerization with (i) a maximum in proximity to a degree of polymerization of about 13, and (ii) a maximum in proximity to a degree of polymerization of about 26. (A profile of the oligomeric composition of a starch hydrolysate (the "oligomer profile") can be obtained by the method described by K. Koizumi, et al., "High-Performance Anion-Exchange Chromatography of Homogeneous D-Gluco-Oligosaccharides and -Polysaccharides (Polymerization Degree equal to or greater than 50) With Pulsed Amperometric Detection", Journal of Chromatography, 46, pp. 365-373 (1989), the disclosure of which is incorporated by reference herein.)
The starch hydrolysates, and fragmented dispersions thereof, can be analyzed by a variety of techniques. For example, low angle (or "small angle") X-ray scattering experiments can be performed on an aqueous dispersion of a fragmented starch hydrolysate and the results (particularly those in the Porod region of the spectrum) may show an ordering (or lack thereof) in the dispersion in the range of tens to hundreds of angstroms. Such low-angle X-ray scattering techniques are described in F. Reuther, et al., "Structure of Maltodextrin Gels--A Small Angle X-Ray Scattering Study", Colloid and Polymer Science, 261, 271-276 (1983), the disclosure of which is incorporated by reference. Further, wide angle X-ray scattering techniques (e.g. those described by S. Nara, et al., "Study on Relative Crystallinity of Moist Potato Starch", Starke/Starch, Vol. 30, pp. 111-114 (1978)) can be performed on the starting starch, the starch hydrolysate powder and on the aqueous dispersion of fragmented starch hydrolysate to examine the effects of hydrolysis and/or fragmentation on the ordering of the starch material in the range of about 1-15 angstroms, i.e. ordering related to the distances between atoms in the starch material.
Nuclear magnetic resonance techniques (e.g. those described by S. Richardson, "Molecular Mobilities of Instant Starch Gels Determined by Oxygen-17 and Carbon-13 Nuclear Magnetic Resonance", Journal of Food Science, Vol. 53, No. 4, pp. 1175-1180 (1988)) can be used to show the electronic environment of atomic nuclei in the starch hydrolysate, e.g. C.sup.13 and thus give information relating to molecular structure and disposition (e.g. carbohydrate ring conformations, Vander Waals bonding, etc.). The technique of measuring water mobility (or immobility, its inverse) by oxygen-17 NMR may be supplemented with Raman infra-red spectroscopy techniques in the "water-band" of the infra-red portion of the spectrum (e.g. techniques such as those described by C. Luu, et al., "Model Structure for Liquid Water", Travaux de la Societe de Pharmacie de Montpellier, Vol. 41, No. 3, pp. 203-212 (1981), the disclosure of which is incorporated herein by reference). Differential Scanning Calorimetry (DSC) can be employed to examine the solubility of the starch hydrolysate in water (before and/or after fragmentation) over various temperatures. Such DSC techniques are described, for example, by D. C. White and G. N. Lauer, "Predicting Gelatinization Temperatures of Starch/Sweetener Systems for Cake Formulation by Differential Scanning Calorimetry. I. Development of a Model", Cereal Foods World, vol. 35, No. 8, pp. 728-731 (August 1990), the disclosure of which is incorporated by reference.
It should also be noted that the mean particle size of the starch hydrolysate, before and after fragmentation, can be measured by a variety of different means. However, the utility of such information must be considered carefully in view of the considerations noted by C. Orr, "Particle Size Measurement", Encyclopedia of Chemical Technology, Vol. 21, pp. 106-131 (Kirk-Othmer, eds., John Wiley & Sons, Inc., N.Y., N.Y., 1983), the disclosure of which is incorporated by reference. With this caveat in mind, it should be mentioned that the mean particle size, as measured by certain techniques, of the starch hydrolysate may appear to be substantially the same, e.g. about 10 microns (by light scattering techniques). However, when the aqueous dispersion of fragmented starch hydrolysate is analyzed to determine the surface area of the fragments, a mean particle size on the order of 50 angstroms to 200 angstroms may be inferred therefrom. Without wishing to be bound by any particular theory, unless otherwise noted, this particle size information suggests that the aqueous dispersion of fragmented starch hydrolysate contains agglomerates of fragments, such agglomerates being on the order of 10 microns in size and being comprised of individual fragments on the order of 50-200 angstroms. Further, it may be theorized that the agglomerates are malleable in the dispersion such that they deform (and perhaps undergo inter-agglomerate exchange of fragments) in a manner that imparts the property of plasticity to the dispersion. This plasticity may then give rise to the fat-like or salve-like consistency of the dispersion. This theory may also account for the fat-like mouth-clearing of the dispersion observed in many foods, e.g. frozen desserts. However, it should again be noted that these theories must be considered as such, unless otherwise expressly noted herein.
The acid hydrolysis can be accomplished in an essentially aqueous slurry of the starch. Typical conditions will include a starch slurry at 30% to 40% starch solids in 0.25N to 2.5N mineral acid (e.g. hydrochloric acid or sulfuric acid) maintained at a temperature of from about 50.degree. C. to about 70.degree. C., preferably from about 55.degree. C. to about 60.degree. C., more preferably from about 57.degree. C. to about 62.degree. C., for from about 8 to about 20 hours, preferably from about 10 to about 16 hours, when the acid is about 1N (and from about 8 to about 48 hours, preferably from about 20 to about 30 hours when the acid is about 0.5N). Variations within and around the scope of these parameters to optimize a particular set of conditions in conjunction with the means and degree of mechanical disintegration described below will be within the skill of the art given the examples set forth below.
It is believed that the moderate temperatures employed will reduce the amounts of reversion products produced during hydrolysis. Because reversion products tend to contribute off-flavors to the hydrolysate, minimizing their production should enhance the organoleptic acceptability of the hydrolysate by ensuring the production of a hydrolysate with a desirably bland taste. Likewise, the moderate reaction times will reduce opportunity for the development of rancidity in the hydrolysate that may occur over longer reaction times, e.g. more than a few days, as a result of the breakdown of even small amounts of residual lipids.
The hydrolysis medium is essentially aqueous. Generally, it will contain no more than a trace, if any, of organic solvents (e.g. ethanol). Organic solvents may react with the saccharide by-products (e.g. dextrose to form at least traces of ethyl glucoside), may otherwise affect the hydrolysis reaction (e.g. solvent effects) and/or may contaminate the starch hydrolysate product.
The progress of the hydrolysis may be followed by taking small samples of slurry from an in-progress batch of the starch hydrolysate, adjusting the pH of the slurry (e.g. to 4-5), isolating the solid starch hydrolysate residue from the slurry sample, and mechanically disintegrating the residue under the conditions intended for the batch as a whole. The yield stress of a 20% aqueous dispersion can then be measured to determine if the acid-hydrolysis has progressed to a desired degree. Also, samples of insoluble residue can be isolated for a determination of peak molecular weight (or weight average molecular weight) by gel permeation chromatography or of supernatant for dextrose content and the results used as a measure of the degree of hydrolysis; both molecular weight (particularly M.sub.w) and dextrose content have been found to correlate well with yield stress of the resulting starch hydrolysate upon fragmentation, as discussed below.
It has been found that there is very little, if any, change in the degree of branching of the glucan chains of the starch as a result of the acid hydrolysis. Thus, the ratio of 1,4 linkages to 1,6 linkages in the hydrolysate will generally be substantially the same as that of the starting amylopectin starch. Given the typical degree of branching of amylopectin and amylose, a starch comprised of a major proportion of amylopectin (i.e. greater than 50% by weight of the dry solids of the starch is glucan in the form of amylopectin) will exhibit a ratio of alpha-1,4 linkages to alpha-1,6 linkages of less than about 40:1. Thus, the starch hydrolysates will generally have a ratio of alpha-1,4 linkages to alpha-1,6 linkages of less than about 40:1, typically, from about 20:1 to about 40:1.
It has also been found that the crystalline form of the parent starch, as determined by X-ray diffraction, is retained without substantial change, although the relative crystallinity of the starch hydrolysate is generally greater than the parent starch. Thus, native waxy maize and native common corn starch (both of which are substantially free of the "B" type crystalline form) will generally yield hydrolysates that are substantially free of the "B" type as determined by X-ray diffraction.
The fragmented starch hydrolysate may also be otherwise chemically modified. Examples of such chemical modification include the product of reaction with bleaching agents (e.g. hydrogen peroxide, peracetic acid, ammonium persulfate, chlorine (e.g. calcium and/or sodium hypochlorite or sodium chlorite), and permanganate (e.g. potassium permanganate); esterifying agents (e.g. acetic anhydride, adipic anhydride, octenyl succinic anhydrides, succinic anhydride, vinyl acetate); including phosphorous compounds (e.g. monosodium orthophosphate, phosphorous oxychloride, sodium tripolyphosphate, and sodium trimetaphosphate); and/or etherifying agents (e.g. acrolein, epichlorohydrin, and/or propylene oxide). Such chemical modifications will typically be accomplished after the acid hydrolysis step, but may be accomplished prior to the acid hydrolysis or effected by using a modified starch as a starting material for the acid hydrolysis step. Even esterified starches (e.g. starch modified with octenyl succinic anhydride) can be used as a starting material and significant ester functionality will be retained.
The starch hydrolysis product of the slurry is isolated as the solid phase residue by separation thereof from the aqueous phase of the slurry. Techniques for such isolation include filtration (e.g. horizontal belt filtering), centrifugation (e.g. disk, decanter or solid bowl), sedimentation, and other suitable dewatering operations. It should also be noted that the efficiency of the separation of the insoluble starch hydrolysate residue from the aqueous liquid phase of the hydrolysate slurry and the degree of washing of the residue will affect the relative amounts of cold-water insoluble hydrolysate and cold-water soluble hydrolysate in the residue. However, it appears that the residue is relatively resistant to washing in the sense that relatively large amounts of cold-water solubles remain after washing (by simple reslurrying and recentrifugation at ambient temperatures). Thus, while the washing of the residue will affect the amount of cold-water soluble hydrolysate, conventional washing appears to have a surprisingly small effect.
The acid in the slurry can be neutralized either before or after isolation of the hydrolysate. However, it has been found particularly advantageous (in terms of obtaining a desirably bland flavor for the hydrolysate) to (i) only partially neutralize the slurry to a weakly acidic pH (e.g. from about 2.0 to about 3.5) and (ii) then hold the slurry at a moderately elevated temperature (e.g. 25.degree. C. to 75.degree. C.) for a short period of time (e.g. 15 minutes to 24 hours), prior to isolation, followed by washing and then neutralization of the solid hydrolysate residue to a substantially neutral pH (e.g. about 4.5 to about 5.0). This acid washing of the starch hydrolysate is particularly advantageous when employed in the context of microfiltration of the starch hydrolysate slurry using a ceramic microfiltration membrane contained within an acid resistant (e.g. polyvinyl chloride) housing.
It has been found that microfiltration is an effective means of separating an insoluble starch hydrolysate residue from an aqueous slurry thereof which also contains a relatively large amount of dissolved species, e.g. salt and saccharides. Microfiltration is described generally in D. R. Paul and C. Morel, "Membrane Technology", Encyclopedia of Chemical Technology, Vol. 15, pp. 92-131 (Kirk-Othmer, eds., John Wiley & Sons, N.Y., N.Y., 3d ed., 1981 ), the disclosure of which is incorporated herein by reference.
Typically, a liquid including small dissolved molecules is forced through a porous membrane. Large dissolved molecules, colloids and suspended solids that cannot pass through the pores are retained. Components retained by the membrane are collectively referred to as a concentrate or retentate. Components which traverse the membrane are referred to collectively as flitrate or permeate. Diafiltration is a microfiltration process in which the retentate is further purified or the permeable solids are extracted further by the addition of water to the retentate. This process is analagous to washing of a conventional filter cake. The use of microfiltration removes salts formed by the neutralization of the alkaline solution and other small molecular species.
Ultrafiltration is generally described and discussed by P. R. Klinkowski, "Ultrafiltration", Encyclopedia of Chemical Technology, Vol. 23, pp. 439-461 (Kirk-Othmer, eds., John Wiley & Sons,
N.Y., N.Y., 3d ed., 1983), the disclosure of which is incorporated by reference herein. Ultrafiltration is a pressure-driven filtration on a molecular scale. The porous membrane typically has a pore size ranging from 0.005 to 20 micrometers (or microns). While a distinction is often made in the separation art between ultrafiltration (pore size range of 2 to 20 nanometers) and microfiltration (pore size greater than 20 nanometers), the terms will be used interchangeably herein unless expressly noted otherwise.
By "microporous ceramic membrane" is meant any ceramic layer (including "supported layer articles") having micropores and sufficient structural integrity to withstand the pressure needed to isolate the insoluble starch hydrolysate residue from the liquid phase of the aqueous slurry over a desired period of time (e.g. from 15 minutes to 24 hours). It is believed that the high pressure used to isolate the insoluble starch hydrolysate residue creates turbulent flow at the membrane's surface which prevents small particles in the slurry from "blinding off" the pores of the membrane (as has been observed with conventional filtration equipment as discussed below).
A typical microporous ceramic membrane is comprised of a microporous ceramic article having at least one macroscopic passage therethrough (typically a cylindrical article having cylindrical passages) substantially parallel to the axis of symmetry of the cylindrical article. While the article may be "microporous" itself, the ceramic cylinder may act principally as a support (i.e. in a "supported layer article") for a microporous layer (or layers with regard to multi-passage articles) which covers the surfaces defined by the passages through the ceramic article. The porosity of the ceramic article, and any microporous layer associated therewith as described above, can be varied as desired, with the pore size of any such layer being smaller than that of the article. In typical operation, such a ceramic filter element (i.e. cylindrical and microporous ceramic article) is contained in hollow cylindrical housing and slurry is fed into the passages under pressure through a feed manifold that prevents leakage into the housing. The exit of the isolated starch hydrolysate residue from the passages at the other end of the ceramic filter element is controlled by an exit manifold which also prevents leakage into the housing where the flitrate or permeate is contained. Ceramic filter elements and their use are described in "Solve Tough Process Filtration Problems with Ceraflo Ceramic Systems", a technical bulletin, Lit. No. SD113, 2/89 89-418, published (1989) by Millipore Corporation, Bedford, Mass., the disclosure of which is incorporated by reference.
The isolated starch hydrolysate is typically washed and then dried (e.g. to a low moisture content, typically 3-8%) after isolation to allow for handling and storage prior to further processing. Examples of drying techniques include spray drying, flash drying, tray drying, belt drying, and sonic drying. The dried hydrolysate may be hygroscopic, given the presence of the cold-water soluble hydrolysate therein. Thus, some rehydration during handling and storage may occur. Depending upon the precise composition of the hydrolysate and the conditions (including length of time) of storage, steps to maintain the moisture at a low content may be necessary (e.g. moisture barrier packaging and/or control of humidity in the storage environment). If the moisture content is allowed to rise too far (e.g. greater than about 20%, or possibly greater than 15%), bulk handling problems and/or microbiological stability problems might arise.
A granular starch hydrolysate useful in the practice of this invention is commercially available from the A. E. Staley Manufacturing Company, Decatur, Ill., as STELLAR.TM. fat replacer.
In certain embodiments, this invention relates to a dry granular starch hydrolysate composition consisting essentially of a major amount by weight of cold-water insoluble hydrolysate and a minor amount by weight of cold-water soluble hydrolysate, said dry, granular starch hydrolysate having (a) weight average molecular weight of from about 4,000 g/mol to about 7,500 g/mol, (b) a bland organoleptic character, and (c) an essentially dry moisture content.
It has been found that the preferred hydrolysis process results in a granular starch hydrolysate composition that is particularly advantageous because of (i) the relative amounts of hydrolysate insolubles and hydrolysate solubles, (ii) weight average molecular weight, (iii) the bland organoleptic character of the granular starch hydrolysate, and (iv) edibility. This combination of properties is important to the use of the hydrolysate as a food ingredient, especially as a fat mimicking ingredient in foods. An essentially dry moisture content is important with respect to the edibility of the composition, e.g. the ability to handle and process the composition into a food product and the microbiological stability of the composition on storage thereof. The composition consists essentially of the major and minor amounts of hydrolysates of different solubility in the sense that it is essentially free of organic solvents and reaction products thereof with hydrolysate components (e.g. ethanol and ethyl glucosides).
In certain embodiments, this invention employs a composition of matter comprising (i) a major amount by weight of a granular starch hydrolysate, said granular starch hydrolysate having a weight average molecular weight of less than about 12,000 g/mol and being comprised of a major amount by weight of cold-water insoluble hydrolysate and a minor amount by weight of a cold-water soluble hydrolysate, and (ii) a minor amount of salt selected from the group consisting of alkali metal chlorides, alkali metal sulfates, alkaline earth metal chlorides, alkaline earth metal sulfates, and mixtures of two or more thereof, said salt being present in an amount sufficient to produce an organoleptically fat-like aqueous dispersion upon fragmentation of said composition in an essentially aqueous medium at about 20% dry solids of said starch hydrolysate. Typically, said salt is present in an amount of at least 0.1% basis dry weight of said granular starch hydrolysate, preferably at least about 1%, and more preferably about 1% to about 3%.
In certain embodiments, this invention employs a composition of matter comprising a major amount by weight of a granular starch hydrolysate having a weight average molecular weight of less than about 12,000 g/mol and being comprised of a controlled amount of salt present in an amount sufficient to enhance the fat-like characteristics of the composition upon shearing in an aqueous medium, said salt selected from the group consisting of alkali metal chlorides, alkali metal sulfates, alkaline earth metal chlorides, alkaline earth metal sulfates, and mixtures thereof.
In another aspect, this invention employs a composition of matter comprising (i) a major amount by weight of a granular starch hydrolysate, said granular starch hydrolysate having a weight average molecular weight of less than about 12,000 g/mol and being comprised of a major amount by weight of cold-water insoluble hydrolysate and a minor amount by weight of cold-water soluble hydrolysate, and (ii) a carbohydrate saccharide (in addition to said cold-water soluble hydrolysate) in an amount effective (e.g. a comparable amount by weight, see below) in relation to the amount of said fragmented granular starch hydrolysate and said water to enhance the fat-like properties of said dispersion following either freezing or heating to a temperature of about 72.degree. C.
In another aspect, this invention employs an aqueous dispersion useful as a replacement for fats and/or oils comprising a major amount by weight of water and a minor amount by weight of a fragmented granular starch hydrolysate, said fragmented granular starch hydrolysate being (i) comprised of a major amount by weight of cold-water insoluble hydrolysate material and a minor amount by weight of cold-water soluble hydrolysate material and (ii) capable of imparting to said dispersion at about 20% solids a yield stress of from about 100 to about 1,500 pascals.
It is believed that the cold-water soluble hydrolysate material improves the water immobilization capability of such cold-water insoluble hydrolysate material, as compared to an aqueous dispersion containing only cold-water insoluble material at the same level of cold-water insoluble material solids. In general, the "minor amount" will be a significant amount in terms of its effect on the properties of the composition, e.g. the ratio of cold-water insoluble to cold-water soluble will be no greater than about 9:1, typically less than about 5:1, and preferably from about 3.0:1 to about 4.0:1. It is also believed that the cold-water soluble hydrolysate material improves the water immobilization capability of such cold-water insoluble hydrolysate material, as compared to aqueous dispersion containing only cold-water insoluble material at the same level of cold-water insoluble material solids.
Following acid-hydrolysis (and neutralization of the slurry), the granular starch hydrolysate is subjected to a physical fragmentation as by mechanical disintegration, i.e. fragmented. As used herein, "fragmented" means that a majority of the starch granules have been so fragmented that they no longer exhibit, under microscopic examination, the macro-organization of the granule, e.g. the shape characteristic of that variety of granule. Generally, the concentric shells of material that are observed in the granule after the hydrolysis are not observed in a majority of the granules after fragmentation. However, the native crystallites present in the granule are retained (as confirmed by X-ray diffraction of the salves).
The mechanical disintegration of the hydrolysate may be carried out in several ways, as by subjecting it to attrition in a mill, or to a high speed shearing action, or to the action of high pressures. Disintegration is generally carried out in the presence of a major amount by weight of a liquid medium, preferably water. Although tap water is the preferred liquid medium for the dispersion of fragmented starch hydrolysate, other liquids are suitable provided sufficient water is present to hydrate the fragmented starch hydrolysate and, thus, result in a dispersion having a suitable yield stress. Sugar solutions, polyols, of which glycerol is an example, alcohols, particularly ethanol, isopropanol, and the like, are good examples of suitable liquids that can be in admixture with water in the liquid medium. It may also be convenient to fragment the starch hydrolysate in a non-hydrating medium (e.g. 95% ethanol), then solvent exchange with water, and finally redisperse the fragmented starch hydrolysate to form an aqueous dispersion. Typically, however, the starch hydrolysate will be physically fragmented in potable water. Thus, this invention relates to a method of making an aqueous dispersion useful as a replacement for fats and/or oils comprising physically fragmenting a minor amount by weight of an amylopectin starch hydrolysate in the presence of a major amount by weight of a liquid consisting essentially of water, said physically fragmenting being effective to yield an aqueous dispersion having a yield stress of from about 100 pascals to about 1,500 pascals.
The mechanical disintegration is preferably accomplished by subjecting an aqueous dispersion of the hydrolysate to high shear, e.g. in a Waring blender or a homogenizer such as that disclosed in U.S. Pat. No. 4,533,254 (Cook et al.) and commercially available as a .-+.MICROFLUIDIZER" from Microfluidics Corporation, Newton, Mass., or a homogenizer such as the RANNIE.TM. high pressure laboratory homogenizer, Model Mini-lab, type 8.30 H, APV P, annie, Minneapolis, Minn. Other suitable homogenizers include the model M3-10TBS from APV Gaulin, Arlington Heights, Ill. In general, the performance of homogenizers of the colloid mill type is improved by using a relatively low flow rate with back pressure with temperature at 55.degree.-65.degree. C. Other suitable devices, which provide mechanical shear, include continuous mixers, e.g. model 4M1H15A, from E. T. Oakes Corp., Islip, N.Y., and batch mixers, e.g. Breddo Likiwifier model LORWWSS-200, from American Ingredients, Kansas City, Mo.
The temperature of the starch hydrolysate must be maintained below the gelatinization (i.e. solubilization) temperature of the hydrolysate. Thus, it may be necessary to cool the hydrolysate during disintegration. For example, when shearing starch hydrolysate derived from waxy maize starch, the temperature of the aqueous dispersion is typically maintained between about 55.degree. C. and about 65.degree. C. Whatever method is used, the disintegration is carried out to such an extent that the resulting finely-divided product is characterized by its ability to form a salve-like suspension in the liquid medium in which it is attrited or in which it is subsequently dispersed. By a salve-like suspension or dispersion is meant one which will exhibit, at about 20% hydrolysate solids, a yield stress of at least about 100 pascals, typically from about 100 pascals to about 2,000 pascals.
It should be noted that it has been found that an aqueous dispersion of the hydrolysate generally exhibits an increase in viscosity over a period of hours following the mechanical disintegration. Thus, the yield stress values herein denote the yield stress about three hours after mechanical disintegration unless otherwise noted. It should also be noted that mechanical disintegration may be sufficient to produce an aqueous dispersion having the desired yield stress, but still leave a sufficient number of particles of sufficient size to exhibit a "particulate" or "chalky" mouthfeel when ingested. Such chalkiness can be reduced by reducing the particle size of the starch hydrolysate before, during or after mechanical disintegration so that substantially all (typically at least about 95%, preferably at least 99%) of the hydrolysate will pass a U.S. #400 mesh sieve (i.e. substantially all particles are less than 15 microns). An example of a milling device suitable for such size reduction is a TROST.TM. Air Impact Mill from Garlock, Inc., Newton, Pa.
In general, the fragmented granular starch hydrolysate is incorporated into the food as an aqueous dispersion, typically comprised of a major amount (i.e. greater than 50% by weight) of water or other liquid medium and a minor amount (i.e. less than 50% by weight, typically 10% to 40%) of starch hydrolysate solids. Thus, this invention relates to an aqueous dispersion useful as a replacement for fats and/or oils comprising a major amount by weight of water and a minor amount by weight of a fragmented granular starch hydrolysate, said fragmented granular starch hydrolysate being capable of imparting to said dispersion at about 20% solids a yield stress of from about 100 to about 1,500 pascals. Alternatively, the isolated hydrolysis product can be mixed with the food along with water and then subjected to disintegration in those instances when the other ingredients of the food are capable of withstanding the condition of disintegration, e.g. a salad dressing or imitation sour cream.
It is contemplated that commercial production and use may involve hydrolysis, mechanical disintegration, and drying (e.g. spray drying) of the fragmented starch hydrolysate to produce an item of commerce. This item of commerce will then be purchased by a food processor for use as an ingredient. To incorporate the dried, fragmented granular starch hydrolysate into a food product, it may be useful and/or necessary to further mechanically disintegrate the starch hydrolysate while dispersing it into the foodstuff in which it will be employed. However, the techniques employed for such mechanical disintegration should not need to be nearly as vigorous as the original mechanical disintegration prior to drying.
The fragmented, amylopectin starch hydrolysate, as well as other granular starch hydrolysates within the scope of this disclosure, should not be subjected to conditions (e.g. elevated temperature) which will cause the hydrolysate fragments (i.e. a majority by weight thereof) to dissolve. Thus, if the food formulation is to be cooked or otherwise heated, to temperatures sufficient to gelatinize (i.e. dissolve) the hydrolysate, such heating should be completed prior to the addition of the hydrolysate to the food. It should be noted, however, that in many foods that are heated, e.g. pastuerized, the duration of the elevation of temperature may be insufficient to dissolve the starch hydrolysate fragments.
It has further been found that the use of a homogenizer as disclosed in U.S. Pat, No. 4,533,254 is facilitated by the addition of a small amount (e.g. 5% by weight of the starch hydrolysate dry solids) of an emulsifier to the aqueous slurry of starch hydrolysate fed to the homogenizer. When relatively high solids slurries of starch hydrolysate are fed into the homogenizer without added emulsifier, the homogenizer tends to plug after extended operation. The addition of emulsifier (for example, a mixture of mono- and all-fatty acid glycerides, e.g. DUR-LO.TM. emulsifier from Van den Bergh Foods) prevents this plugging of the homogenizer. Other emulsifiers include polyglycerol esters, polysorbates, ethoxylated monoglycerides, sorbitan monostearate, lactylated esters, and lecithin. Homogenizers useful in forming suspensions or emulsions are described generally by H. Reuter, "Homogenization", Encyclopedia of Food Science, pp. 374-376, (M. S. Peterson and A. H. Johnson, eds., AVI Publ. Co., Westport, Conn., 1978), L. H. Rees and W. D. Pandolfe, "Homogenizers", Encyclopedia of Food Engineering, pp. 467-472 (C. W. Hall et al., eds., AVI Publ. Co., Westport, Conn., 1986 ), and W. C. Griffin, "Emulsions", Encyclopedia of Chemical Technology, vol. 8, pp. 900-930 (Kirk-Othmer eds., John Wiley & Sons, N.Y., N.Y., 3d ed., 1979), the disclosures of which are incorporated herein by reference.
The use of the fragmented, amylopectin starch hydrolysate allows for the replacement of a substantial portion (e.g. from 10% to 100% by weight) of the fat and/or oil in a table spread formulation, preferably more than about 50%, which for a margarine at about 80% oil translates to a fat content of less than about 40% by weight. The precise level of replacement that is possible without significantly decreasing the organoleptic quality of the food will generally vary with the type of table spread and the use for which it is intended. The term "fats and/or oils" is intended to broadly cover edible lipids in general, specifically the fatty triglycerides commonly found in foods. The terms thus include solid fats, plastic shortenings, fluid oils, and the like. Common fatty triglycerides include cottonseed oil, soybean oil, corn oil, peanut oil, canola oil, sesame oil, palm oil, palm kernel oil, menhaden oil, whale oil, lard, and tallow. The technology of fats and/or oils is described generally by T. H. Applewhite, "Fats and Fatty Oils", Encyclopedia of Chemical Technology, Vol. 9, pp. 795-831 (Kirk-Othmer, eds., John Wiley & Sons, N.Y., N.Y., 3d ed., 1980), the disclosure of which is incorporated by reference.
Generally, it will be desirable to remove sufficient fat from a given food formulation to achieve a reduction in calories of at least one-third per customary serving or make a label claim of "cholesterol-free". (In this regard, see, for example, the list of standard serving sizes for various foods published in Food Labelling; Serving Sizes, 55 Fed. Reg. 29517 (1990) (to be codified at 21 C.F.R. 101.12), the disclosure of which is incorporated herein by reference, and the restrictions on labelling "cholesterol-free" at Food Labelling; Definitions of the Terms Cholesterol Free, Low Cholesterol and Reduced Cholesterol, 55 Fed. Reg. 29456 (1990)). It should also be noted that the fat removed from a particular formulation may be replaced with an equal amount by weight of an aqueous dispersion of fragmented starch hydrolysate, but that such equality may not be necessary or desirable in all instances. Further, it may be desirable to remove fat and add another ingredient (e.g. a gum, polydextrose, a protein, etc.) along with the aqueous dispersion of starch hydrolysate.
While this invention is generally directed to the replacement of fat and/or oil in a food formulation, it is of course within the contemplation of this invention that a fragmented granular amylopectin starch hydrolysate will be used in an entirely new formulation to which it contributes fat-like organoleptic qualities but is not, in the strictest sense, replacing a pre-existing fat or oil ingredient. Moreover, it is contemplated that the fragmented granular amylopectin starch hydrolysate will have utility as a thickener, bodying agent, or the like in foods that normally do not have a significant fat or oil component. Further, it is contemplated that the combined use of fragmented granular amylopectin starch with fragmented, granular amylose starch (e.g. as a blend) may have certain advantages in many of the compositions described herein. For example, the amylopectin based material may promote a unique consistency while the amylose based material provides greater heat stability to the blend.
This invention relates to table spreads having an aqueous phase which contains the fragmented granular starch hydrolysate described above. As discussed above, the granular starch hydrolysate can be fragmented in an aqueous medium and then mixed with the oil component of the margarine or, preferably, the granular starch hydrolysate is fragmented during homogenization as part of a premix with the oil that is employed in the table spread.
The table spreads of this invention are, thus, a blend of an oil and a fragmented granular starch hydrolysate. As discussed above, the fragmented granular starch hydrolysate is dispersed in an aqueous phase. The table spreads are prepared by homogenizing a blend of the oil and an aqueous phase. In general, the blend will be at an elevated temperature during homogenization. The blend is cooled to or below ambient temperature (e.g. between 5.degree. and 10.degree. C.) after homogenization, generally with continued agitation during cooling.
Preferred oils for use in the table spreads of this invention include oils which have a solid fat index (SFI) that is relatively constant over the temperature range of 35.degree.-75.degree. F., and have an SFI of 0 at 95.degree. F. and higher. These oil properties will give a margarine that is plastic and spreadable at refrigerator temperature and at room temperature. The margarine will melt completely in the mouth and not leave a waxy coating.
Examples of such oils include STALEY.RTM. 400-3 margarine oil and STALEY 454-03 margarine oil which are intended for use in stick and tub margarines, respectively, and available from A. E. Staley Manufacturing Company. The stick margarine oils have a higher SFI. The higher SFI decreases spreadability, but increases firmness to allow the stick form of packaging.
Among the other functional ingredients in the table spread formulations of this invention include colors (e.g. beta-carotene), proteins (e.g. milk proteins), emulsifiers (e.g. lecithin, mono- and di-glycerides), salts (e.g. sodium chloride), thickeners (e.g. starches and hydrophilic colloids), preservatives (e.g. potassium sortbate), nutrients (e.g. carbohydrates, proteins, lipids, etc.), antioxidants, antimicrobial agents, non-fat milk solids, acidulants, and so on.
Hydrophilic colloids can include natural gum material such as xanthan gum, gum tragacanth, locust bean gum, guar gum, algin, alginates, gelatin, Irish moss, pectin, gum arabic, gum ghatti, gum karaya and plant hemicelluloses, e.g. corn hull gum. Synthetic gums such as water soluble salts of carboxymethyl cellulose can also be used. Starches can also be added to the food. Examples of suitable starches include corn, waxy maize, wheat, rice, potato, and tapioca starches.
Non-fat milk solids which can be used in the compositions of this invention are the solids of skim milk and include proteins, mineral matter and milk sugar. Other proteins such as casein, sodium caseinate, calcium caseinate, modified casein, sweet dairy whey, modified whey, and whey protein concentrate can also be used herein.
For flavored spreads, dry or liquid flavoring agents may be added to the formulation. These include cocoa, vanilla, chocolate, coconut, peppermint, pineapple, cherry, nuts, spices, salts, and flavor enhancers, among others.
Acidulants commonly added to foods include lactic acid, citric acid, tartaric acid, malic acid, acetic acid, phosphoric acid, and hydrochloric acid.
The following examples will illustrate the invention and variations thereof within the scope and spirit of the invention will be apparent therefrom. All parts, percentages, ratios and the like are by weight throughout this specification and the appended claims, unless otherwise noted in context.
EXAMPLES Example 1A reduced oil table spread, containing only 20% oil, was prepared as follows.
Stage 1: Multicomponent Dispersion for 20% Oil ______________________________________
Ingredients Wt. %
______________________________________
Part A
Deionized water (total) 76.43
Xanthan gum 0.089
Potassium sorbate 0.12
Calcium disodium EDTA 0.009
Salt 1.252
MYVATEX emulsifier (Texture Lite, Eastman)
0.5
(distilled propylene glycol monoesters,
monoglycerides and sodium stearoyl lactylate)
Part B
Starch hydrolysate powder, Run No. 6F (d.s.)
21.6
Total 100.00
______________________________________
Procedure
1. Put water in blender and stir at variac setting of 70.
2. Add other Part A ingredients and continue stirring for 1 minute.
3. Transfer to plastic beaker and stir vigorously with Servodyne.
4. Add dispersion powder slowly while stirring vigorously.
5. Run through MICROFLUIDIZER as immediately above.
Stage 2: Reduced Calorie Table Spread--20% Oil ______________________________________
Ingredisnts Wt. %
______________________________________
Part A
Margarine oil with TENOX
19.8
(a 0.05% solution of TENOX (Eastman)
in STALEY 400-03 oil)
MYVEROL 18-92 emulsifier (Eastman)
0.25
(monoglycerides)
MYVEROL 18-99 emulsifier (Eastman)
0.25
Lecithin (single bleached)
0.30
Beta-carotene (0.3% in oil)
0.20
(a 0.3% solution of beta-carotene (Roche)
in STALEY 400-03 oil)
Flavor (Firmenich 57.752/A)
0.07
Part B
Multicomponent dispersion
79.11
Total 100.00
______________________________________
Procedure to Make 500 Grams
1. Prepare multicomponent dispersion as directed.
2. Place Part A ingredients in a 600 ml plastic beaker and heat to 60.degree. C. on a steam bath.
3. Place Part B ingredients in a 600 ml glass beaker and heat to 50.degree.-60.degree. C. in a water bath.
4. Start stirring Part A vigorously with a Servodyne mixer.
5. Add Part B to Part A while continuing vigorous stirring.
6. Blend with Tekmar mixer for 4 minutes at variac setting of 70.
7. Transfer to an ice jacketed Kitchen Aid mixer and stir on speed 4 with a cake paddle until the temperature is 10.degree.-12.degree. C.
8. Transfer to a 600 ml plastic beaker and mix with the Tekmar mixer until a smooth uniform texture is obtained.
9. Refrigerate.
Example 2Another reduced oil table spread, containing only 20% oil, was prepared as follows:
Stage 1: Multicomponent Dispersion for 20% Oil Table Spread ______________________________________
Ingredients Wt. %
______________________________________
Part A
Deionized water (total) 76.48
Potassium sorbate 0.12
Calcium disodium EDTA 0.01
Salt 1.25
MYVATEX emulsifier 0.50
Part B
Starch hydrolysate powder, Run No. 6F (d.s.)
21.64
Total 100.00
______________________________________
Procedure
1. Heat water to 42.degree. C.
2. Put water in a beaker and start stirring vigorously with Servodyne.
3. Add other Part A ingredients while continuing vigorous stirring.
4. Run through MICROFLUIDIZER as above.
Stage 2: Reduced Calorie Table Spread--20% Oil ______________________________________
Ingredients Wt. %
______________________________________
Part A
Margarine oil with TENOX
19.82
(a 0.05% solution of TENOX (Eastman)
in STALEY 400-03 oil)
MYVEROL 18-92 emulsifier
0.25
MYVEROL 18-99 emulsifier
0.25
Lecithin (single bleached)
0.30
Beta-carotene (0.3% in oil)
0.20
(a 0.3% solution of beta-carotene (Roche)
in STALEY 400-03 oil)
Flavor (Firmenich 57.752/A)
0.07
Part B
Multicomponent dispersion
79.11
Total 100.00
______________________________________
Procedure to Make 500 Grams
1. Prepare multicomponent dispersion as directed.
2. Place Part A ingredients in a 600 ml plastic beaker and heat to 50.degree.-60.degree. C. on a steam bath.
3. Place Part B ingredients in a 600 ml glass beaker and heat to 50.degree.-60.degree. C. in a water bath.
4. Start stirring Part A vigorously with a Servodyne mixer.
5. Add Part B to Part A while continuing vigorous stirring.
6. Blend with Tekmar mixer for 4 minutes at variac setting of 80.
7. Transfer immediately to an ice jacketed Kitchen Aid mixer and stir on speed 4 with a cake paddle until the temperature is 10.degree.-12.degree. C.
8. Refrigerate.
Example 3A table spread, 20% oil, can be prepared without the use of a MICROFLUIDIZER type homogenizer, or extended Waring blender use, by the following two-stage procedure.
Stage 1:Multicomponent Dispersion ______________________________________
Ingredients Wt. %
______________________________________
Part A
Deionized water 75.03
Xanthan gum 0.089
Potassium sorbate 0.12
Calcium disodium EDTA 0.009
Salt 1.252
MYVATEX emulsifier 0.5
Part B
Starch hydrolysate powder, Run No. 6J (d.s.)
23.0
Total 100.00
______________________________________
Procedure
1. Heat water to 50.degree. C.
2. Put water in beaker and stir vigorously with Emil Greiner mixer.
3. Pre-mix dry ingredients by hand.
4. Add dry ingredients while continuing stirring.
5. Mix with Tekmar mixer about 2 minutes.
Stage 2: Reduced Calorie Table Spread--20% Oil ______________________________________
Ingredients Wt. %
______________________________________
Part A
Margarine oil with TENOX
19.82
(a 0.05% solution of TENOX (Eastman)
in STALEY 400-03 oil)
MYVEROL 18-92 emulsifier
0.25
MYVEROL 18-99 emulsifier
0.25
Lecithin (single bleached)
0.30
Beta-carotene (0.3% in oil)
0.20
(a 0.3% solution of beta-carotene (Roche)
in STALEY 400-03 oil)
Flavor (Firmenich 57.752/A)
0.07
Part B
Multicomponent dispersion
79.11
Total 100.00
______________________________________
Procedure to Make 500 Grams
1. Prepare multicomponent dispersion as directed.
2. Place Part A ingredients in a 600 ml plastic beaker and heat to 60.degree. C. on a steam bath.
3. Place Part B ingredients in a 600 ml glass beaker and heat to 50.degree.-60.degree. C. in a water bath.
4. Start stirring Part A vigorously with a Servodyne mixer.
5. Add Part B to Part A while continuing vigorous stirring.
6. Blend with Tekmar mixer for 4 minutes at variac setting of 80.
7. Transfer immediately to an ice jacketed Kitchen Aid mixer and stir on speed 3 with a cake paddle until the temperature is 7.degree.-10.degree. C.
8. Refrigerate.
Examples 4-6Reduced calorie table spreads (with 20% oil) were prepared as follows using the starch hydrolysates described in Examples 47-49 at pages 229 and 230 of PCT Appln. No. PCT/US91/01029, published Sep. 5, 1991, the disclosure of which is incorporated by reference.
______________________________________
Example
4 5 6
Washed High Unwashed
Waxy Amylose Waxy
Ingredients (parts by weight)
______________________________________
Part A
Margarine oil 19.82 19.82 19.82
(with antioxidant)
MYVEROL 18-99 emulsifier
0.25 0.25 0.25
MYVEROL 18-92 emulsifier
0.25 0.25 0.25
Lecithin (single bleached)
0.30 0.30 0.30
Beta-carotene (0.3% in
0.25 0.25 0.25
corn oil)
Flavor (Firmenich 57.752/A)
0.07 0.07 0.07
Part B
Xanthan gum 0.07 0.07 0.07
Potassium sorbate
0.04 0.04 0.04
Calcium disodium EDTA
75 ppm 75 ppm 75 ppm
Salt 1.20 1.20 1.20
Distilled water 17.74 18.94 18.94
Part C
Washed waxy dispersion
60.00 -- --
(25% d.s.)
High amylose dispersion
-- 60.00 --
(25% d.s.)
Unwashed waxy dispersion
-- -- 60.00
(40% d.s.)
______________________________________
Procedure to Make 500 Grams
1. Place Part A ingredients in a 600 ml plastic beaker and heat to 60.degree. C. on a steam bath. (Margarine oil is a 0.05% solution of antioxidant (TENOX, Eastman) in oil (STALEY 400-03).)
2. Weigh 20% more of Part B than needed and put in blender. Blend at variac setting of 70 for 2 minutes, then weigh the amount of this solution that is needed into a 250 ml plastic beaker.
3. Heat to 50.degree.-60.degree. C. in a microwave oven.
4. Start stirring Part A vigorously with a Servodyne mixer.
5. Pour Part B into Part A while continuing vigorous stirring.
6. Heat Part C to 50.degree.-60.degree. C. in a water bath.
7. Add Part C to the beaker while continuing vigorous stirring.
8. Blend with Tekmar mixer (ULTRA-TURREX, SD-45) for 4 minutes at variac setting of 70.
9. Transfer to an ice jacketed Kitchen Aid mixer and stir in speed 2 with a cake paddle until the temperature is 7.degree.-10.degree. C.
10. Transfer to a 600 ml plastic beaker and mix with the Tekmar mixer until a smooth uniform texture is obtained.
11. Refrigerate.
Calculated moisture levels for the table spreads were 62.7% for each of the washed waxy and high amylose and 54.9% for the unwashed waxy.
The 20% oil table spreads were evaluated with the following results.
Washed Waxy--Flavor was good, about the same as at 40% oil. The texture was more pasty than in any of the 40% oil products but still acceptable. The appearance after spreading on hot toast was about the same as for the 40% oil washed waxy spread. After freezing and thawing, the product lost some oil, the texture was more pasty than when fresh and the flavor was not quite as strong.
High Amylose--Flavor had a strong bitter and rancid aftertaste which made the product unacceptable. The texture was firmer and smoother and overall better than the waxy spread's texture at this oil level. The appearance after spreading on hot toast was about the same as for the 40% oil high amylose spread. After freezing and thawing, the product lost much oil and had a curdled grainy appearance and texture.
Unwashed Waxy--Flavor was less salty than the washed hydrolysate products. There was a slight bitter or metallic aftertaste. The texture was very soft and rendered the product unacceptable. Release from the mouth was very rapid. The appearance after spreading on hot toast was wet and pasty, the worst of all six spreads tested. After freezing and thawing, the product lost some oil. The texture was more pasty than when fresh and the flavor was sweeter.
Example 7A 20% oil table spread was prepared as follows:
Stage 1: Multicomponent Dispersion for 20% Oil Table Spread ______________________________________
Ingredients Wt. %
______________________________________
Deionized water 76.48
Potassium sorbate 0.12
Calcium disodium EDTA 0.01
Salt 1.25
MYVATEX emulsifier 0.50
Gelatin 0.40
(Hormel GP-8 Flavorset Gelatin;
250 bloom, 30 mesh)
Starch hydrolysate powder (d.s.)
21.24
Total 100.00
______________________________________
Procedure
1. Heat water to 42.degree. C.
2. Put water in a beaker and start stirring vigorously with Lightnin mixer.
3. Add other ingredients while continuing vigorous stirring.
4. Run through MICROFLUIDIZER as for other dispersions.
Inlet temperature=36.degree. C.
Pressure=13,000 psi
Outlet temperature=54.degree. C.
Stage 2: Reduced Calorie Table Spread--20% Oil ______________________________________
Ingredients Wt. %
______________________________________
Part A
Corn oil (liquid, non-hydrogenated)
19.84
MYVEROL 18-92 emulsifier
0.25
MYVEROL 18-99 emulsifier
0.25
Lecithin (single bleached)
0.30
Beta-carotene (0.3% in oil)
0.18
(a 0.3% solution of beta-carotene (Roche)
in STALEY 400-03 oil)
Flavor (Firmenich 57.752/A)
0.07
Part B
Multicomponent dispersion
79.11
Total 100.00
______________________________________
Procedure to Make 500 Grams
1. Prepare multicomponent dispersion as directed.
2. Place Part A ingredients in a 600 ml plastic beaker and heat to 50.degree.-60.degree. C. on a steam bath.
3. Place Part B ingredients in a 600 ml glass beaker and heat to 50.degree.-60.degree. C. in a water bath.
4. Start stirring Part A vigorously with a Servodyne mixer.
5. Add Part B to Part A while continuing vigorous stirring.
6. Blend with Tekmar mixer for 4 minutes at variac setting of 80-100.
7. Transfer immediately to an ice jacketed Kitchen Aid mixer and stir on speed 6-8 with a cake paddle until the temperature is 7.degree.-10.degree. C.
8. Transfer to 600 ml plastic beaker and mix with Tekmar mixer until smooth and firm (typically 40-60 seconds at variac 100).
9. Refrigerate.
Run 1The gelatin was dry blended with starch hydrolysate powder and creme was made normally.
Run 2Air whipped in on step 7 until final specific gravity was 0.90.
Run 3Same as Run 2, but STALEY margarine oil (400-03) replaced corn oil. Final specific gravity was 1.02.
Example 8A 20% oil table spread was prepared as follows:
Stage 1: Multicomponent Dispersion for 20% Oil Table Spread ______________________________________
Ingredients Wt. %
______________________________________
Deionized water 76.48
Potassium sorbate 0.12
Calcium disodium EDTA 0.01
Salt 1.25
MYVATEX emulsifier 0.50
Starch hydrolysate powder (d.s.)
21.64
Total 100.00
______________________________________
Procedure
1. Heat water to 42.degree. C.
2. Put water in a beaker and start stirring vigorously with Servodyne.
3. Add other ingredients while continuing vigorous stirring.
4. Run through MICROFLUIDIZER as for other dispersions. Targets are:
Inlet temperature=37.degree. C.
Pressure=15,000 psi
Outlet temperature=59.degree. C.
Stage 2: Reduced Calorie Table Spread--20% Oil ______________________________________
Ingredients Wt. %
______________________________________
Part A
Corn oil (liquid, non-hydrogenated)
20.02
MYVEROL 18-92 emulsifier
0.25
MYVEROL 18-99 emulsifier
0.25
Lecithin (single bleached)
0.30
Beta-carotene (0.3% in oil)
0.0018
(a 0.3% solution of B-carotene (Roche)
in STALEY 400-03 oil)
Flavor (Firmenich 57.752/A)
0.07
Part B
Multicomponent dispersion
79.11
Total 100.00
______________________________________
Procedure to Make 500 Grams
1. Prepare multicomponent dispersion as directed.
2. Place Part A ingredients in a 600 ml plastic beaker and heat to 50.degree.-60.degree. C. on a steam bath.
3. Place Part B ingredients in a 600 ml glass beaker and heat to 50.degree.-60.degree. C. in a water bath.
4. Start stirring Part A vigorously with a Servodyne mixer.
5. Add Part B to Part A while continuing vigorous stirring.
6. Blend with Tekmar mixer for 4 minutes at variac setting of 80-100.
7. Transfer immediately to an ice jacketed Kitchen Aid mixer and stir on speed 6-8 with a cake paddle until the temperature is 7.degree.-10.degree. C. Air whipped in step to final specific gravity of 0.80.
8. Transfer to 600 ml plastic beaker and mix with Tekmar mixer until smooth and firm (typically 40-60 seconds at variac 100).
9. Refrigerate.
Example 9A 20% oil table spread was prepared as follows:
Reduced Calorie Table Spread--20% Oil ______________________________________
Ingredients Wt. %
______________________________________
Part A
Margarine oil with TENOX
19.84
(a 0.05% solution of TENOX (Eastman)
in STALEY 400-03 oil)
MYVEROL 18-92 emulsion 0.25
MYVEROL 18-99 emulsion 0.25
Lecithin (single bleached)
0.30
Beta-carotene (0.3% in oil)
0.18
(a 0.3% solution of beta-carotene (Roche)
in STALEY 400-03 oil)
Flavor (Firmenich 57.752/A)
0.07
Part B
Multicomponent dispersion
79.11
Total 100.00
______________________________________
Procedure to Make 500 Grams
1. Prepare multicomponent dispersion as directed in Example 8.
2 Place Part A ingredients in a 600 ml plastic beaker and heat to 50.degree.-60.degree. C. on a steam bath.
3. Place Part B ingredients in a 600 ml glass beaker and heat to 50.degree.-60.degree. C. in a water bath.
4. Start stirring Part A vigorously with a Servodyne mixer.
5. Add Part B to Part A while continuing vigorous stirring.
6. Blend with Tekmar mixer for 4 minutes at variac setting of 80.
7. Transfer immediately to an ice jacketed Kitchen Aid mixer and stir on speed 8 with a cake paddle until the temperature is 7.degree.-10.degree. C.
8. Mix with Waring blender to final specific gravity of 1.04.
9. Refrigerate.
Example 10A 20% oil table spread was prepared as follows:
Reduced Calorie Table Spread--20% Oil ______________________________________
Ingredients Wt. %
______________________________________
Part A
Xanthan gum (Rhodigel CA. 86204.01)
0.10
Deionized water 25.00
Part B
Deionized water 28.70
Color 0.20
(a 0.4% solution of Warner Jenkinson
egg shade 08038 in deionized water.
Contains FD&C yellow #5 and FD&C yellow #6.)
Salt 1.00
Calcium disodium EDTA 0.01
Potassium sorbate 0.10
Starch hydrolysate powder (d.s.) (H126)
15.00
STAR-DRI .RTM. 15 maltodextrin
9.00
(Staley, 15 D.E.)
Part C
Margarine oil with TENOX 19.84
(a 0.05% solution of TENOX (Eastman)
in STALEY 400-03 oil)
MYVEROL 18-92 emulsifier 0.25
MYVEROL 18-99 emulsifier 0.25
Lecithin (single bleached) 0.30
Beta-carotene (0.3% in oil)
0.18
(a 0.3% solution of beta-carotene (Roche)
in STALEY 400-03 oil)
Flavor (Firmenich 57.752/A)
0.07
Total 100.00
______________________________________
Procedure to Make 800 Grams
1. Put Part A ingredients in Waring blender and blend on high speed for 1.5 minutes.
2. Place Part A ingredients in a Kitchen Aid mixer. Stir on low speed with cake paddle for about 10 minutes.
3. Heat Ingredients in Kitchen Aid mixer to about 50.degree. C. by putting "ice bath" on Kitchen Aid mixer and filling with water at 70.degree. C.
4. Heat Part C to 50.degree. C. on a steam bath.
5. Start stirring Part C vigorously with Lightnin mixer.
6. Add aqueous slurry (Parts A and B) to Part C while continuing vigorous stirring.
7. Run entire mixture through MICROFLUIDIZER.
Inlet temperature=42.degree. C.
Pressure=9,000 psi
Outlet temperature=54.degree. C.
8. Transfer immediately to an ice jacketed Kitchen Aid mixer and stir on speed 8 with a cake paddle until temperature is 13.degree.-15.degree. C. (about 15 minutes).
9. Refrigerate.
Example 11A 20% oil table spread was prepared as follows:
Reduced Calorie Table Spread--20% Oil ______________________________________
Ingredients Wt. %
______________________________________
Part A
Water 25.00
Xanthan gum, Rhodigel 0.10
Part B
Water 32.7306
Starch hydrolysate power 12.90
STAR-DRI 15 maltodextrin (Staley, 15 D.E.)
7.00
Whey powder, sweet, #27231
1.00
Salt 0.90
Potassium sorbate 0.10
Calcium disodium EDTA 0.0075
Artificial color, egg shade #08038
0.0004
Part C
STALEY 400-03 partially hydrogenated
corn oil 19.83
Monoglycerides (Dimodan LSK)
0.24
Lecithin (M-C-Thin AF1/SB)
0.15
Flavor (Firmenich 57.752/A)
0.03
Antioxidant (TENOX 2) 0.01
Beta-carotene, 30% in vegetable oil
0.0015
Total 100.00
______________________________________
Procedure
1. Use a high speed mixer to mix Part A ingredients until xanthan gum is dissolved.
2. Combine Part A and Part B ingredients and mix at slow speed until uniform.
3. While mixing, heat Part A and Part B mixture to 120.degree.-130.degree. F.
4. Mix Part C ingredients together and heat to 120.degree.-130.degree. F.
5. Pour aqueous phase (Parts A and B) into oil phase (Part C) while stirring vigorously.
6. Homogenize the entire mixture at a pressure of 8,000 to 15,000 psi and an output temperature of 140.degree.-150.degree. F.
7. Immediately cool to 50.degree. F. while stirring.
8. Pack off and refrigerate.
Example 12A 20% oil table spread was prepared as follows:
Reduced Calorie Table Spread ______________________________________
Ingredients Wt. %
______________________________________
Part A
Starch hydrolysate powder
14.00
STAR-DRI 15 maltodextrin 8.00
Salt 0.90
Calcium disodium EDTA 0.0075
Potassium sorbate 0.10
Citric acid monohydrate 0.02
Water 56.7485
Part B
Margarine oil (STALEY 400-03)
19.84
Monoglycerides (Dimodan LSK, Grinsted)
0.24
Lecithin (single bleached)
0.15
Beta-carotene 0.002
Flavor (Ottens #2964) 0.012
Total 100.00
______________________________________
Procedure
1. Weigh all Part A ingredients together and mix until homogenous.
2. Weigh all Part B ingredients together, heat to 120.degree. F., and stir well.
3. Mix all ingredients together until homogenous. It does not matter which part is poured into which.
4. Run the entire mixture through an APV Gaulin homogenizer and/or CR mixer (Cherry-Burrell, Louisville, Ky.).
5. Cool on scraped surface heat exchanger (Votator, Cherry-Burrell, Louisville, Ky.).
Example 13A 20% oil table spread was prepared as follows:
Reduced Calorie Table Spread ______________________________________
Ingredients Wt. %
______________________________________
Part A
Starch hydrolysate powder
14.00
STAR-DRI 10 maltodextrin 7.00
Salt 0.90
Calcium disodium EDTA 0.0075
Potassium sorbate 0.10
Citric acid monohydrate 0.02
Water 57.9505
Part B
Margarine oil (STALEY 400-03)
19.60
Monoglycerides (Dimodan LSK, Grinsted)
0.24
Lecithin 0.15
Beta-carotene 0.002
Flavor 0.03
Total 100.00
______________________________________
Procedure
1. Weigh all Part A ingredients together and mix until homogenous.
2. Weigh all Part B ingredients together, heat to 120.degree. F., and stir well.
3. Mix all ingredients together until homogenous. It does not matter which part is poured into which.
4. Run the entire mixture a 4" Oakes rotary mixer at 20 psi and 600 grams/min. flow rate. Input temperature to the Oakes mixer should be adjusted to obtain an output temperature of 80.degree. C.
5. Product from Oakes mixer was cooled to 10.degree. C. by stirring in a Kitchen Aid mixer over an ice bath.
Claims
1. A composition of matter useful as a table spread comprising a macroscopically homogenous blend of:
- (i) a disperse aqueous phase having dispersed therein a fragmented granular starch hydrolysate derived from a starch having a major proportion of amylopectin and having a molecular weight of from about 4,000 to about 7,500 g/mol and comprised of a major amount of cold-water insoluble starch hydrolysate and a minor amount of cold-water soluble hydrolysate, the ratio of said major amount of cold-water insoluble starch hydrolysate to said minor amount of cold-water soluble starch hydrolysate is from about 3.0:1 to no greater than about 9:1, wherein said granular starch hydrolysate will form an aqueous dispersion having a yield stress of from about 100 to about 1,500 pascals when fragmented in a aqueous medium at 20% starch hydrolysate solids, and
- (ii) a disperse oil phase, wherein the oil of said dispersed oil phase is a partially hydrogenated oil selected from the group consisting of corn oil, soybean oil, canola oil, cottonseed oil, peanut oil, and mixtures of two or more thereof, and wherein the amount of said oil is less than about 40% by weight of the composition and wherein the amount of said fragmented granular starch hydrolysate dispersed in said aqueous phase is sufficient in relation to the amount of said oil to make said composition non-flowable, said composition further comprising a salt selected from the group consisting of alkali metal chlorides, alkali metal sulfates, alkaline earth metal chlorides, alkaline earth metal sulfates, and mixtures of two or more thereof, in an amount of at least about 0.1% by weight of said starch hydrolysate.
2. A method of preparing a composition useful as a table spread comprising:
- preparing a premix of (i) a granular starch hydrolysate derived form a starch having a major proportion of amylopectin and having a molecular weight of from about 4,000 to about 7,500 g/mol and comprised of a major amount of cold-water insoluble starch hydrolysate and minor amount of cold-water soluble hydrolysate, the ratio of said major amount of cold-water insoluble starch hydrolysate to said minor amount of cold-water soluble starch hydrolysate is from about 3.0:1 to no greater than about 9:1, wherein said granular starch hydrolysate will form an aqueous dispersion having a yield stress of from about 100 to about 1,500 pascals when fragmented in a aqueous medium at 20% starch hydrolysate solids, and (ii) a partially hydrogenated oil selected from the group consisting of corn oil, soybean oil, canola oil, cottonseed oil, peanut oil, and mixtures of two or more thereof, wherein the amount of said oil is less than about 40% by weight of the premix, said premix further comprising a salt selected from the group consisting of alkali metal chlorides, alkali metal sulfates, alkaline earth metal chlorides alkaline earth metal sulfates, and mixtures of two or more thereof, in an amount of at least about 0.1% by weight of said starch hydrolysate, and
- homogenizing said premix under conditions effective to fragment said granular starch hydrolysate by mechanical disintegration and result in the production for macroscopically homogeneous blend of (i) a partially continuous aqueous phase having dispersed therein a fragmented granular starch hydrolysate comprised of a major amount of cold-water insoluble starch hydrolysate and a minor amount of cold-water soluble hydrolysate, and (ii) an oil phase, wherein the amount of said oil is less than about 40% by weight of the blend and wherein the amount of said fragmented granular starch hydrolysate dispersed in said aqueous phase is sufficient in relation to the amount of said oil to make said blend non-flowable.
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Type: Grant
Filed: May 22, 1992
Date of Patent: Jan 3, 1995
Assignee: A. E. Staley Manufacturing Company (Decatur, IL)
Inventor: Patrick C. Dreese (Decatur, IL)
Primary Examiner: Shean Wu
Law Firm: Arnold, White & Durkee
Application Number: 7/887,977
International Classification: A23D 700; A23L 105; A23G 300;
