Note: Descriptions are shown in the official language in which they were submitted.
2~795~
A WATER-DISPERSIBLE COMPLEX AND A PROCESS
FOR THE PRODUCTION THEREOF
FIELD OF THE INVENTION
The present invention relates to a water-dispers-
ible complex from which a cellulose colloid can be obtained
and a method of producing that complex. More particularly,
it relates to a water-dispersible complex capable of beinq
utilized as a stabilizer such as a suspension stabilizer,
an emulsion stabilizer, a thickening stabilizer, as well as
a texture-imparting agent, a clouding agent, an abrasive,
a dietary fiber, a fat and oil substitute, etc., in a wide
variety of industrial products such as foods, medicaments,
cosmetics, coating materials, ceramics, resins, catalysts,
etc. The invention also relates to a method of producing
such a water dispersible complex.
BACKGROUND OF THE INVENTION
Fine particles of cellulose exist in water in a
colloidal state and show properties of various stabilizers
and body imparting agents as disclosed in Industrial And
Enqineerinq Chemistry, vol.54, pp.20-29 (1962). That is,
the fine cellulose particles have a number of hydroxyl
groups on the surface thereof, which hydroxyl groups
provide a hydrate structure to give a stable colloidal
cellulose when dispersed in water.
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An example of a water-dispersible complex utiliz-
ing this property of cellulose is described in JP-B-40-
12174 (the term "JP-B" as used herein means an ~'e~m;ned
published Japanese patent application~). There, an aqueous
colloid dispersion is obtained by adding an interfering
agent to a united body of cellulose crystallites. Also,
JP-B-56-31094 and JP-B-57-14771 disclose a water-
dispersible complex composed of a combination of fine
crystal cellulose with a dispersing ~gent or a disintegra-
tor. According to these conventional techniques, water
dispersible complexes are obtained by mixing a cellulose
particles with a water-soluble polymer, saccharide, etc.,
in the presence of water, and then grinding the mixture,
followed by drying and pulverizing the ground mixture.
However, the cellulose dispersion obtained from
the complex thus prepared has an extremely sandy texture.
Therefore, when this complex is used as a stabilizer for
foods, etc., it is necessary to increase the addition
amount thereof to obtain satisfactory performance as a
colloid. As a result, the viscosity is increased because
of a water-soluble polymer and original taste of the food
is lost. Alternatively, the complex or the ~ood to which
the complex is added is treated with a homogeni~er having
a strong dispersing faculty. But, in this case, there is
a restriction on the dispersing means employed and also
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2079558
there is a limit on the increase of the colloid perform-
ance.
Also, a dispersion obtained from the complex has
a small colloid fraction and includes coarse particles
because of an insufficient attrition effect on the cellu-
lose particles. Therefore, there is the problem of
precipitation of the coarse particles when the dispersion
is used in materials having a relatively low v~scosity,
such as beverages. Also, a sandy feeling is caused in food
additives wherein importance is attached to the taste of
food. Moreover, there is a limitation on the use thereof
in materials wherein a smooth aftertaste and apparent
texture are required. Additionally, there is a problem of
clogging fine pipes and screens during transporting the
slurry.
Thus, efforts have been made to develop suffi-
ciently fine cellulose particles to solve these problems.
For example, EP-0415193A2 discloses a water dispersion of
cellulose particles having an average particle size of not
larger than 6 ~m; WO-9102461 and U.S. Patent 5,011,701
disclose a method for making fine cellulose particles for
use in low-calorie cheese; and JP-B-62-30220 discloses a
method for making uniform a suspension of fine cellulose
crystalline.
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2~9~8
However, in these techniques, the fine cellulose
particles are stored and used in the form of an aqueous
slurry, and hence there are large restrictions on the usage
thereof. That is, there is the problem that microorganisms
generate during storage. Transportation in the form of
aqueous slurry is troublesome. Also, the aqueous slurry
cannot be used at a high concentration. Thus, the tech-
niques disclosed in the foregoing patents are unsatisfac-
tory. When these fine cellulose particles are dried along
with the aforementioned interfering agents, etc., to obtain
a complex, a sufficient dispersion cannot be obtained when
the complex is re-dispersed in water.
SUMMARY OF THE INVENTION
An object of the present invention is to provide
a water-dispersible complex composed mainly of a cellulose,
which is known to give a unique refreshing feeling as a
taste improving agent of foods. The complex should be a
dry product which is convenient for transporting and stor-
age. It should give a smooth texture and form a colloid
dispersion without sandy feeling when dispersed in water.
According to studies by the present inventoxs,
strong hydrogen bonds are formed between the surfaces of
fine cellulose particles when the cellulose slurry is
dried, providing a material firm in structure which cannot
be re-dispersed in water. Also, it was confirmed that the
21D79~5~
finer cellulose particles, the firmer the structure of the
material obtained, because fine cellulose particles move
easily during drying and have a large surface area.
Furthermore, it was confirmed that, in the conventional
complexes aforementioned, the colloid fraction is less than
80%, the particles having a particle size of at least 10 ~m
constitute at least 30 % of all the particles, and the
aspect ratio (the ratio of a long diameter to a short
diameter of the particles) is at least 3.8 with respect to
the cellulose particles having a particle size (long
diameter) of at least 10 ~m.
As a result of investigations taking the above
into consideration, it has been found that the afore-
mentioned object can be achieved by uniformly dispersing
(1) cellulose particles having a size, form and colloidal
fraction which fall within specific ranges and (2) water-
soluble gum and/or a hydrophilic material, and then drying
the dispersion. This method is effective even if very fine
particles are not employed, which require a considerable
effort to prepare.
Accordingly, the present invention is a waker-
dispexsible complex comprising from 50 to 98 % by weight
fine cellulose particles and from 2 to 50 % by weight
water-soluble gum and/or hydrophilic material, as solid
component ratio by weight. The composition of the complex
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2~795~
is such that: an aqueous dispersion of the complex
comprises particles having a particle size of at least 10
~m in a particle size distribution of not more than 40 %;
the aspect ratio of the particles having a particle size of
at least 10 ~m is not higher than 3.0 when the ratio of the
particles having a particle size of at least 10 ~m in the
particle size distribution is from 5 to 40 %; and the
dispersion has a colloid fraction of at least 65 ~.
~RIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is a schematic view showing the result
of a microscopic observation of the aqueous dispersion
obtained in Example 2, wherein the m;n;mnm scale is 10 ~m.
Figure 2 is a schematic view showing the result
of a microscopic observation of the aqueous dispersion
obtained in Comparative Example 1, wherein the ~; n;
scale is 10 ~m.
Figures 3 to 5 are photographs obtained by a
scanning type electron microscope showing the cross
section, the surface and the cross section, respectively,
of the film obtained in Example 4. In Figures 3, "A"
indicates the upper surface of the film and "B" indicates
the lower surface of the film. In Figure 5, "C" indicates
i the upper surface of the film.
Figures 6 to 8 are photographs obtained by a
scanning type electron microscope showing the form, the
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surface and the cross section, respectively, of the powder
obtained in Comparative Example 3. In Figure 8, "D"
indicates the center portion of the powder.
DETAILED DESCRIPTION OF THE INVENTION
There are two factors which influence the taste
of a re~dispersed complex, i.e., "smoothness" and "sandi-
ness". The term "smoothness" means that a sample dispers-
ion uniformly has a fine texture so that one feels melting
on the tongue as a creamy taste, the opposite of which is
"roughness'~. On the other hand, the term ~sandiness~ means
that the presence of grains is recognized in a sample
dispersion and an extraneous feeling remains on the tongue
as an aftertaste.
The main factors causing a sandy feeling in a
cellulose particle dispersion are the amount of course
particles and the form thereof. That is, a particularly
strong sandiness may be felt when the content of particles
having a particle size of at least 10 ~m is over 5 %.
Also, even when the ratio of the cellulose particles having
particles size of at least 10 ~m is over 5 %, a sandy
feeling is not given if the aspect ratio of the particles
having a particle size of at least 10 ~m is not higher than
3Ø Furthermore, even when the aspect ratio of the
particles having a particle size of at least 10 ~m is not
higher than 3.0, they give an extraneous feeling on the
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2~7~
tongue of sandiness when the ratio of the particles having
a particle size of at least 10 ~m is higher than 40 ~.
On the other hand, the smooth feeling depends on
the colloid fraction which is a practical characteristics
for measuring colloidal cellulose.
That is, the colloid fraction of a cellulose
dispersion in water of a water-dispersible complex of the
present invention is at least 65 % for obtaining a smooth
texture therein. For removing a sandy feeling in the
aqueous dispersion of the complex of the present invention,
the ratio of the particles having a particle size of at
least 10 ~m in the particle size distribu~ion is not more
than 40 ~ by volume, the aspect ratio of the particles
having a particle size of at least 10 ~m being not higher
than 3.0 when the ratio of the particles having a particle
size of at least 10 ~m in the particle size distribution is
5 to 40 %. In this case, the average particle size of the
cellulose particles may be not more than about 8 ~m.
Furthermore, for effectively achieving the object of the
present invention, it is preferable that the ratio of the
particles having a particle size of at least 10 ~m is ~ot
more than 5 % and that the colloidal fraction is at least
80 %. In this case, the average particle size of the
cellulose particles may be not more than about ~ ~m.
The term "colloid fraction~ is the weight ratio
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2~7~
(~) of the solid components in the dispersed phase wherein
the solid components are floated and dispersed without
being precipitated even when a definite centrifugal force
is applied to an aqueous dispersion of a cellulose complex.
That is, the colloid fraction is the ratio of the colloidal
portion which can be stably dispersed in an aqueous
dispersion and shows the faculty of dispersibility and
stability for practical use. Also, the average particle
size is the particle size of 50 % of the integrated volume
by a laser method and the ratio of the particle having a
particle size of at least 10 ~m shows a ratio (%) in the
volume distribution. These measurement methods are
described in detail in the examples set forth below.
The cellulose particles to be used in the present
invention have a colloid fraction of at least 50%, wherein
the ratio of the particles with a particle size of at least
10 ~m is not more than 40 %, preferably not more than 5 %,
the aspect ratio of the particles having a particle size of
at least 10 ~m being not higher than 3.0 when the ratio of
the particles with a particle size of at least 10 ~m is 5
to 40 %. With respect to the average particle size o~ such
cel].ulose particles, it is generally not more than about 8
~m, preferably 4 ~m.
The fine cellulose particles can be obtained by
subjecting cellulose materials such as wood pulp and
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2~7~
purified linter to a depolymerization treatment such as
acid hydrolysis, alkali oxidation-decomposition, enzyme
decomposition, or steam explosion decomposition, to provide
a cellulose having an average polymerization degree of from
to 375 and wet-grinding the cellulose by applying
thereto a mechanical shear. The wet-ground cellulose can
be further subjected to a fractional treatment by
centrifugal sedimentation to collect the colloidal portion.
The wet-grinding machines suitably used in the
present invention include medium mills such as a wet
vibration mill, a wet planetary vibration mill, a wet ball
mill, a wet roll mill, a wet coball mill, a wet bead mill
and a wet paint shaker, high-pressure homogenizers, and the
like. Among the high-pressure homogeni~ers, those wherein
the slurry is introduced into a fine orifice and made to
collide against each other at a high flow rate, at a high
pressure of at least about ~00 kg/cm2, are preferable.
From among the conventional wet-grinding machines
illustrated above, a suitable machine can be selected
depending on the physical properties required in the final
product. For example, a medium mill is suitable for
efficiently grinding a cellulose. On the other hand, if a
high-pressure homogenizer is employed, the colloid fraction
value of the dispersion of the cellulose fine particles
obtained is increased to provide a smooth texture. For
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example, a colloid fraction of at least 50% in an aqueous
dispersion can be obtained by first lowering the average
particle size below 6 ~m when a wet bead mill is employed,
while the same fraction value can be achieved at the
average particle size is about 8 ~m with a high-pressure
homogenizer.
Also, the particle form and viscosity of fine
cellulose can be controlled by suitably selecting a
grinder. For example, the aspect ratio of the particles
having the particle size of at least 10 ~m, which is the
main factor causing a sandy feeling, is lower with a high-
pressure homogenizer than with a wet bead mill. As to the
viscosity, a higher viscosity is obtained with a high-
pressure homogenizer than with a wet bead mill.
The foregoing grinding machines can be used
solely, or can be used in a combination of two or more.
The optimum concentration during grinding using
these mills depends upon the kind of the mill, but is
generally from 2 to 25 % in its solid component concen-
tration, preferably from 5 to 15 % for a medium mill and
from 5 to 20 % for a high-pressure homogenizer.
A water-soluble gum and/or a hydrophilic material
are used in the present invention for preventing the re-
aggregation of the fine cellulose particles by hydrogen
bonding during drying. Thus, the water-dispersible complex
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of the present invention is easily returned to an initial
colloid dispersion in water, that is, can be easily re-
dispersed in water.
The water-soluble gum used in the present
invention has a high water-swelling property and a good
compatibility with cellulose in water. Examples include a
locust bean gum, a guar gum, a tamarind gum, a quins seed
gum, a karaya gum, a gum arabic, a tragacanth gum, a gatty
gum, arabinogalactan, agar, carrageenan, alginic acid and
the salts thereof, farseleran, pectin, marmero, a xanthane
gum, kardran, purulan, dextran, a geran gum, gelatin,
cellulose derivatives such as sodium cellulose glycolate,
etc.
Of these materials, sodium cellulose glycolate
can be used solely since the material has both a swelling
property and a hydrophilic property. However, it is
desirable to use the other water-soluble gums together with
a hydrophilic material, since a large additi~n amount
thereof is required, resulting in the viscosity of the
whole system being greatly increased. In view of the
above, the content of water-soluble gums i.n the complex may
be not more than 45 %, preferably from 2 to 25 %, by
weight. Also, the ratio of the content of water-soluble
gums to that of the hydrophilic materials may be 1/9 to
, 9/1.
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2~7~8
The hydrophilic material used in the present
invention has an excellent solubility in cold water and
scarcely increases the viscosity of a dispersion system.
Examples include hydrolyzed cereal solids; dextrins; water-
soluble monosaccharides such as glucose, fruit sugar and
xylose; water-soluble oligosaccharide such as sucrose,
lactose, maltose, isomerized sugar, coupling sugar,
parathinose, neosugar, mannitol, reduced starch
saccharified wheat gluten, maltose, lactulose, poly-
dextrose, fructoligosacchaside and galactoligosaccharide;
sugar alcohols such as multitol, xylitol, mannitol and
sorbitol; sorbose; and the like.
The water-soluble gum quickens the dispersion of
the fine cellulose in water, improves the dispersion
stability of the cellulose, and improves the colloid
fraction as a protective colloid. Also, the hydrophilic
material accelerates the dispersion of the cellulose in
water, which acceleration effect can be improved when
combined with water-soluble gum.
For increasing the colloid fraction in an aqueous
dispersion o~ the complex and remarkably improving the
dispersibility and stability thereof, it is preferred that
the total amount of the water-soluble gums and/or the
hydrophilic materials is from 2 to 50 %, preferably 3 to 30
~, based on the total weight of the complex. If the amount
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2~7955~
of the water-soluble gums and/or the hydrophilic materials
is less than 2%, it is difficult to prevent the re-
aggregation of the cellulose particles caused by hydrogen
bonding during the drying step. If the amount is over 50
%, the viscosity of the complex dispersion increases as a
result of the water-soluble gum to lower the taste of the
food. Also, the faculty as a stabilizer is undesirably
reduced with a lowering of the relative cellulose content.
The colloid fraction of the fine cellulose
particles indicates the colloidal faculty of the cellulose
itself when measured solely, while the colloid fraction of
the complex is influenced to some extent by the viscosity
and content of the water-soluble gum and/or the hydrophilic
material. Generally, the water-dispersible complex has a
colloidal fraction value higher than that of the fine
cellulose as the main component thereof. That is, the
smoothness of the texture of the re-dispersion of a complex
is same as or greater than that of the fine cellulose as a
raw material.
Whether or not the complex is completed may be
confirmed by re-dispersing the dried compl~x in water to
prepare a dispersion having the same particle size as that
of the original cellulose and measuring the apparent
viscosity of the dispersion. As compared with a simple
mixture before the formation of the complex, the increase
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of the slurry viscosity is recognized as a result of the
increase in the particle stability with the formation of
the complex imparting body.
The colloid fraction value and the viscosity of
an a~ueous dispersion of water-dispersible complexes are
generally in proportion to those of cellulose particles as
a raw material, but they can be controlled by changing the
water-soluble gums and/or hydrophilic materials. In the
present invention, these properties of an aqueous
dispersion of the complex can be determined according to
the purpose of the final product. For example, in the case
of a complex being added to food, a higher viscosity may
result in a heavy taste.
For ensuring the re-dispersion of the water-
dispersible complex in water, it is preferred that the
dried product of the complex has a water-permeable pore
structure having innumerable, network-form, fine cracks and
voids inside thereof. The water-permeable pores may have
openings of a width of from about at least 0.05 to 0.5 ~m
and it is preferable that intervals between the pores are
3 ~m or less.
The complex of the present invention having the
above pore structure is preferable for the following
reason. In conventional complexes containing unground
particles, the unground particles existing on the surface
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2~79~5~
of the dried complex introduce water into the inside of the
complex through capillary tubes of the unground particles
themselves. Furthermore, the unground particles themselves
fall off because of stirring during re-dispersing to form
holes, which holes function to further permeate water into
the inside of the dried particles.
On the other hand, in the water-dispersible
complex of the present invention containing an extremely
small amount of such unground particles, the foregoing
water permeation effect by the unground particles can not
be expected and thus it is preferable that the dried
product has the specific water-permeating structure as
described above.
The water dispersible complex of the present
invention has a water content of from 2 to 20%, preferably
3 to 10%, based on the total weight of the complex. If the
water content in the dried product is higher than 20%,
there are problems with the inferior handling property,
sticking, putrefaction, collapse of the pore structure from
shear in the steps of drying, grinding, particle size
control, and the like.
The water-dispersible complex of the presen~
invention can be prepared by treating cellulose so that the
colloid fraction is at least 50 %, mixing the cellulose
with a water-soluble gum and/or a hydrophilic material in
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water to prepare a slurry, and then drying the slurry.
Alternatively, the cellulose after a depolymerization
treatment can be mixed with a water-soluble gum and/or a
hydrophilic material, the mixture can be ground by a wet
type medium mill or a high-pressure homogenizer and
dispersed to provide a slurry, and then the complex can be
obtained by drying the slurry.
In any case, during mixing the cellulose
particles with a water-soluble gum and/or a hydrophilic
material and dispersing the mixture, care should be taken
to sufficiently dissolve and to uniformly mix the water-
soluble gum, in particular. For that puxpose, it is
preferred that the water-soluble components are mixed with
sufficient stirring in water of at least 75 % of the total
weight of the slurry. It is possible that after previously
dispersing the water-soluble components in a small amount
of water, the dispersion is added to the residue water and
mixed therein. A heating treatment at about from 40 to
90~C may be an effective method for accelerating the
dissolution and for accelerating the formation of the
complex. In particular, i.n the case of using a xanthane
gum or carrageenan, it is necessary that the slurry
obtained is heat-treated for at least one minute (up to
about 100 hrs.) at 60~C or higher (up to about 200~C)
before or during the drying of the slurry.
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Drying methods employed in the present invention
include lyophilization, spray drying, and drying in a film
form, preferably drying in a film form which can
effectively provide the aforementioned pore structure.
When a spray drying is employed, it is preferable to
control the particle size of the sprayed particles to be
small and to quicken the drying speed as fast as possible
for stabilizing the re-dispersibility of the dried product.
For example, preferred is a spraying condition in which the
dried product has such particle size so that, when placed
on a JIS (Japanese Industrial Standard) 100 mesh sieve, the
particles remaining on the sieve are not more than 5% of
the total particles. In a preferable drying condition, the
difference between the temperature of the inlet for the hot
blast and that of the outlet thereof can be at least 100~C,
and the ratio of the amount of the blast for drying to that
of the evaporated water can be about 150 Nm3/T.
Drying the slurry in a film form can be carried
out by casting a uniformly mixed slurry of the fine
cellulose particles and the water-soluble gum and/or the
hydrophilic material on a base material such as a glass
sheet, a stainless steel plate, an aluminum plate and a
nickel-chromium plated steel plate, followed by drying.
Casting the slurry when drying the complex in a
film form is carried out, for example, by extruding the
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slurry from a slit, by applying the slurry with a roll or
a brush, by blowing the slurry, by sinking a base material
into the slurry and then taking it up, by placing an excess
amount o~ the slurry on a base material and then blowing
air thereon, or by transferring the slurry to a base
material using a transferring roll.
The base materials on which the slurry is casted
during drying in a film form may be previously heated.
Alternatively, the casted film of the slurry may be heated
by infrared rays, hot blast, high frequency, etc., after
casting the slurry. The drying temperature is preferably
about 15 to 200~C, more preferably 40 to 150~C. In the
case of a system to which a xanthane gum or carrageenan is
added, a drying temperature of at least 60~C is preferred
since the heat treatment of the system can be omitted.
The slurry when dried in a film form may have a
concentration capable of spreading the slurry in a film
form and there is no particular restriction thereon.
However, the solid component concentration of the slurry is
generally from about 1 to 30 %, preferably 5 to 20 %, in
view of facilities in working to provide a good dried
product. The thickness of cast film may be 0.1 to 10 mm,
pre~erably 0.5 to 7 ~m of the thickness o~ the slurry.
For industrial practice, a dryer such as a steel
belt dryer, a drum dryer and a disk dryer can be employed
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for drying the slurry in a film form.
The product thus dried in a film form may then be
peeled off with care so as not to destroy the pore
structure of the film. Therefore, a drying condition is
preferable whereby the dried film causes self-peeling
because of the difference in shrinkage during drying
between the upper side and the bottom side of the film.
For that purpose, it is preferred that the base material
has a smooth surface from which the film is easily peeled
off or that the surface of the base material is subjected
to a parting agent treatment, Teflon-coating, etc. A
drying condition which can provide an excellent peeling
ability of the dried film can be suitably selected
depending, for example, on the complex system, on the
slurry concentration, on the slurry viscosity, on the
properties of the base material, and on the drying means.
In general, the thicker the film, the better the peeling
ability thereof.
.The products dried in the film form include so-
called film-form products as well as foil-form, thin piece-
'form, flake-form, linear-form, powder-form products, and
the like.
The dried product obtained by the film-form
drying method can be used as a product as it is. When the
dried product is a bulky film because of compounding of the
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composition, slurry concentration, drying system, etc., the
product may be subjected to a crushing treatment, which is
preferably conducted in a mild manner to maintain the pore
structure. As a crushing machine, an impact type crusher
such as a hammer mill, a pin mill and a jet mill can be
used, but these crushers tend to lower the re-
dispersibility of the product. Accordingly, a cutter-type
crusher with a low rotation number (e.g., 300 to 10,000
rpm), in particular, one having a sharp cutter which can be
handled at a relatively low rotation number, is preferably
used.
The water-dispersible complex of the present
invention can be effectively used as an additive with
various functions in the industrial fields of food,
medicine, cosmetics, and the like. The content of the
present complex during use may be 0.1 to 3% when used as a
suspension stabilizer, 0.1 to 5% as an emulsion aid agent,
l to 10~ as a fat substitute, 0.1 to 3% as a suspension
agent, 1 to 20% as a base for ointment, 0.5 to 50% as a
disintegration aid agent, 0.5 to 80% as a liberation
controlling agent, and 0.5 to 10 % as an extrusion
improving agent.
According to the water-dispersible complex of the
present invention, a high colloid fraction of at least 65%
can be achieved even in a low-viscosity complex system
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(with an apparent viscosity of 700 cps or lower in 3%
aqueous dispersion). Furthermore, a very high colloid
fraction of at least 80% can be achieved in a high-
viscosity complex system (with an apparent viscosity of 700
cps or higher in 3% aqueous dispersion), which fraction
value has not been obtained by any conventional complexes
even having an apparent viscosity of 2,000 cps.
As is clear from the definition described above,
the colloid fraction shows a performance capable of stably
dispersing without causing precipitations in an aqueous
dispersion. That is, the water-dispersible complex of the
present invention having the foregoing colloid fraction has
an excellent effect in the fields wherein a uniform
dispersibility and stability over a period of long time are
reyuired, for example, as a suspension stabili2er, an
emulsion stabilizer, a thickener stabilizer, a cloudy agent
and the like. Also, when the complex is used for a texture
imparting agent, a dietary fiber, etc., the complex gives
a smooth and good texture.
Furthermore, in the present invention, cellulose
particles are fine, the ratio of lar~e particles is
reduced, and the form of the particles is a roundish
particle form. That is, the problem of a sandy feeling is
solved to obtain a product having a good apparent texture.
Additionally, the water-dispersible complex of the present
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invention can generate a large amount of colloid particles
wlthout using a specific dispersing means, whereby its
performance as a stabilizer is remarkably improved and its
field of use can be extended.
The present invention is described by the follow-
ing examples in more detail. The measurement methods used
in the examples and the comparative examples are described
below.
Colloidal Fraction
(1) A sample (0.75 g as the solid components)
and distilled water are placed in an ace homogenizer (Type
AM-T, made by Nippon Seiki K.K.) and the total amount is
adjusted to 300 g;
(2) the sample is dispersed for 2 minutes at
15,000 r.p.m.;
(3) in a weighing bottle is placed lO ml of the
dispersion and the weight is measured;
(4) a residue dispersion is placed in a
centrifugal tube and is subjected to a centrifugal
separation for 15 minutes at 2,000 r.p.m. (Type H-300, made
by Kokusan Enshinki K.K.) and 10 ml of the supernatant
liquid is placed in a weighing bottle, and the weight is
measured;
(5) the weighing bottles (3) and (4) are
subjected to evaporation to dryness for 10 hours in an oven
- 23 -
' ~ '' ~'",
. - : , .
2~7~
at 105~C;
(6) the weight of the solid components of (3) is
measured to obtain the value A;
(7) the weight of the solid components of (4) is
accurately measured to obtain the value B; and
(8) water-soluble components (sum of a water-
soluble gum and a hydrophilic material) are corrected.
When the weight of the water-soluble components
is S%, Colloid fraction (~) = (B - AS/100)/A(1-S/100) x
100 .
Aqqreqate
(1) A sample (3.0 g as solid components) and
distilled water are placed in Ace homogenizer (AM-T, made
by Nippon Seiki K.K.) and the total weight is adjusted to
300 g;
(2) the sample is dispersed for 5 minutes at
15,000 r.p.m.; and
(3) the dispersion is observed by an optical
microscope (Nikon Optiphoto-pol) at 50 magnification~
~veraqe Particle Size, Ratio of Particles of at least 10 um
(1) A sample (3.0 g as solid components) and
distilled water are placed in Ace Homogenizer (AM-T, made
by Nippon Seiki K.K.) and the total weight is adjus~ed to
300 g;
(2) the sample is dispersed for 5 minutes at
- 24 -
:
2~7~
15,000 r.p.m.; and
(3) the particle size distribution is measured
using Horiba Laser Diffraction Type Particle Size
Distribution Measuring Apparatus (LA-500).
The average particle size is the particle size of
an integrated volume of 50% and the ratio of the particles
having a particle size of at least 10 ~m is shown by the
ratio (%) in the volume distribution.
Aspect Ratio of Particles havinq Lenqth of at Least 10 ~m
In a photograph obtained by photographing a
sample prepared under the same conditions as for the
average particle size by an optical microscope or an
electron microscope, the long diameter and the short
diameter of the particles having a length of at least 10 ~m
are measured, and the ratio is obtained from the mean value
of the measured values of at least 20 particles.
EXAMPLE 1
; After finely cutting a commercially available
dissolving pulp, the pulp was hydrolyzed in 10% hydro-
chloric acid at 105~C for 20 minutes and the acid-insoluble
residue obtained was filtered and washed to provide a cakey
material having a water content of 60%. The cakey material
was subjected to a grinding treatment for one hour by a
planetary mixer. To the ground cakey material was added
water, followed by dispersion by a homo mixer to provide a
- 25 -
: . - . ~ :
,1 . . ;
: .
''
2~795~
cellulose dispersion having a solid component ratio of 7%.
The dispersion was subjected to a centrifugal separation
for 5 minutes at 2,000G, whereby a dispersion having a
solid component ratio of 4.6% was obtained as the upper
layer portion. The cellulose thus obtained by the
fractional centrifugal treatment had a colloid fraction of
65% and a particle size of an integrated volume of 50% of
4.2 ~m.
~ hen, an aqueous dispersion having a total solid
component concentration of 3.5% composed of the cellulose
having the colloid fraction of 65% thus obtained by the
fractional centrifugal treatment, a xanthane gum ~Bistop,
trade name, made by Sanei Kagaku Kogyo K.K.) and a
maltodextrin ~Foodtex, trade name, made by Matsutani Kagaku
Kogyo K.K.) in the compounding ratio of 75/5~20 by solid
component ratio was prepared. The dispersion was heat-
treated for 60 minutes at 80~C with stirring and then
spray-dried ~tem. of dry hot blast: 230~C, tem. of exhaust
air: 80~C, speed of slurry feeding: 6 kg/hr) to provide the
dried powder of the water-dispersible complex.
~ he water content of the water-dispersible
complex obtained was 5.1%, the colloid fraction when the
complex was re-dispersed in water was 93%, the particle
size of an integrated volume of 50% was 4.2 ~m, and the
ratio of the particles having a particle size of at least
- 26 -
''J
2 ~J ~ 8
10 ~m was 4.5%.
EXAMPLE 2
After finely cutting a commercially available
dissolving pulp, the pulp was hydrolyzed in 10% hydro-
chloric acid at 105~C for 20 minutes and the acid-insoluble
residue obtained was filtered and washed to provide a
cellulose dispersion having a solid component ratio of 10%.
The cellulose dispersion obtained was subjected to a
pulverizing treatment by passing twice a medium stirring
wet type pulverizing apparatus (Apex Mill Type AM-1, trade
name, made by Kotobuki Giken Kogyo K.K.) using zirconia
beads having a diameter of 1 mm and under the conditions of
a stirring wing rotation number of 1,800 r.p.m. and a
supplying amount of cellulose dispersion of 0.4 liter/min.,
to provide a pasty cellulose. The colloid fraction of the
cellulose was 73% and the particle size of integrated
volume of 50% was 3.1 ~m.
Then, a dispersion having a total solid component
concentration of 3.5% composed of the cellulose having the
colloid fraction of 73~ thus obtained, a xanthane gum
(Bistop, trade name, made by Sanei Kagaku Kogyo K.X.) and
glucose, having a compounding ratio of 75/5/20 by solid
component content was prepared. The dispersion was heat-
treated for 60 minutes at 80~C with stirring and then
spray-dried (tem. of dry hot blast: 230~C, tem. of exhaust
- 27 -
: -
- .
' ~ ~' ' . ~ . ;
2~7~9~
air: 80~C, speed of slurry feeding: 6 kg/hr) to provide a
dried powder of the water-dispersible complex.
The water content of the water-dispersible
complex obtained was 5.3~, the colloid fraction when the
complex was re-dispersed in water was 97~, the particle
size of an integrated volume of 50% was 3.3 ~m, and the
ratio of the particles having a particle size of at least
10 ~m was 1.5~.
Also, when the aqueous dispersion was observed by
microscope, the cellulose particles were uniformly
dispersed and aggregations of coarse particles were not
observed. The schematic view of the dispersion observed by
the microscope is shown in Fig. 1, wherein the minimum
scale is 10 ~m.
EXAMPLE 3
A dispersion having a total solid component
concentration of 5.0 % composed of the cellulose having a
colloid fraction of 73 % obtained in Example 2 and CMC-Na
(carboxymethyl cellulose sodium) (Celogen, trade name, made
by Dai-Ichi Kogyo Seiyaku Co., Ltd.) having a compounding
ratio of 89/11 by solid component content was prepaxed.
The dispersion was heat-treated for 30 minutes at 80~C with
stirring and spray-dried (tem. of dry hot blast: 230~C,
tem. of exhaust air: 80~C, speed of slurry feeding: 6
kg/hr) to provide a dried powder of the water-dispersible
"
- 28 -
:;-
$
complex.
The water content of the water-dispersible
complex obtained was 4.8%, the colloid fraction when the
complex was re-dispersed in water was 92%, the particle
size of an integrated volume of 50~ was 3.1 ~m, and the
ratio of the particles having a particle size of at least
10 ~m was 1.5~.
EXAMPLE ~
A dispersion having a total solid component
concentration of 10.5 % composed of the cellulose having a
colloid fraction of 73% obtained in Example 2 and CMC-Na
(carboxymethyl cellulose sodium) (Celogen, trade name, made
by Dai-Ichi Kogyo Seiyaku Co., Ltd.), having a compounding
ratio of 95/5 by solid component content was prepared. The
dispersion was casted in a thicXness of 3 mm on an aluminum
plate by means of an applicator and dried by an oven dryer
for 60 minutes at 80~C to form a dry film having a
thickness of about 70 ~m.
When the dry film was observed by electron
microscope, fine cellulose particles were exposed on the
surface thereo~ and innumerable gaps were observed. Also,
on a cross section were distributed fine holes having a
width of from 0.05 to 0.5 ~m with an interval of about 1 ~m
or less in network form in the whole system.
The results obtained by photographing the surface
- 29 -
:,~
' :
,
2~795~;~
and a cross section of the film by a scanning type electron
microscope are shown in Fig. 3, Fig. 4, and Fig. 5.
Furthermore, the dispersion having a total solid
component concentration of 10.5% was dried in film form to
50 ~m in thickness by a drum dryer (Type KDD-l, made by
K.K. Kusuki Xikai Seisakusho) at a steam pressure of 1.8
kg/cm2 and a rotation number of 1.5 r.p.m. to provide dried
powder of the water-dispersible complex.
The water-dispersible complex obtained had a
water content of 5.3% and was in a thin piece-form and
flaky powder. When the powder was observed by electron
microscop~, fine cellulose particles were observed on the
surfaces and innumerable gaps were observed between the
fine cellulose particles. A~so, on a cross section were
distributed fine holes having a width of from 0.05 to 0.5
~m with an interval of from about 0.5 to 2 ~m in the whole
system. When the complex powder was re-dispersed in water,
the colloid fraction was 85%, the particle size of an
integrated volume of 50% was 3.1 ~m, the ratio of the
particles having a particle size of at least 10 ~m was
1.5%, and the aqueous 5% dispersion thereof had smooth
~aste for food with no sandy feeling.
EXAMPLE S
A dispersion having a total solid component
concentration of 8.0% composed o~ the cellulose having a
- 30 -
~7~
colloid fraction of 73% obtained in Example 2, a xanthane
gum (Bistop, trade name, made by Sanei Xagaku Kogyo X.K.)
and a hydrolyzed cereal solid (Paindex, trade name, made b~
Matsutani Kagaku Kogyo K.K.), having a compounding ratio of
75/5/20 by solid component content was prepared. Then,
after treating the surface of a drum dryer (Type XDD-1,
made by K.K. Kusuki Kikai Seisakusho) with a silicone
releasing agent for food, the pasty composition obtained in
the above step was dried by the drum dryer at a steam
pressure of 1.2 kg/cm2 and at a rotation number of 1.0
r.p.m. to provide a film-form complex.
The water content of the complex obtained was
5.3% and when the film was observed by electron microscope,
the complex had almost the same structure as the complex in
Example 4. Also, when the complex was re-dispersed in
water, the colloid fraction was 97%, the particle size of
an integrated volume of 50% was 2.8 ~m, the ratio of the
particles having a particle size of at least 10 ~m was
1.0%, and the aqueous 5~ dispersion of the complex had a
smooth taste for food without showing a sandy feeling.
EXAMPLE 6
A dispersion having a solid component concen-
tration of 8.0% composed of the cellulose having a colloid
fraction of 73% obtained in Example 2, ~-carrageenan (CS-
67, trade name, made by Sanei Kagaku Kogyo X.K.) and
':
,
~79;~
sorbitol, having a compounding ratio of 80/10/10 by solid
component content was prepared. The dispersion was casted
in a thickness of 3 mm on an aluminum plate by means of an
applicator and dried by an oven dryer for 60 minutes at
80~C to provide a film-form complex. Then, by finely
cutting the complex to the size of 1,000 ~m or below by
means of a household food cutter to provide a thin piece-
form and flaky powder.
The water content of the complex obtained was
4.5% and when the powder was observed by electron micro-
scope, the complex had almost the same structure as that of
the complex in Example 4. Also, when the complex was re-
dispersed in water, the colloid fraction was 82%, the
particle size of an integrated volume of 50% was 2.8 ~m,
the ratio of the particles having the particle sizes of at
least 10 ~m was 1.5%, and an aqueous 5% dispersion of the
complex had a smooth taste for food without showing a sandy
feeling.
EXAMPLE 7
After finely cutting a commercially available
dissolving pulp, the pulp was hydrolyzed in 10% hydro-
chloric acid at 105~C for 20 minutes and the acid-insoluble
residue obtained was filtered and washed to provide a
cellulose dispersion having a solid component content of
10%. The average particle size of the cellulose particles
- 32 -
:'
,
207~5~
was 17 ~m. The cellulose dispersion was subjected to a
pulverizing treatment by passing the dispersion twice
through a high-pressure pulverizing apparatus (Nanomizer
Type LA-31, trade name, made by Nanomizer K.K.) at 1,300
kg/cm2 to provide a pasty cellulose.
The colloid fraction of the cellulose was 80% and
the particle size of an integrated volume of 50~ was 6.5
~m.
Then, a dispersion having a solid component
concentration of 7.9% composed of the cellose having the
colloid fraction of 80% thus obtained, a xanthane gum
(Bistop, trade name, made by Sanei Kagaku Kogyo K.K.), and
a hydrolyzed cereal solid (Paindex, trade name, made by
Matsutani Xagaku Kogyo X.K.), havin~ a compounding ratio of
75/S/20 by solid component content was prepared. After
treating the surface of a drum dryer (Type KDD-1, trade
name, made by K.K. Kusuki Kikai Seisakusho) with a silicone
releasing agent for food, the pasty composition thus
obtained was dried by the drum dryer at a steam pressure of
1.5 kg/cm2 and a rotation number of l.0 r.p.m. to provide a
film-form complex. Then, the complex was pulverized to the
size of 1,000 ~m or below by a cutting type pulverizer
having knife-type edges to provide a thin piece-form and
flaky powder.
The water content of the complex obtained was
.
- 33 -
2~7~
5.7% and when the powder was observed by electron micro-
scope, the complex had almost the same structure as that of
the complex in Example 4. When the complex was re-
dispersed in water, the colloid fraction was 75%, the
particle size of an integrated volume of 50% was 6.5 ~m,
the ratio of the particles having a particle size of at
least 10 ~m was 22%, and the aspect ratio of the particles
having a length of at least 10 ~m was 2Ø The aqueous 5~
dispersion thereof had smooth taste for food without
showing a sandy feeling.
EXAMPLE 8
Using the cellulose dispersion having a solid
component ratio of 10% obtained by hydrolyzing a commer-
cially available dissolving pulp in Example 7 and CMC-Na
(carboxymethyl cellulose sodium) (Celogen, trade name, made
by Dai-Ichi Kogyo Seiyaku Co. Ltd.), a dispersion having a
total solid component concentration of 10.0~ of the
cellulose dispersion and CMC-Na of a compounding ratio of
95/5 by solid component content was prepared. The
dispersion was simultaneously subjected to a mixing,
dispersing, and pulverizing treatment by passing it 5 times
through a high-pr0ssure pulverizer (Microfluidizer T~pe M-
610, trade name, made by Microfluidics Co.) to provide a
pasty composition.
Then, the pasty composition was adjusted to a
- 34 -
'': : ,
~-~
2~7~
total solid component concentration of 8.0% with water.
After treating the surface of a drum dryer (Type KDD-1,
made by K.K. Kusuki Kikai Seisakusho) with a silicone
releasing agent for food, the composition was dried by the
drum dryer at a steam pressure of 1.8 kg/cm2 and a rotation
number of 1.5 r.p.m. to provide a film-form complex. Then,
the complex was pulverized to the size of 1,000 ~m or below
by a cutting type pulverizer having knife type edges to
provide a thin piece-form and flaky powder.
The water content of the complex obtained was
5.2% and when the powder was observed by electron micro-
scope, the complex had almost the same structure as that of
the complex in Example 4. Also, when the complex was re-
dispersed in water, the colloid fraction was 90%, the
particle size of an integrated volume of 50% was 3.5 ~m,
and the ratio of the particles having a particle size of at
least 10 ~m was 2.0%. The aqueous 5% dispersion thereof
had a smooth taste for food without showing a sandy
feeling.
COMPARATIVE EXAMPLE 1
By following the same procedure as Example 2
except that a dispersion treatment for 60 minutes at 10~C
was carried out in place of the heat treatment for 60
minutes at 80~C, a dry powder of a complex was obtained.
The water content of the complex obtained was
. .
- 35 -
,, , ~ ', '
. ' ,
, ~
2~7~
5.5%. When the powder was re-dispersed in water, the
colloid fraction was 88~, the particle size of an
integrated volume of 50% was 22.0 ~m, and the ratio of the
particles having a particle size of at least 10 ~m was 59%.
Also, when the aqueous dispersion thereof was observed by
microscope, coarse aggregations having an almost spherical
form were observed. The schematic view thereof is shown in
Fig. ~, wherein the minimum scale is 10 ~m.
COMPARATIVE EXAMPLE 2
After finely cutting a commercially available
dissolving pulp, the pulp was hydrolyzed in 10% hydro-
chloric acid at 105~C for 20 minutes and the acid-insoluble
residue obtained was filtered and washed to provide a
cellulose dispersion having a solid component ratio of 10%.
The cellulose dispersion was subjected to a pulverization
treatment by passing the dispersion once through a media
stirring wet pulverizer (Apex Mill Type AM-1, trade name,
made by Kotobuki Giken Kogyo K.K.) using zirconia beads
having a diameter of 1 mm as the media under the conditions
of a stirring wing rotation number of l,800 r.p.m. and
supply amount of the cellulose dispersion of 0.4 liter/min.
to provide a pasty cellulose. The colloid fraction of the
cellulose was 47% and the particle size of an integrated
volume of 50~ was 6.5 ~m.
A dispersion having a total solid component
- 36 -
:,
:
,
2~7~55~
concentration of 10.5% of the cellulose having the colloid
fraction of 47% thus obtained and CMC-Na (carboxymethyl
cellulose sodium) (Celogen, trade name, made by Dai-Ichi
Kogyo Seiya~u Co., ~td.), having a compounding ratio of
9S/S by solid component content was prepared. The
dispersion was casted in a thickness of 3 mm on an aluminum
plate by an applicator and dried by an oven dryer for 60
minutes at 80~C to provide a dry film having a thickness of
about 70 ~m.
The water content of the dry ~ilm obtained was
4.0~ and when the film was re-dispersed in water, the
colloid fraction was 60%, the particle size of an
integrated volume of S0~ was 6.7 ~m, the ratio of the
particles having a particle size of at least 10 ~m was 26%,
and the aspect ratio of the particles having a length of at
least 10 ~m was 6.5. The aqueous 5% dispersion thereof had
a rough texture and showed a sandy feeling.
COMPARATIVE EXAMPLE 3
The dry film having a thickness of about 70 ~m
obtained by the casting method in Examp~e 4 wa~ pulverized
by an impact type pulverizer to provide a powder having a
diameter of not larger than 150 ~m. The results of
photographing the surface and the cross section of the
powder by a scanning type electron microscope are shown in
Fig. 6, Fig. 7, and Fig. 8. As shown in the photographs,
- 37 -
,
2~
the network disposition of the cellulose is not seen on the
surface, there are some gaps at the cross section, but the
innumerable fine crack and gap structure seen before
pulverizing was vanished. Also, when the aqueous
dispersion of the powder was observed by an optical
microscope, coarse aggregates were observed, the average
particle size was 15 ~m, and the ratio of the particles
having a particle size of at least 10 ~m was 45%.
COMPARATIVE EXAMPLE 4
By following the same procedure as Example 8
except that the dispersion was subjected to a mixing,
dispersing, and pulverizing treatment by passing the
dispersion once through a high-pressure pulverizer (Micro-
fluidizer Type M-610, trade name, made by Microfluidics
Co.) at 1,000 kg/cm2, a complex was obtained.
The colloid fraction of the complex was 55%, the
average particle size was 10 ~m, and the ratio of the
particles having a particle size of at least 10 ~m was 51%.
The aqueous 5% dispersion of the complex had rough texture
and showed a sandy feeling.
Then, the products obtained by the examples and
the comparative examples were tested on the texture
thereof.
The texture test was made by 15 young women
having no smoking habit. By re-dispersing each dried
i~
- 38 -
' ~ ' . :
,- ~ . . . : .
, ' ' . ~ '
207955~
complex in water, an aqueous dispersion of 5% by weight of
each complex was prepared and the texture test was carried
out by a random test system.
Questions of 1) whether or not you felt "smooth-
ness" and 2) whether or not you felt ~sandiness~ were asked
of each panelist and the answers were collected. The
results are shown in Table 1 below.
- 39 -
. - : ~ , ~. ~:. :
",: :
....
:' : ~ ,,. : : '.:, -
2079S~8
~¦ o,~ ,trt ~t~ C t
~, r1 1/7 tr~, r1
rlu,, I I t~
_) r~ ~ r~
~ I ~ tr,t
t~l tD~t tLt Ot~,t 1~70
~I tD r~
lJ I
r~ ~~t I tXt Ot~ ~t
,~tr,, t~ct r~
tx~ ~ J I o
O~ r~
U~
I~ tDC~ tr~ O~t t~~l
~ ~ r~
Xt
tD t ~ r~ ,t ~ O
tXt r~
tXt
,~ tr,t ~ ~ tr~, o o
, ~~a ,~
¢ I
~ o
t~U~
t;~t.,i I ~ rl ~ ~
~,, ,,, ':
tl~ ,; I .I~ tr~o o
: I ~r~
~ ~ t~ t't
: r~~ ~ I ~ttr~t r~ O 1~
O't r~
.,t
r ~ .
~ O
t~ r~ ~c t
~t ~r 4~
~ ~ ~ *a ,~ , ~' t
~" ~ + ~ ~ t~
O C r O ~ O ~ O
r~ r ~r
O t~ rc o ~
' + ~ Z Z Z ~r~
.
-- 4 0
.;
,.. - . . - - -' ~ .. " . . .. . -. - .
': - :
2~7~5~8
COMPARATIVE EXAMPLE 5
The process described in JP-B-57-14771 was
repeated using cellulose particles subjected to hydrolysis
in the same manner as in Example 1 (particle size: 17.0 ~m,
colloid fraction: 12 %).
That is, a mixture of wet crystal cellulose/
karaya gum/dextrin in a ratio of 7/1/2 as a solid component
by weight, wherein the water content was controlled to 50%,
was kneaded and ground for 2 hours using a kneader. The
ground mixture was then dried by an oven dryer and finely
pulverized to provide a complex powder having a colloid
fraction of 54%. Furthermore, even when the kneading and
grinding were continued for an additional 3 hours, the
colloid fraction was not i Loved.
As described above, the colloid dispersible
complex of the present invention is a dry product
convenient for transportation and storage and when the
complex is dispersed in water, it gives a colloid
dispersion texture which i5 smooth and gives no sandy
feeling. This property is suitable for a fat substitute
which is recently required for reducing ~at of foods for
health reasons, and simultaneously gives a good taste which
has been required for many years.
Also, the colloid dispersing complex of the
present invention has a greatly improved colloid fraction
- 41 -
~'
~ . , . ~ . -
2~795~
and is effective for uses requiring uniform dispersibility
and stability over a period of long time, such as a
suspension stabilizer, an emulsion stabilizer, a thickening
stabilizer, a cloudy stability agent, etc., in foods,
medicaments, cosmetics, coating materials, ceramics,
resins, and other industrial products. Furthermore, the
colloid dispersible complex of the present invention can
generate a large amount of colloid particles without using
a specific dispersing means, whereby the performance
thereof as a stabilizer is greatly improved and also the
range of uses can be expanded.
For example, in the field of foods, the water-
dispersible complex of the present invention can be used as
a suspension stabilizer, an emulsion stabilizer, a
thickening stabilizer, a foam stabilizer, a cloudy agent,
a texture imparting agent, a fluidity improving agent, a
form holding agent, a water release inhibitor, a dough
improving agent, and a powdering base in favorite beverages
such as a cocoa drink, a juice drink, a powdered green tea
drink, Shiruko (adzuki-bean soup), etc.; milky beverages
such as milk cocoa, milk coffee, an acidophilus drink,
soybean milk, etc.; ice beverages such as ice cream, soft
cream, sherbet, etc.; gelatinous foods such as custard
pudding, jelly, jam, soft adzuki-bean jelly, e~c.; milk
shaXe, coffee whitener, whipped cream, mayonnaise,
- 42 -
. .. . .:.. ; . : ..
2~79~
dressings, spreads, seasoning soy, soup, kneaded mustard,
flower paste, food in a can, enteral nutrition, filling and
topping for bread and cake, adzuki-bean jam cakes, fondant,
processed marine product, breads, cakes, Japanese cakes,
noodles, pasta, freezed dough, powdered fat, powdered
perfume, powdered soup, powdered spice, cream powder, etc.
Furthermore, the comple~ of this invention can be
used as a low calorie bases such as dietary fiber bases,
fats and oils substitutes, etc., in the foregoing whole
foods.
While the invention has been described in detail
and with reference to specific embodiments thereof, it will
be apparent to one skilled in the art that various changes
and modifications can be made therein without departing
from the spirit and scope thereof.
- 43 -
:
~' '
