WO1993024016A1 - Methode de preparation de produits a tartiner a faible teneur en matieres grasses - Google Patents

Methode de preparation de produits a tartiner a faible teneur en matieres grasses Download PDF

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Publication number
WO1993024016A1
WO1993024016A1 PCT/US1993/004409 US9304409W WO9324016A1 WO 1993024016 A1 WO1993024016 A1 WO 1993024016A1 US 9304409 W US9304409 W US 9304409W WO 9324016 A1 WO9324016 A1 WO 9324016A1
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Prior art keywords
oil
starch hydrolysate
amount
hydrolysate
cold
Prior art date
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PCT/US1993/004409
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English (en)
Inventor
Patrick C. Dreese
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A.E. Staley Manufacturing, Inc.
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Application filed by A.E. Staley Manufacturing, Inc. filed Critical A.E. Staley Manufacturing, Inc.
Publication of WO1993024016A1 publication Critical patent/WO1993024016A1/fr

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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
    • A23D7/005—Edible oil or fat compositions containing an aqueous phase, e.g. margarines characterised by ingredients other than fatty acid triglycerides
    • A23D7/0056—Spread compositions
    • 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"
    • 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
    • A23D7/02—Edible oil or fat compositions containing an aqueous phase, e.g. margarines characterised by the production or working-up
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
    • A23L29/30—Foods or foodstuffs containing additives; Preparation or treatment thereof containing carbohydrate syrups; containing sugars; containing sugar alcohols, e.g. xylitol; containing starch hydrolysates, e.g. dextrin
    • A23L29/35—Degradation products of starch, e.g. hydrolysates, dextrins; Enzymatically modified starches

Definitions

  • This invention relates to food formulations in which at least a portion of the fat and/or oil is replaced by a carbohydrate.
  • U.S. Patent No. 4,510,166 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 pregeiatinized prior to use or cooked during use.
  • a product bulletin entitled "Paselli SA2; 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 pregeiatinized prior to use or cooked during use.
  • thermoreversible gels of a starch hydrolysate formed by enzymatic hydrolysis
  • a starch hydrolysate formed by enzymatic hydrolysis
  • the preparation of ready-to-spread frostings having reduced levels of calories is disclosed in U.S. Patent 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. Patent No. 4,536,408 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 . Patent 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 PA. s when measured at 5°C and at a shear rate of 17090 sec
  • Gelling agents are stated to include gelling hydrolyzed starch derivatives , for example Paselli SA2, which is described as a gelling maltodextrin .
  • U . S . Patent No. 4,591 , 507 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 . Patent No. 4, 587 , 131 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.
  • This 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.
  • 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.
  • 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) .
  • 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 .
  • 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
  • SUBSTITUTE SHEET composition This has been confirmed by measu ring the electrical conductivity of the composition .
  • 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 granula r 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 f ragment said g ranular starch hydrolysate and result in the production of a macroscopically homogeneous blend of (i ) a pa rtially continuous aqueous phase having dispersed therei n a f ragmented granular starch hydrolysate comprised of a major amount of cold-water insoluble starch hydrolysate and a minor amount of cold-water sol uble hydrolysate , and ( i i ) an oil phase, wherein the amount of said oil is less than about
  • This 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 September 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.
  • 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.
  • 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.
  • 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%.
  • native granular starches one with an amylose content of 55% to 60% and the other with about 70%, are available from National
  • 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.
  • 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 a minor amount of the granular starch starting material is within the scope of the granular starch hydrolysate, unless otherwise noted .
  • 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. Patent No. 4,477,480 (Seidel et al.),
  • TE SHEET the disclosu re of which is incorporated herein by reference, and/or a solvent extraction as described in U . S . Patent 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 .
  • the acid-hydrolysis of the granular starch is performed to permit mechanical disintegration of the granular starch hydrolysate residue to a deg ree that will allow the formation of an aqueous dispersion that is salve-li ke .
  • 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- li ke consistency of the aqueous dispersion .
  • the aqueous dispersion wi ll generally exhibit a fat-like consistency.
  • yield stress may not correlate well with properties other than consistency.
  • 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).
  • yield stress may not hold in the converse for all fragmented starch hydrolysates described herein.
  • a particular fragmented starch hydrolysate may exhibit a fat-like consistency under some conditions, but not exhibit an appropriate yield stress.
  • 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.
  • G' dynamic elastic modulus
  • 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.
  • 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/moi, 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.
  • M weight average molecular weight
  • the M 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.
  • M also correlates to peak molecular weight, but some factors
  • 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.
  • 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 can be obtained by the method described by K. Koizumi, et al., "High-Performance Anion-Exchange Chromatography of
  • 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
  • T TE SHEET 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)
  • 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. Lun, et al., "Model
  • DSC Differential Scanning Calorimetry
  • 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.
  • 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.
  • the acid hydrolysis can be accomplished in an essentially aqueous slurry of the starch .
  • Typical conditions will include a starch slu rry at 30% to 40% starch solids in 0.25 N to 2.5 N mineral acid (e. g . hydrochloric acid or sulfuric acid) maintained at a temperature of from about 50°C to about 70°C, preferably from about 55°C to about 60°C , more preferably from about 57°C to about 62°C, for from about 8 to about 20 hours , preferably from about 10 to about 16 hours , when the acid is about 1 N (and from about 8 to about 48 hours , preferably from about 20 to about 30 hours when the acid is about 0. 5 N ) .
  • 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 .
  • 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 thei r production should enhance the organoleptic acceptability of the hydrolysate by ensu ring the production of a hydrolysate with a desi rably bland taste . Li kewise, the moderate reaction times will reduce opportunity for the development of rancidity in the hydrolysate that may occu r 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) . Organ ic 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.
  • organic solvents e. g . ethanol
  • Organ ic 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 slu rry 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 .
  • samples of insoluble residue can be isolated for a determination of peak molecular weight (or weight average molecula r weight) by gel permeation chromatography or of supernatant for dextrose content and the results used as a measu re of the degree of hydrolysis; both molecular weight (particularly M ) and dextrose content have been found to correlate well with yield stress of the resulting starch hydrolysate upon fragmentation , as discussed below .
  • the ratio of 1 , 4 lin kages to 1 , 6 lin kages in the hydrolysate will generally be substantially the same as that of the starting amylopectin starch .
  • a starch comprised of a major proportion of amylopectin (i.e.
  • 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.
  • the fragmented starch hydrolysate may also be otherwise chemically modified.
  • 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.
  • the starch hydrolysis product of the slu rry 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 . dis k, decanter or solid bowl) , sedimentation , and other suitable dewatering operations .
  • filtration e. g . horizontal belt filtering
  • centrifugation e . g . dis k, decanter or solid bowl
  • sedimentation e.g . dis k
  • the acid i n the slurry can be neutralized either before or after isolation of the hydrolysate .
  • E SHEET temperature e.g. 25°C to 75°C
  • a short period of time e.g. 15 minutes to 24 hours
  • washing and then neutralization of the solid hydrolysate residue 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.
  • 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.
  • 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 filtrate 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.
  • 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
  • microporous ceramic membrane 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
  • 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
  • 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.
  • a ceramic filter element i.e. cylindrical and microporous ceramic article
  • 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 filtrate or permeate is contained.
  • Ceramic filter elements and their use are described in "Solve Tough Process Filtration Problems with Ceraflo
  • 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.
  • 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.
  • UTE SHEET 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, Illinois , as STELLAR fat replacer.
  • 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
  • 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
  • the TE SHEET 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) .
  • 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 f rom the group consisting of al kali metal chlorides , al kali metal sulfates , al kaline earth metal chlorides , al kaline earth metal sulfates , and mi xtu res of two or more thereof , said salt bei ng present in an amount sufficient to produce an organoleptically fat-li ke aqueous dispersion upon fragmentation of said composition in an essentially aqueous medium at about 20% dry solids of said starch hydrolysate .
  • 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%.
  • this invention employs a composition of matter comprising a major amou nt by weight of a granular starch hydrolysate havi ng a weight average molecular weight of less than about 12 , 000 g/mol
  • BSTITUTE SHEET 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 sait selected from the group consisting of alkali metal chlorides , alkali metal sulfates , alkaline earth metal chlorides , alkaline earth metal sulfates , and mixtures thereof .
  • 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 .
  • 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 f rom about 100 to about 1 , 500 pascals .
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 .
  • tap water is the preferred liquid medium for the dispersion of f ragmented starch hydrolysate
  • other liquids are suitable provided sufficient water is present to hydrate the f ragmented 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 li ke 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 .
  • 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 f rom about 100 pascals to about 1 , 500 pascals .
  • the mechanical disintegration is preferably accomplished by subjecting an aqueous dispersion of the
  • HEET hydrolysate to high shear e.g. in a Waring blender or a homogenizer such as that disclosed in U.S. Patent No. 4,533,254 (Cook et al.) and commercially available as a "MICROFLUIDIZER" from Microfluidics Corporation, Newton, Massachusetts, or a homogenizer such as the
  • RANNIE high pressure laboratory homogenizer Model Mini-lab, type 8.30 H, APV Rannie, Minneapolis, Minnesota.
  • suitable homogenizers include the model M3-10TBS from APV Gaulin, Arlington Heights, Illinois.
  • the performance of homogenizers of the colloid mill type is improved by using a relatively low flow rate with back pressure with temperature at 55-65°C.
  • suitable devices which provide mechanical shear, include continuous mixers, e.g. model 4M1H15A, from E. T. Oakes Corp., Islip, New York, and batch mixers, e.g. Breddo Likiwifier model LORWWSS-200, from American Ingredients, Kansas City, Missouri.
  • 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.
  • the temperature of the aqueous dispersion is typically maintained between about 55°C and about 65°C.
  • 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.
  • a salve-like suspension or dispersion is meant one which Will exhibit, at about 20% hydrolysate solids, a yield
  • TITUTE SHEET stress of at least about 100 pascals, typically from about 100 pascals to about 2,000 pascals.
  • an aqueous dispersion of the hydrolysate generally exhibits an increase in viscosity over a period of hours following the mechanical disintegration.
  • the yield stress values herein denote the yield stress about three hours after mechanical disintegration unless otherwise noted.
  • 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).
  • 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.
  • 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
  • BSTITUTE SHEET being capable of imparting to said dispersion at about 20% solids a yield stress of from about 100 to about 1,500 pascals.
  • 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.
  • 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.
  • conditions e.g. elevated temperature
  • the hydrolysate fragments i.e. a majority by weight thereof
  • 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.
  • TITUTE SHEET that are heated, e.g. pastuerized, the duration of the elevation of temperature may be insufficient to dissolve the starch hydrolysate fragments.
  • TM acid glycerides e.g. DUR-LO emulsifier from Van den Bergh Foods
  • emulsifiers include polyglycerol esters, polysorbates, ethoxy iated monoglycerides, sorbitan monostearate, lactylated esters, and lecithin.
  • Homogenizers useful in forming suspensions or emulsions are described generally by H. Reuter, "Homogenization",
  • TITUTE SHEET 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.
  • fragmented granular amylopectin starch with fragmented , granular amylose sta rch may have certain advantages i n many of the compositions described herein .
  • 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 f ragmented granular starch hydrolysate described above .
  • the granula r starch hydrolysate can be fragmented in an aqueous medium and then mixed with
  • 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 . I n general, the blend will be at an elevated temperature during homogenization . The blend is cooled to or below ambient temperature (e. g . between 5 and 10°C) after homogenization , generally with continued agitation during cooling .
  • 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 35-75°F, and have an SFI of 0 at 95°F and higher. These oil properties will give a margarine that is plastic and spreadabie at refrigerator temperature and at room temperatu re . The margarine will melt completely in the mouth and not leave a waxy coating .
  • SFI solid fat index
  • Examples of such oils include STALEY ⁇ 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 .
  • UTE SHEET 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 sorbate), nutrients (e.g. carbohydrates, proteins, lipids, etc.), antioxidants, antimicrobial agents, non-fat milk solids, aciduiants, and so on.
  • 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 sorbate
  • nutrients e.g
  • 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.
  • 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.
  • Aciduiants commonly added to foods include lactic acid, citric acid, tartaric acid, malic acid, acetic acid, phosphoric acid, and hydrochloric acid.
  • MYVATEX emulsifier (Texture Lite, Eastman) 0.5 (distilled propylene glycol monoesters, monoglycerides and sodium stearoyl lactylate)
  • Beta-carotene (0.3% in oil) 0.20
  • Flavor (Firmenich 57.752/A) 0.07
  • Beta-carotene (0.3% in oil ) 0.20
  • a table spread , 20% oil can be prepared without the use of a MICROFLU I DIZER type homogenizer, or extended Waring blender use, by the following two- stage procedure.
  • 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
  • Reduced 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 September 5, 1991 , the disclosure of which is incorporated by reference.
  • SUBSTITUTE SHEET 10 Transfer to a 600 ml plastic beaker and mix with the Tekmar mixer until a smooth uniform texture is obtained.
  • 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
  • SUBSTITUTE SHEET 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.
  • a 20% oil table spread was prepared as follows:
  • Flavor (Firmenich 57.752/A) 0.07
  • the gelatin was dry blended with starch hydrolysate powder and creme was made normally .
  • a 20% oil table spread was prepared as follows:
  • 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
  • a 20% oil table spread was prepared as follows:
  • Margarine oil with TENOX 19.84 (a 0.05% solution of TENOX (Eastman) in STALEY 400-03 oil) MYVEROL 18-92 emulsion 0.25
  • a 20% oil table spread was prepared as follows:
  • Xanthan gum (Rhodigel CA. 86204.01) 0.10 Deionized water 25.00
  • Flavor (Firmenich 57.752/A) 0.07
  • Parts A and B Add aqueous slurry (Parts A and B) to Part C while continuing vigorous stirring.
  • a 20% oil table spread was prepared as follows :
  • a 20% oil table spread was prepared as follows :
  • Flavor (Ottens #2964) 0.012
  • a 20% oil table spread was prepared as follows :

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Abstract

Composition alimentaire destinée à être consommée en tartines et présentant une faible teneur en matières grasses et/ou en huile. Cette composition est un mélange macroscopiquement homogène d'une huile et d'une phase aqueuse associées à un hydrolysat d'amidon granulaire fragmenté. Cet hydrolysat permet d'obtenir une dispersion aqueuse à 20 % de matières solides d'hydrolysat d'amidon présentant une contrainte-limite d'environ 100 à 1 500 pascals. L'invention porte également sur une méthode de préparation de produits à tartiner consistant à mélanger préalablement l'hydrolysat d'amidon granulaire et l'huile puis à homogénéiser ce premier mélange pour fragmenter l'hydrolysat d'amidon granulaire et obtenir un mélange macroscopiquement homogène.
PCT/US1993/004409 1992-05-22 1993-05-10 Methode de preparation de produits a tartiner a faible teneur en matieres grasses WO1993024016A1 (fr)

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US07/887,977 USH1394H (en) 1992-05-22 1992-05-22 Method of preparing reduced fat spreads
US07/887,977 1992-05-22

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