[0001] The present invention relates to a method of preparing a stabilizing syrup for use
in acidified milk beverages.
[0002] Non-starch polysaccharides ("gums") such as pectin, carboxymethyl cellulose or soybean
polysaccharides traditionally have been used in acidified milk beverages, particularly
drinking yogurts, to prevent the precipitation of milk proteins, a phenomenon also
know as "wheying-off".
[0003] The milk protein (casein) has a roughly spherical sub-micelle aggregate structure
held together by hydrophobic bonds and salt bridges. These sub-micelles, which are
sterically stabilized by κ-casein "hairs", destabilize and begin to coagulate at a
pH of less than about 5.2. Destabilization is maximized at a pH of about 4,6, the
isoelectric point of casein, which is a pH typical of fermented milk beverages, including
drinking yogurts. A gum, such as high methoxy pectin, is traditionally added to such
beverages in order to stabilize the beverage and prevent precipitation of the proteins.
It is thought that the pectin adsorbs to the surface of the casein aggregates, probably
by electrostatic attraction and acts as a dispersing agent, preventing coagulation
by virtue of the adsorbed casein/pectin particle's electronic and/or steric properties.
[0004] Such gums are expensive ingredients, especially relative to starch. Replacement of
gum is therefore desirable in order to reduce the cost of the yogurt. However, the
removal or reduction of gums negatively impacts the stability of the beverage as well
as other organoleptic and structural properties. Consumers demand that food products
in which at least a portion of the gum has been removed retain the quality of the
corresponding conventional products. Previous attempts to stabilize drinking yogurts
with starch have indicated that starch must be added at levels that caused undesirable
thickening/viscosity as well as unacceptable mouthfeel and taste.
[0005] RU-C-2 183 407 discloses a modified com starch used in cultured milk products, these
being free of gums. US-A-4 590 077 discloses acidified milk beverages which are thickened
with starch. WO 01 96405 A disdoses acidic milk beverages which are stabilized by
pectin. US-A-6 093 439 reveals stabilizers and their uses to stabilize milk products,
including yoghurts and sour cream.
[0006] Accordingly, there is an ongoing need to replace the more expensive components of
acidified milk beverages such as gums, as well as to provide stability while maintaining
acceptable organoleptic and structural properties.
[0007] The present invention is directed to a process for preparing stabilizing syrup including
the steps of mixing starch such as waxy starches including hydroxypropylated and succinylated
types, starch acetates and starch phosphates, sugar and water and then cooking the
mixture to give a fully dispersed mixture. Stabilizing syrups prepared via this process
are taught by the present invention. The invention is also directed to a process for
preparing acidified milk beverages wherein the stabilizing syrup is blended with milk
product solids, and the acidified milk beverages prepared thereby.
[0008] These and other objects of the present invention will become apparent to one skilled
in the art from the following detailed description and examples below.
[0009] As previously noted, the present invention is directed to a method of preparing a
stabilizing syrup for use in acidified milk beverages comprising the steps of mixing
starch, sugar and water components together, cooking the mixed components to give
a dispersed stabilizing syrup, and blending the stabilizing syrup with milk product
solids.
[0010] All starches and flours (hereinafter "starch") may be suitable for use herein. Cold
temperature stable starches are particularly suitable. As defined herein, a cold temperature
stable starch is a starch which can be formulated in 1% w/w amount in a milk beverage
having a pH of less of between 3.9 to about 4.6, a solids content of less than 20%,
and a viscosity increase of less than 300 mPas (centipoise ("cP")), particularly less
than 200 mPas (cP), and more particularly less than 100 mPas (cP), wherein the viscosity
is measured at 50 RPM at 4 °C over two weeks time.
[0011] Starches suitable for use herein may be derived from a native starch or flour. As
used herein a native starch or flour is one as it is found in nature. Also suitable
are starches and flours derived from a plant obtained by standard breeding techniques
including crossbreeding, translocation, inversion, transformation or any other method
of gene or chromosome engineering to include variations thereof. In addition, waxy
starch or flours derived from a plant grown from artificial mutations and variations
of the above generic composition, which may be produced by known standard methods
of mutation breeding, are also suitable herein.
[0012] Typical sources for the starches and flours are cereals, tubers, roots, legumes and
fruits. The native source can be corn, pea, potato, sweet potato, banana, barley,
wheat, rice, sago, amaranth, tapioca, arrowroot, canna, sorghum, and waxy or high
amylose varieties thereof. As used herein, the term "waxy" is intended to include
a starch or flour containing at least 95% by weight amylopectin and the term "high
amylose" is intended to include a starch or flour containing at least 40% by weight
amylose. Low amylose and waxy starches are particularly suitable for use in the present
application, with waxy starches bering preferred. The term "starch" as used herein
is intended to specify single starches as well as blends of the suitable starches
described herein.
[0013] Suitable starches for use herein also include chemically modified starches,
i.
e., starch derivatives. Suitable modified derivatives include, without limitation,
starch esters and ethers such as starch acetate and starch succinate. Such modified
derivatives particularly suited in the present application include starch acetate
derivatives treated with up to 10% w/w reagent on the starch, and preferably with
up to 4% w/w reagent. Such modified derivatives particularly suited in the present
application also include starch hydroxyalkylates, particularly hydroxypropylated starch
treated with up to 25% w/w propylene oxide on starch, and preferably up to 10% w/w
propylene oxide. The preparation and properties of such starches are known and described
in the art in, for example, R. L. Whistler, J.N. BeMiller, and E. F. Paschall,
Starch Chemistry and Technology, 2
nd Ed., Academic Press, Inc., London, Chpt. 9, Sect 5, pp. 343-349 (1984), and R. L
Whistler and J. R. Daniel,
Carbohydrates,
Food Chemistry, 2
nd Ed., O. R. Fenenma Ed., Marcel Dekker, Inc., New York, Chpt. 3, p. 119 (1985).
[0014] One skilled in the art will recognize that degraded starches are useful in the present
invention. However, non-degraded starches are preferred in that a lesser amount of
non-degraded starch is required in the beverage than degraded starch. Further, degraded
starches tend to negatively affect other characteristics of the beverage, such as
taste, versus non-degraded starches.
[0015] A particularly useful process for the preparation of the phosphorylated starches
is described in co-pending U.S. Serial No. 09/633,832, filed August 7, 2000. The process
includes impregnating the desired starch with a phosphate reagent, and optionally,
an oligosaccharide. From its fluidized state, the impregnated starch is then dried
to a virtually anhydrous state, preferably one percent by weight of the starch or
less, and heat-treated to effect phosphorylation. The impregnation of the starch by
oligosaccharide and phosphate reagent may be done in any order. The pH of the resultant
slurry can then be adjusted to between 3 and 12, preferably between 6 and 9.5.
[0016] "Phosphate reagent" as used herein includes any phosphate reagent used for phosphorylating
starch, such as ortho-, pyro-, meta- and tripolyphosphates. Illustrative phosphate
reagents are the alkali metal phosphates, such as sodium and potassium ortho-phosphate,
phosphoric acid, phosphorus oxychloride, sodium and potassium tripolyphosphate, and
sodium and potassium trimetaphosphate. The reagent may be a mono-, di- or trialkyl
metal phosphate or combinations thereof. Sodium tripolyphosphate is particularly ("STP")
useful.
[0017] Impregnation by the phosphate reagent may be accomplished by adding the reagent in
an amount of less than 15% by weight of starch, preferably less than 10%. The phosphate
reagent may be added in the dry state to wet starch granules, or by dissolving the
reagent in water to form an aqueous solution which is then mixed with the starch granules.
These impregnation techniques are described in U.S. Patent Nos. 4,166,173 and 4,216,310.
[0018] Any oligosaccharide may be suitable for use herein and may be derived from any native
source such as those listed above, The source may be the same as or different from
that of the starch component. As defined herein, oligosaccharide contains from one
to twenty sugar units joined by glycosidic bonds. Oligosaccharide is intended to include
monosaccharides, disaccharides, oligosaccharides, maize syrup solids, and malto dextrins.
Oligosaccharide suitable for the present invention include, but are not limited to,
debranched starches, maize syrup solids, dextrose, fructose, maltose, particularly
maize syrup solids with a DE of from 20 to 40. Although oligosaccharide is intended
to include monosaccharides, these generally add color and/or flavor that may be undesirable
in many industrial applications. Therefore, particularly suitable oligosaccharides
for the present invention are those which contain at least two sugar units joined
by glycosidic bonds.
[0019] Addition of the oligosaccharide to the starch may be achieved by adding the oligosaccharide
dry or as an aqueous solution. In particular, the oligosaccharide may be added to
an agitated starch slurry, or starch may be added to a stirred, aqueous solution of
the oligosaccharide, In addition, an aqueous solution of the oligosaccharide may be
sprayed onto dry or wet starch granules.
[0020] The starch, impregnated with phosphate and optionally with oligosaccharides, is then
subjected to a fluidized state and heat-treated to effect the phosphorylation. Though
the heat treatment may be carried out in one step, it is preferably carried out in
two steps. First, the impregnated starch is subjected to the fluidized state and dried
at less than 140 °C, preferably between 60 °C and 140 °C, and most preferably between
100 and 125 °C, to virtually anhydrous conditions, preferably less than 1% moisture
content by weight of starch. Secondly, while still in the fluidized state, the dried
product is heated to between 100 and 185 °C, preferably between 120 and 140 °C for
30 to 300 minutes. At temperatures higher than about 150 °C, the processing time is
preferably less than 45 minutes.
[0021] The fluidized state is achieved by vigorous mixing of the solid starch particles
in vacuum or in a gas whereby a uniform distribution of starch throughout the vacuum
or gas may be attained. Vigorous mixing may be accomplished by using air or gas, at
or above atmospheric pressures in a fluidized bed reactor or by sufficient mechanical
agitation. Where pressurized gas is used to effect the fluidized state, the velocity
of the gas must achieve a minimum rate such that the particles are free to move and
exhibit a "fluidized state." The fluidized state results in very efficient heat transfer
and allows the starch to rapidly dry to a virtually anhydrous state at low temperature.
[0022] Suitable starches also useful in the present invention include cold temperature stable
starches that are known to be inherently low temperature solution stable, or starches
that are genetically modified to favor the low temperature, solution stability phenotype.
Such starches include, without limitation, waxy maize starches having at least one
recessive
sugary-2 allele. An example of such a starch includes waxy maize starch derived from a plant
having endosperm tissue which is heterozygous, with either one or two doses, for the
recessive
sugary-2 allele, described further in U.S. Patent No. 5,954,883. Another example includes
starch derived from a waxy maize plant of a wxsu2 (homozygous) genotype and translocations,
inversions, mutants and variants thereof, discussed in U.S. Patent No. 4,428,972.
[0023] Physically modified starches derived from the foregoing suitable starches may also
be suitable for use herein, including pregelatinized and converted starches. Pre-gelatinization
techniques include drum drying and spray drying, including spray drying using the
methods described in U.S. Patent Nos. 4,280,851; 4,600,480; 5,131,953; and 5,149,799,
and alcohol treatments as described in U.S. Patent No. 4,465,702. Conversion (degradation)
products derived from any of the starches, including fluidity or thin-boiling starches
prepared by oxidation, enzyme conversion, acid hydrolysis, heat and or acid dextrinization,
and/or sheared products may also be useful herein.
[0024] Any starch having suitable properties for use herein may optionally be purified by
any method known in the art to remove starch off flavors (also known as "off-notes")
and colors that are native to the starch or created during starch modification processes.
Suitable purification processes for treating the instant starches are disclosed in
European Patent Application No. 93101520.0 (Publication No. 0 554 818) to Eden
et al. Alkali washing techniques, for starches intended for use in either granular or pregelatinized
form, are also useful and described in U.S. Patent Nos. 4,477,480 to Seidel and 5,187,272
to Bertalan
et al. Purification by the starches by extraction with a fluid in the supercritical or
liquid phase is also useful and described in U.S. Serial No. 60/317,572, filed September
6, 2001.
[0025] Generally, suitable starches are used to prepare stabilizing syrups. These syrups
are subsequently blended with a milk solids solution. As stated above the invention
is directed to a process for preparing stabilizing syrup comprises mixing sugar, starch
and water and cooking the mixture to give a fully dispersed mixture. As defined herein,
a fully dispersed mixture indicates a mixture in which no starch granules are left
intact.
[0026] Useful cooking techniques may include, without limitation, low temperature and long
time processes ("LTLT"), high temperature and short time ("HTST") processes, and ultra
high temperature processes ("UHT"). LTLT pasteurization takes place at a minimum of
about 63 °C for about 30 minutes, allowing starch hydration and cooking. Higher temperature
processing covers a wide range of conditions and are described more fully in U.S.
Patent No. 6,247,507. Generally, HTST involves pasteurization at a minimum temperature
of about 72 °C for about 15 seconds. Under UHT conditions, the product must typically
reach a minimum temperature of about 138 °C for a minimum of about two seconds, more
particularly from about 4 to about 6 seconds.
[0027] Cooking may be achieved by a variety of methods known in the art including, without
limitation, tubular heat exchange, plate heat exchange, etc. A particularly useful
cooking technique is via HTST pasteurization conducted, for example, in a tubular
or plate heat exchanger at about 115 °C for about 3 seconds, or under such conditions
that a fully dispersed syrup is obtained.
[0028] The resultant stabilizing syrup is then optionally stored or used directly for preparing
acidified milk beverages. Preparation involves mixing the stabilizing syrup under
low shear (mechanical stirring). The syrup is mixed in a ratio of 10 to 60 percent
by weight with 0 to 3.5 % fat and 9 to 17 % milk solids product, which has been fermented
to a pH of 3.9 to 4.6, and homogenized according to techniques known in the art. The
ratio of stabilizing syrup to the fermented milk product solution can be adjusted
according to processing limitations and the desired characteristics of the acidified
milk product. The resultant acidified milk beverage may be further subjected to heat
treatment in order to extend storage life. Flavoring, coloring and other ingredients
characteristic of traditional acidified milk beverages may optionally be added to
the acidified milk beverage of the present invention.
[0029] As used herein, the term "acidified milk beverage" is defined as a beverage having
a total solids content of less than 20%, a pH of between 3.9 to 4.6, and a Brookfield
viscosity measured at 50 RPM and 4°C of less than 400 mPas (cP). More particularly,
the beverage has a viscosity of less than 300 mPas (cP). Even more particularly, the
beverage has a viscosity of between 100 mPas (cP) and 200 mPas (cP).
[0030] The starches of the method of the present invention may be used to replace substantially
all the gum traditionally used to stabilize acidified milk beverages. In order to
adequately stabilize acidified milk beverages, typically about 0.3% by weight gum
is used. Accordingly, the acidified milk beverages of the present invention contain
less than 0.15% by weight gum, particularly less than 0.1% by weight gum, and more
particularly less than 0.05% by weight gum of the beverage.
[0031] In addition to stabilizing acidified milk beverages, certain starches of the method
of the present invention may desirably retain certain organoleptic and structural
properties of the acidified milk beverages, particularly viscosity stability, mouthfeel
and taste. For example, the acidified milk beverages obtained by the method of the
present invention containing hydroxypropylated waxy corn starch substantially retain
their viscosity stability, mouthfeel and flavor in comparison to a corresponding beverage
containing 0.3% w/w of an industry standard pectin stabilizer.
[0032] The following examples will more fully illustrate the embodiments of this invention.
In the examples, all parts and percentages are by weight and all temperatures in degrees
Celsius unless otherwise noted.
EXAMPLES
Procedures
Measurement of Viscosity Stability
[0033] The viscosity of the acidified milk beverages was measured with a Brookfield LV/DV-III
viscometer equipped with a small sample adapter and a computer loaded with Brookfield's
Rheocalc software (Brookfield Rheocalc for Windows - Brookfield Engineering Laboratories,
Inc., Stoughton, Massachusetts). One ounce samples of the beverages stored at 4°C
were inverted once and then poured into the Brookfield Thermocel accessory (both accessory
and a SC4-31 spindle were pre-chilled in ice). A 50-250 RPM scan was then conducted
on the samples over approximately 2.5 minutes.
Measurement of Beverage Stability (also known as "Wheying-off")
[0034] Digital photos were taken of each acidified milk beverage after 1, 7 and 14 days
of storage at 4°C. The images were then analyzed using Sigma Scan Pro V 4.0 image
analysis software by manual definition (tracing with the mouse) of the clear liquid
region (or liquid separated from solids). A "trace measurement" was then run for total
area, thereby defining the total number of pixels in the defined area. The percent
wheying-off was determined based on the trace measurements.
Measurement of Organoleptic Proporties
[0035] Each sample of acidified milk beverage was evaluated by an expert for mouthfeel and
flavor on a scale of -4 to +4. Zero (0) is the value of the corresponding acidified
milk beverage prepared according to the procedure described in Example 3,
infra, and containing 0.3% of an industry standard pectin.
[0036] Mouthfeel describes the overall textural characteristics of the beverage as it is
experienced in the mouth. A negative value for mouthfeel indicates the presence of
factors such as mouth-drying and astringency as compared to the control beverage.
A positive value indicates the presence of factors including the degree of mouth-coating
and lubricity. A negative value for taste (flavor) indicates the presence of off-notes
or masking of the dairy flavor or masking of sweetness as compared to the control
beverage. A positive value indicates that the beverage has less masking of dairy flavor
or sweetness compared to the control.
Description of Starches Used in the Examples
[0037]
Starch A - Waxy maize starch.
Starch B - A total of 1000 parts waxy maize starch was introduced into a reaction vessel containing
a solution of 18.75 parts sodium sulfate in 1500 parts water. The required amount
of propylene oxide was then added (3% w/w in one case, 9% w/w in the other case) and
the vessel sealed. The contents were allowed to react for 16 hours at 40°C while the
vessel was continuously tumbled to assure uniform suspension of the starch throughout
the mixture. The pH of the resultant suspension was adjusted to 5.5 by the addition
of a 25% sulfuric acid solution. The hydroxypropylated starch was recovered by filtration,
washed two times with 1500 parts water and dried.
Starch C - A total of 100 parts waxy maize starch was slurried in 150 parts water and the pH
was adjusted to 8.2 with 3% sodium hydroxide solution. The indicated amount of acetic
anhydride (1% or 4% w/w) was slowly added while maintaining the pH between 7.8 and
8.2 with the above alkali. The reaction was complete when no further addition of alkali
was necessary. The pH was adjusted to between 4.0 and 6.5 and the resulting derivative
was recovered by filtration and washed two times with 150 parts water.
Starch D - A total of 100 parts waxy maize starch was slurried in 150 parts water and the pH
was adjusted to 8.2 with 3% sodium hydroxide solution. The indicated amount of finely
ground succinic anhydride (1% w/w on starch) was slowly added while maintaining the
pH between 7.8 and 8.2 with the above alkali. The reaction was complete when no further
addition of alkali was necessary. The pH was adjusted to between 4,0 and 6.5 and the
resulting derivative was recovered by filtration and washed two times with 150 parts
water.
Starch E - Several slurries were prepared by adding 3000g of waxy corn starch to 3750 ml of
water, followed by the addition of 75 or 150g of sodium tripolyphosphate (STP) at
2.5% or 5% by weight on starch. The pH of each slurry was adjusted to 7.0 using 10%
hydrochloric acid, stirred for about 10 minutes and filtered on a Buchner funnel.
The resultant STP impregnated starch was then air-dried to a moisture content of about
10% and ground using a Prater mill.
[0038] A fluid bed reactor (obtained from Procedyne Corporation, New Brunswick, New Jersey)
was pre-heated to 115°C and the impregnated starch was loaded into the reactor. The
temperature was maintained at 115°C until the moisture of the impregnated starch was
less than 1%. Afterwards, in order to effect phosphorylation, the temperature of the
reactor was increased to 127°C and maintained for 60 minutes. The heat treatment for
each level of STP treatment resulted in levels of 0.13% and 0.31% inorganic phosphorus
content.
Example 1- Preparation of the Stabilizing Syrup
[0039] Sugar (sucrose, 17.0% w/w) and starch (hydroxypropylated waxy maize starch, 2.0%
w/w) were blended thoroughly and added to water (81.0% w/w) under high agitation.
Using a tubular heat exchanger (Model 25-2S, available from Microthermics, Inc. Raleigh,
North Carolina) the mixture was preheated to 90°C and then cooked at 115°C for 3 seconds
(HTST process).
Example 2 - Preparation of the Acidifed Milk Beverages
[0040] Non-fat dry milk powder was added to non-fat milk to achieve a solids level of 10%.
The powder was mixed until dissolved. Using a tubular heat exchanger, the mixture
was then preheated to 65°C, homogenized at 1500 psig, pasteurized at 93°C for two
minutes, and cooled to 43-44°C. The homogenized and pasteurized mixture was inoculated
with yogurt culture (0.1%, "Jo-Mix® NM 1-20", available from Danisco Cultor), incubated
at 44°C until a pH of 4.3 to 4.6 was obtained, and cooled to about 4°C. The curd of
the acidified milk product was then broken up and then homogenized at 2500/500 psig
to further reduce the particle size. The stabilizer syrup prepared according to Example
1 was cooled to 4°C, then blended with the acidified milk product in a 50:50 w/w ratio
and agitated with a slight vortex for two minutes. The resultant beverages prepared
via the foregoing procedure contained a total 1% w/w starch.
Example 3 - Properties of the Acidified Milk Beverages
[0041] A variety of acidified milk beverages were prepared according to the method described
in Example 2. In addition, a "control" beverage was prepared by the method of Example
2, using a stabilizing syrup prepared via the method of Example 1, except that a pectin
(Genu® Pectin type JMT, available from CP Kelco, US, Inc., Wilmington, Delaware) was
substituted for the starch in a syrup formulation w/w % ratio of 0.6:17.0:82.4 (pectin:sucrose:water).
This resulted in a total 0.3% percent gum beverage, the industry standard concentration.
[0042] The properties of each beverage containing the starches and an industry standard
gum (the "control") were measured according to the above Procedures. The results,
listed in the Table below, indicate that beverages containing the starches of the
present invention (Examples 3a-3e) have better stability as indicated by % wheying-off
throughout the two week storage time of the beverages as compared to the control beverage
(Example 3f). Moreover, in addition to exhibiting improved stability, the beverages
of the present invention containing hydroxyalkylated starches (Examples 3b and 3c)
substantially retain a number of desirable organoleptic properties characteristic
of the control beverage (Example 3f) as demonstrated by similar mouthfeel, taste and
viscosity stability.
