Note: Descriptions are shown in the official language in which they were submitted.
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TITLE OF THE INVENTION
SYNERGISTIC COMPOSITIONS OF POLYSACCHARIDES
AS NATURAL AND BIODEGRADABLE ABSORBENT MATERIALS OR
SUPERABSORBENTS
FIELD OF THE INVENTION
The present invention relates to synergistic compositions of
polysaccharides as natural and biodegradable absorbent materials or
superabsorbents. The compositions of the present invention show synergistic
effects in their capacity to absorb water, saline solutions, biological
fluids, and
the like, at normal pressure or under load, and to retain these fluids.
BACKGROUND OF THE INVENTION
Superabsorbent polymers are mainly used as absorbents
for biological fluids, water, aqueous solutions and the like. These absorbents
are primarily used in diapers, adult incontinence products as well as in
feminine hygiene applications. Polyacrylates and polyacrylamides, as well as
their copolymers, are among the best known superabsorbents. Alternative
acrylic superabsorbent polymer forms, including partially biodegradable
materials, are described in "Modem Superabsorbent Polymer Technology'
(Buchholz F. L. and Graham A. T. Eds., lNiley-VCH, New York, 1998).
Commercial superabsorbents are mainly polyacrylate-based
polymers. However, their biodegradability is questionable, especially for high
molecular weight polymers. These polymers are synthesized from monomers
such as acrylic acids and acrylamides. Following the polymerization process,
there are still residual monomers or oligomers showing toxicity and allergenic
potential.
CA 02426478 2003-04-24
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These synthetic polymers have also been grafted onto
polysaccharides. Superabsorbent polysaccharide-based grafted-polymers are
obtained through the grafting of an unsaturated monomer (acrylonitrile,
acrylic
acid, acrylamide) onto starch or, less frequently, cellulose. The so-obtained
polymers, also called "Super Slurper", illustrate a water absorption capacity
ranging from 700 to 5300 g/g for deionised water, and up to 140 glg in a 0.9
saline solution (weight by volume of NaCI, referred hereinafter as saline
solution) (Riccardo P.O., l9Vater-Absorbent Polymers: A Patent Survey. J.
MacromoLSci., Rev. Macromol. Chem. Phys., 1994, 607-662 (p.634) and cited
references). Despite their high water absorption capacity, these grafted
polysaccharides, prepared by radical polymerization, are hypoallergenic and
are not known to be biodegradable.
Among other polymers, polyaspartates have been
recognized as offering good absorbent properties and as being biodegradable
(Ross et al., US Patent 5,612,384). However, polyaspartates appear to have
several drawbacks regarding their low molecular weight. Furthermore,
polyaspartates are produced synthetically (l~Coskan et al., US Patent
5,221,733) from non-renewable sources such as for example malefic anhydride
(obtained from butane). Finally, these polymers are strongly ionic and subject
to performance fluctuations in saline solutions.
Polymeric blends and mixtures, used as absorbents or
superabsorbents, are known. IVlore specifically, the synergistic effect on the
absorption against pressure of two synthetics polyacrylate-based hydrogel-
forming particles has been reported (Schmid et al., EP 0 691 133 A1 ). Since
these formulations comprise synthetic polymers, they are unsuitable in light
of
allergenic, abrasive, ecological or toxicological concerns.
Chmelir and Klimmek (US Patent 5,340,853), teach a
synergistic absorbing and swelling agent consisting of at least two
CA 02426478 2003-04-24
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components. The agent is made from a water-swellable synthetic polymer or
copolymer, crosslinked with a multifunctional compound, and a second
component. The second component is a. polysaccharide such as
galactomannans or polygalactomannans. Alternatively, it could comprise
admixtures of a gaiactomannan or polygalactomannans with other naturaB or
synthetic polymers such as starch and modified starch. Even though the
inventors refer to a synergistic effect when mixing the two components, no
clear evidence for the synergy has been demonstrated when only
polysaccharide components are used. Furthermore, since these formulations
require synthetic polymers, such as polyacrylates, they are unsuitable for
many
uses in light of allergenic, abrasive, ecological or toxicological concerns.
Many other polyacrylate-polysaccharide based synergistic
compositions have been disclosed such as those taught by Gunther, Klimmek,
Bruggeman and Chmelir (US Patents 5,721,295; 5,847,031; 5.,736,595;
5,264,471; and 4,693,713 Reissue 33,839). However, since these formulations
again require synthetic polymers, such as polyacrylates, they are unsuitable
in light of allergenic, abrasive, ecological or toxicological concerns.
Renewable resources such as mixtures of polysaccharides
have also been considered as absorbent materials. US Patent 5,801,116,
granted to Rhodia Inc. (Cottrell et al.) discloses one or more polysaccharides
having a particle size of greater than 200 mesh (74 microns), preferably
modified guar gum. This modified guar gum may be used alone as an
absorbent material or in combination with other known materials, such as
natural or synthetic hydrophilic polymers. The inventors describe a potential
synergistic absorbency when the compositions are combined with one or more
of several classes of chemicals including simple carbohydrates (glucose,
fructose, sorbitol, and the like) and synthetic hydrophilic polymers. However,
no specific composition is exemplified to prove the synergistic hypothesis.
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Furthermore, these guar absorbents have an undesirable tendency to give an
syneresis effect (referred as slimy effect) to the wearer.
US Patent 4,454,055 (Richman et al.), issued to National
Starch, teach synergistic interactions between ionically crosslinked
polyelectrolytes (polyacrylates-starches), and modified starches or other
extenders. Because these ionically crosslinked polyelectrolytes are made
mainly from synthetic SAPs (Super Absorbent Polymers), they are again
unsuitable for many uses in light of allergenic, abrasive, ecological or
toxicological concerns.
Polysaccharide-protein synergies have also been reported
in the food industry. The synergistic compositions relate to the viscosity or
texture enhancement of food gels (Alloncle M et al., Cereal Chemistry, 66 (2),
1989, pp. 90-93; Kaletung-Gencer G et al., Journal of Texture Studies, 17 (1
),
1986, pp. 61-70; Alloncie M et al., Food Hydrocolloids, 5 (5), 1991, pp.455-
467; Sudhakar V et al., Food Chemistry, 55 (3), 1996, pp. 259-264; Rayment
P et al., Carbohydrate polymers, 28 (2), 1995, pp. 121-130; Pellicer J et al.,
Food Science and Technology International, 6 (5), 2000, pp. 415-423; Tako
M, Bioscience Biotechnology and Biochemistry, 56 (8), 1992, pp. 1188-1192;
Tako M et al., Agricultural and Biological Chemistry, 52 (4), 1988, pp.1071-
1072; Murayama A et al., Bioscience, Biotechnology and Biochemistry, 59 (1 ),
1995, pp. 5-10; Goycoolea F.M et al., Gums and stabilizers for the food
industry 7: proceedings of the 7th international conference in Wrexham, July,
1993, pp. 333-344)..The reasons for being of these food gels is different when
compared to those used in hygiene applications. Food gels aren't designed to
absorb or retain large amounts of saline or physiological fluids under
pressure.
Indeed, no synergistic effects have been reported in these publications
concerning absorbent or superabsorbent technologies.
CA 02426478 2003-04-24
Glass-like, pregrelatanized starches, have been disclosed
by Groupe Lysac (Huppe et al. CA 2,308,537) as being a useful absorbent for
liquids. However, these pregelatinized starches only absorb 8 g/g, which is
too
low to be useful in the hygiene industry. In order to improve the absorption
5 capacity of these modified starches, they were mixed with xanthan and guar
gums. The modified starches have also been blended in mixtures with sodium
carboxymethyl cellulose (CMC). Some synergistic effects were observed but
only in those cases where starches were admixed with specific concentrations
of guar and xanthan gums. Moreover, the disclosed absorption capacities
remained too low to be useful in the hygiene industry.
There thus remains a need for novel synergistic
compositions of polysaccharides with improved performance as natural and
biodegradable absorbent materials or superabsorbents.
The present invention seeks to meet these and other needs.
SUMMARY OF TFiE IfNVENTION
The present invention relates to synergistic compositions of
polysaccharides as natural and biodegradable absorbent materials or
superabsorbents. These synergistic compositions show an increased capacity
to absorb liquids such as water, saline solutions and biological fluids, at
normal
pressure or under load, and to retain these fluids. Furthermore these
synergistic compositions are based on natural sources, are biodegradable and
non-toxic. More specifically, the present invention relates to synergistic
absorbent or superabsorbent compositions comprising at feast one
polysaccharide and at least one polysaccharide-based component or gelling
protein.
The present invention relates to synergistic compositions of
polysaccharides to be used as natural, renewable and biodegradable
absorbents or superabsorbents for personal hygiene products such as baby
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diapers, incontinence products and sanitary napkins. The compositions can
also be used in several other applications such as in food packaging
absorbent pads; in agricultural and forestry applications to retain water in
the
soil and to release water to the roots of plants; in fire-fighting techniques;
as
bandages and surgical pads; for cleaning-up acidic or basic aqueous solution
spills, including water soluble chemical spills; as polymeric gels for
cosmetics
and pharmaceuticals also known as drug delivery systems for the controlled
release of active substances and; and finally for manufacturing artificial
snow.
The present invention also relates to a rnulti-component
synergistic absorbent composition comprising one or more modified starches
and at least one or more components selected from a first component class
selected from mannose containing polysaccharides, a second component
class selected from ionic polysaccharides, and a third component class
selected from gelling proteins or polypeptides.
The present invention further relates to a multi-component
synergistic absorbent composition comprising one or more ionic
polysaccharides and at least one or more components selected from a first
component class selected from mannose containing polysaccharides and a
second component class selected from gelling proteins or polypeptides.
Further scope and applicability will become apparent from
the detailed description given hereinafter. It should be understood, however,
that this detailed description, while indicating preferred embodiments of the
invention, is given by way of example only, since various changes and
modifications will become apparent to those skilled in the art.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 shows a comparison between measured FSC
values and calculated additive values in 0.9% NaCI solution for different
ratios
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of guar gum and starch. A weak synergistic effect is obsenoed when higher
values are obtained as compared to the corresponding calculated additive
values.
Figure 2 shows a comparison between measured CRC
values and calculated additive values in 0.9% NaCI solution for different
ratios
of guar gum and starch. A weak synergistic effect is observed when higher
values are obtained as compared to the corresponding calculated additive
values.
Figure 3 shows a comparison between measured FSC
values and calculated additive values in 0.9% NaCI solution for different
ratios
of CMC and starch. No synergistic effect is observed.
Figure 4 shows a comparison between measured CRC
values and calculated additive values in 0.9% NaCI solution for different
ratios
of CMC and starch. A strong synergistic effect is observed when higher values
are obtained as compared to the corresponding calculated additive values.
Figure 5 shows a comparison between measured FSC
values and calculated additive values in 0.9% NaCI solution for different
ratios
of CMC and guar gum. A weak synergistic effect is observed when higher
values are obtained as compared to the corresponding calculated additive
values.
Figure 6 shows a comparison between measured CRC
values and calculated additive values in 0.9% NaCI solution for different
ratios
of CMC and guar gum. A strong synergistic effect is observed when higher
values are obtained as compared to the corresponding calculated additive
values.
Figure 7 shows a comparison between measured FSC
values and calculated additive values in 0.9% NaCI solution for different
ratios
CA 02426478 2003-04-24
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of starch, CMC and guar gum. A synergistic effect is observed when higher
values are obtained as compared to the corresponding calculated additive
values.
Figure 8 shows a comparison between measured CRC
values and calculated additive values in 0.9% NaCI solution for different
ratios
of starch, CMC and guar gum. A synergistic effect is observed when higher
values are obtained as compared to the corresponding calculated additive
values. The figure also shows a synergistic effect in the absence of starch.
Figure 9 shows a comparison between measured AUI_
values and calculated additive values in 0.9% NaCI solution for different
ratios
of starch, CMC and guar gum. A synergistic effect is observed when higher
values are obtained as compared to the corresponding calculated additive
values.
Figure 10 shows a comparison between measured viscosity
values and calculated additive values in 4.9% NaCI solution for different
ratios
of starch, CMC and guar gum. No synergistic effects are observed.
DETAILED DESCRIPTION OF THE INVENTION
The present description refers to a number of routinely used
chemical terms. Nevertheless, definitions of selected terms are provided for
clarity and consistency.
As used herein the term polysaccharide refers to a
combination of nine or more monosaccharides, finked together by glycosidic
bonds, and include starch, modified starch, cellulose, etc.
As used herein, the term "modified" starch means a starch
that is pregelatinized, thermally inhibited [Jeffcoat et ai. (US Patents
5,720,822; 6,261,376; 6,016,574), Chung-Wai et al. (US Patents 5,932,017;
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6,231,675; 6,451,121), Shah et al. (US Patent 5,718,770), Shi et al. (US
Patent 6,277,186)], extruded, jet-cooked, dextrinated, hydrolyzed, oxidized,
covalently cross-linked, alkylated, hydroxyalkylated, carboxyalkylated,
esterified, fractionated in its amylose or amylopectin constituents.
As used herein, the term "Free Swell Capacity" (FSC), also
called Absorption, refers to the amount (g} of fluid absorbed (0.9%
Weightlvolume NaCI solution, thereafter called 0,9 % NaCI solution) per gram
of the composition.
As used herein, the term "Centrifuge Retention Capacity"
(CRC) also called Retention, refers to the amount (g) of fluid absorbed (0.9%
NaCI solution) per gram of the composition.
As used herein, the term "Absorption Under Load" (AUL) at
0.3 PSI (2.06 KPa), also called Absorption Against Pressure, refers to the
amount (g) of substance absorbed (0.9% NaCI solution) per gram of the
composition, using 0.1 g of absorbent in the apparatus.
As used herein, the term "ionic polysaccharides° refers to
both anionic or cationic polysaccharides.
In a broad sense, the present invention relates to synergistic
compositions of polysaccharides as natural and biodegradable absorbent
materials or superabsorbents. It was discovered that the absorbing
characteristics of modified starches can be synergistically improved by the
addition of a polysaccharide composed of mannose, an ionic polysaccharide,
gelling proteins or a combination thereof. Furthermore, it was discovered that
the performances of ionic polysaccharides can be improved by the addition of
mannose containing polysaccharides, gelling proteins or a combination
thereof.
Examples of anionic polysaccharides are selected from the
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group consisting of sodium, lithium, potassium, and ammonium salts of
carboxyalkylated cellulose (like carboxymethyl cellulose), as well as oxidized
cellulose, pectin, arabic gum, kappa, iota or lambda carrageenans, agar-agar
or alginates. Examples of cationic polysaccharides are selected from the group
5 consisting of chloride, bromide, iodide, nitrate, phosphates, sulfates and
organic salts of chitosan, as wail as cationic cellulose.
These polysaccharide compositions, in order to be suitable
for absorption purposes, should have a mean particles size ranging from about
80 prn to about 800 lam and more preferably from about 150 pm to about 600
10 Nm. In order to avoid particle migration, the particles should be
homogeneously blended. In order to achieve a homogeneous blending, the
size of the particles should not vary by more than about 200 pm. A process for
producing the compositions is provided.
The absorbent or superabsorberat synergistic
polysaccharides compositions, in accordance with the present invention, are
prepared with different ratios of individual components, as illustrated in
Examples 1 to 57. These compositions are then characterized by their Free
Swell Capacity (FSC), their Centrifuge Retention Capacity (CRC) as well as
their Absorption Under Load (AUL) capacity at 0.3 FSI (2.06 KPa). The FSC
and CRC are standard methods in the field of superabsorbents, used for all
applications in personal hygiene. AUL is a standard test for baby diapers.
A synergistic effect for a multi-component system is
observed when the measured value of the AUL, FSC and CRC is higher than
the calculated additive value.
Typical compositions of polysaccharides, as disclosed in the
present invention, are represented by the following equation:
Aa+~b+(~!n-1
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wherein, A is the composition fraction (weight by weight or referred to
hereinafter as WIW) of modified starch or ionic polysaccharides, when these
polysaccharides are used as the primary constituent; B represents the
composition fraction (WIVII) of a mannose containing polysaccharide, a gelling
protein or an ionic polysaccharide (when starch is the primary constituent of
the composition); represents the composition fraction (W/W) of
supplemental constituents, these constituents being composed of one or more
polysaccharides or proteins, selected from mannose containing
polysaccharides, gelling proteins, ionic polysaccharides or modified starches
(when applicable). It is important to note that N is a optional number and it
is
contemplated that as many fVs as required can be used in order to improve the
synergistic effects.
A specific CRC, AUL and FSC can be attributed to each
component. In other words, the first component of the synergistic blend has an
AUL, FSC, and CRC value corresponding to AULa, FSCa and CRCa, and has
a composition fraction (WIW) A. The second component has a composition
fraction (W/W) B, and has AULb, FSCb and CRCb values. Other optional
components have a composition fraction (WIW) N, and AULn, FSCn and CRCs
values.
The Absorption Under Load (AUL), the Free Swell Capacity
(FSC), and the Centrifuge Retention Capacity (CRC) of the blends, [AULa+b+n,
FSCa+b+n and CRCa+b+n] can be calculated and expressed as follows:
AU La+b+n = A~AU La + B oAU Lb + N EAU Ln
FSCa+b+n = A~FSCa + B~FSGb + N~FSCn
CRCa+b+n = A~CRCa + B~CRCb + NsCRCn
A synergistic effect is observed when the measured AUL,
FSC and CRC results of the composition are higher that the calculated
additive ones, [AULa+b+n, FSCa+b+n and CRCs+b+n].
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Synergistic effects were observed in many complex
polysaccharide compositions comprising at least one polysaccharide and at
least one or more polysaccharide-based components or gelling proteins.
These synergistic effects occur more often, and are more important, when
three or more compounds selected from these classes are present in the
composition. These synergistic effects are also more important when the
primary constituent of the composition is selected from the class of modified
starches or ionic polymers. Significant synergistic effects are also observed
when more then one product of a same class is used.
The first component class of the compositions of the
present invention can be selected from the modifsed starches. These modified
starches can be obtained from diversified sources, such as corn, waxy corn,
wheat, waxy wheat, rice, waxy rice, potato, tapioca, waxy maize, sorghum,
waxy sorghum, sago, barley, and amaranth. In order to be useful for the
applications as contemplated by the present invention, these modified
starches can be dextrinated, hydrolyzed, oxidized, covalently crosslinked,
alkylated, hydroxyalkyiated, carboxyalkylated, carboxymethylated, acetylated
or esterified, fractionated (e.g. amylose and amylopectin), and physically
modified by thermal inhibition, jet-cooking or extrusion.
Oligomeric polyethylene glycol crosslinked polysaccharides
have been previously described by troupe ~ysac (Couture et al., CA
2,362,006) as being particularly useful as modified starches. Other examples
of physically modified starches have been described by troupe Lysac (Huppe
et al., CA 2,308,537). In the latter, a pregelatinized, glass-like starch was
disclosed, which was subsequently found to be useful as a modified starch for
the compositions of the present invention.
Other modified starches, such as those disclosed by
Kimberly-Clark (Qin et al., US Patents 5,550,189; 5,498,705, and 5,470,964),
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SCA (Besemer et ai., WO 00/35504A1, WO 01134656A1 and WO
99129352A1), Beenackers A. A. C. M. et al. (Carbohydr. Polym., 2001, 45,
219-226) and National Starch (Jeffcoat et al. US Patents 5.,720,822;
6,261,376; 6,016,574; Chung-Wai et al. US Patents 5,932,017; 6,231,675; US
6,451,121; Shah et al. US Patent 5,718,770; Shi et al. US Patent 6,277,186),
could also be used in the compositions of the present invention. These
modified starches constitute only a few examples of modified starches useful
for the absorbent compositions of the present invention. Because these
modified starches already have some absorbent properties, and exhibit less
syneresis (slimy effect) than other polysaccharides, they are preferred as the
primary constituent of the compositions of the present invention.
The second component class of the compositions of the
present invention can be selected from the mannose containing
polysaccharides. These polysaccharides comprise glucomannans or
polyglucomannans such as konjac gum, or konjac flour. This class also
comprises galactomannans or polygalactomannans, such as Guar gum,
Locust bean gum, Mesquite gum, Tara gum, Phylium extracts and Fenugreek
extracts, in addition to comprising Aloe mannans.
The mannose containing polysaccharides can be used in
their natural, unmodified form as well as in a physically or chemically
modified
form. The mannose containing polysaccharides can be hydrolyzed, oxidized,
covalently crosslinked, alkylated, hydroxyafkylated, carboxyalkylated,
carboxymethylated, acetylated or esterified, and physically modified by
extrusion, jet-cooking or other processes.
The third component class of the compositions of the
present invention is an ionic polysaccharide-based compound. Tonic
polysaccharides can be both anionic and cationic. Fxamples of suitable
cationic polysaccharides are selected from the group consisting of chlorides,
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bromides, iodides, nitrates, sulfates, phosphates and organic salts of
cationic
polysaccharides, as well as cationic cellulose or- chitosan salts.
/anionic polysaccharides are the preferred third component
class for the compositions of the present invention. They can be in their
sodium, lithium, potassium or ammonium salt forms. Sodium carboxymethyl
cellulose (CMC) is the preferred ionic component. Other useful ionic
polysaccharides are sodium alginate and alginate compositions, xanthan gum,
kappa, iota and lambda carageenan gums, karaya gum, arabic gum, pectin,
agar-agar, oxidized cellulose and sulfated cellulose.
The ionic polysaccharides can be used in their natural,
unmodified form, as wail as in a physically or chemically modified form. The
ionic polysaccharides can be hydrolyzed, oxidized, covaiently crosslinked,
alkylated, hydroxyalkylated, carboxyalkylated, carboxymethylated, acetylated
or esterified, and physically modified by extrusion, jet-cooking or other
processes.
Since the ionic polysaccharides exhibit high absorption
properties, they are also the preferred primary constituent for the
compositions
of the present invention.
The fourth component class of the compositions of the
present invention are gelling proteins or polypeptides. Secause these
compounds are biodegradable and based on renewable sources, they provide
a wide array of synergistic effects suitable to the compositions of the
present
invention. Examples of suitable gelling proteins or polypeptides are gelatin,
collagen, albumin, ovalbumin, bovine albumin, casein, keratin, keratose, Whey
proteins, Whey proteins isolates, soybean proteins, soy proteins, soy proteins
isolate, polyaspartic acid or its salts, zein and gluten. Preferred gelling
proteins
are gelatin, as well as casein and its salts.
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The gelling proteins can be used in their natural, unmodified
form, as well as in a physically or chemically modified form. The gelling
proteins can be hydrolyzed, oxidized, covalently crosslinked, alkylated,
hydroxyalkylated, carboxyalkylated, carboxymethylated, acetylated or
5 esterified, and physically modified by extrusion, jet-cooking or other
processes.
In order to provide the desired synergistic effects, the
selected compounds must be homogeneously mixed. Mixing techniques are
widely known in the art and are described in Perry's Chemical Engineers'
Handbook (7t" edition, McGraw-Hill, 1997, ISBN: 0070498415).
10 Typical compositions can be mixed using double cone
mixers, twin shell mixers, horizontal drum (with or without baffles), double
core
revolving around long axis (with or without baffles), ribbon mixers, vertical
screw mixers, batch Mufler mixers, continuous Muller mixers, twin rotor
mixers,
single rotor or turbine mixers. ~ther mixing techniques applicable to the
15 compositions of the present invention will become apparent to a skilled
technician in the art, and are contemplated as being within the scope of the
present invention.
The polysaccharides and gelling proteins should have a
specific particle size in order for the compositions to be suitable for
absorption
purposes. The mean particulate size of these components should not be below
80 pm, in order to avoid fine particulate problems (Occupational Safety and
Health problems). In order to facilitate water, saline or physiological fluid
penetration inside the parficulates (to avoid a phenomenon called gel
blocking), the particuiates should not have a mean particulate size greater
than 800 pm. Particularly efficient synergistic compositions were obtained
with
mean particulate sizes ranging from about 150 tam to about 600 Nm.
In order to obtain homogenous compositions the additional
components (like B or N components) should have a similar mean particulate
CA 02426478 2003-04-24
16
size. Particulate migration can be avoided if the size of the additional
components of the compositions does not vary by more than 200 pm from the
primary component (modified starches or, when no modified starches are
used, ionic polysaccharides).
The absorbent materials or superabsorbents described in
the present invention, may be incorporated into absorbent personal hygiene
products such as, for example, baby diapers, incontinence products, sanitary
napkins and the like. They could be also used in absorbent members, like
absorbent cores, airlaids or foamed structures. These absorbent members are
mainly made from superabsorbents, cellulosic fibers or man-made fibers and
bi-component thermoplastic fibers (known also as SICO).
Furthermore, the absorbent compositions could also be
used in several other applications, such as in food pads; in agricultural and
forestry applications to retain water in the soil and to release water to the
roots
of plants; in fire-fighting techniques; as bandages and surgical pads; for
cleanup of acidic or basic aqueous spills, including water soluble chemical
spills; as polymeric gels for cosmetics and pharmaceuticals (also known as
drug delivery systems) for the controlled release of active substances; and
for
artificial snow.
As was previously mentioned, a synergistic effect for a
multi-component polysaccharide system is observed when the measured value
of the AUL, FSC and CRC is higher than the calculated additive value. This
can be observed when at least two or more compound classes are used
together. More specifically, synergistic effects were observed in many complex
polysaccharide compositions comprising at least one polysaccharide and at
least one or more polysaccharide-based components or gelling proteins.
A slight but significant synergistic effect can be observed on
the FSC and CRC for two component blends including Guar gum and Starch
CA 02426478 2003-04-24
17
(Table I, Figures 1 and 2). 6Vo synergistic effect on the FSC is observed for
blends containing CMC and Starch. However these blends exhibit a strong
synergistic effect on the CRC (Table I, Figures 3 and 4). A slight but
significant
synergistic effect on the FSC, is also observed for blends containing CMC and
Guar gum (Table I, Figure 5). However, these blends exhibit a strong
synergistic effect on the CRC (Table I, Figure 6).
As demonstrated, an AUL, FSC or CRC can be observed in
two-component compositions, but rarely simultaneously for each
measurement. In order to observe a synergistic effect on all the
measurements, three or more component blends must be used. These multi-
component blends preferably contain a component from each of the three
classes described hereinabove.
Polysaccharide three-component blends containing 0-70
Starch, 9-30 % CMC, and 21-70% Guar Gum, and preferably between 10-60%
Starch, 12-27 % CMC, and 28-63% Guar Gum demonstrate a strong
synergistic effect by increasing values of FSC up to 44 g/g with a synergistic
effect near 5 g/g (Table I!, Figure 7).
Similarly, polysaccharide three-component blends or
mixtures containing 0-70 % Starch, 9-30 % CMC, and 21-70% Guar Gum, and
preferably between 10-60% Starch, 12-27 % CMC, and 28-63% Guar Gum
demonstrate a synergistic effect by increasing values of CRC up to 34 g/g with
a synergistic effect near 9 g/g {Table II, Figure 8).
Similarly, polysaccharide three-component blends or
mixtures containing 0-70 % Starch, 9-30 % CMC, and 21-70% Guar Gum, and
preferably between 10-60% Starch, 12-27 % CMC, and 28-03% Guar Gum
demonstrate a synergistic effect by increasing values of AUL up to 25 g/g with
a synergistic effect near 5 g/g (Table II, Figure 9).
CA 02426478 2003-04-24
18
A synergistic effect on the viscosity was not observed
(Table II, Figure 10).
Examples 51 to 57 illustrate the use of gelling proteins and
polypeptides such as gelatin and calcium caseinates, added to the complex
synergistic polysaccharides formulations.
The use of other natural polysaccharides or gelling proteins
in the composition of the present invention leads to significant synergistic
effects as illustrated in Examples 29 to 50 (Tables III to VII). These results
illustrate synergistic compositions with performances comparable to those
obtained with synthetic superabsorbent polymers such as polyacryiates and
polyacrylamides.
The present invention is illustrated in further detail by the
following non-limiting examples.
Starting Materials
Pre-gelatinized wheat starch A (ADM-~gilvie), sodium
carboxymethyl cellulose (CMC aqualon; Hercules) and crude unmodified guar
gum (L.V. Lomas Ltd.) have been used as starting materials for examples 1
to 28.
Modified starches such as carboxymethylstarch and
esterified starches crosslinked with triglycoldichloride were provided by
Lysac
Technologies Inc.
Crude unmodified guar gum (Starlight), crude unmodified
konjac gum (LIMA~ Agricultural products), CMC aqualon (Hercules), xanthan
gum (ADM), sodium alginate (Tic Gums), carrageenan (CP Kelco), pectin LM
(Tic Gum) and chitosan Chito Clear (Primex) have been used as starting
materials for examples 29 to 57.
CA 02426478 2003-04-24
19
AUL measurements
The Absorption Under load (AUL) in a 0.9% NaCI solution
at 0.3 psi was determined according to the recommended test method 442.1-
99 from EDANA2, using 0.1 gram of the absorbent in the apparatus.
FSC and CRC measurements,~using tea bags)
Tea bags (10 X 10 cm) were made from heat sealable
Ahlstrom filter paper 16.5 ~0.5 glm2.
FSC measuremen
The Free Swell Capacity (FSC) in a 0.9% NaCI solution was
determined according to the recommended test method 440.1-99 from
EDANA.3
CRC measurements
The Centrifuge Retention Capacity (CRC) in a 0.9% NaCI
solution was determined according to the recommended test method 441.1-99
from EDANA.4
Viscosity measurements
The viscosity was measured with a Brookfield RV DV 1l+
viscometer at 50 RPNi with a spindle No 6, using a 2% (WMI) solution made
with a 0.9% NaCI solution and agitated for one llour before measurement.
Gel strength measurements
The gel strength was measured using a TA.XT2i from
Texture Technologies with a cylindrical probe TA-12, load capacity SKg, gain
trigger 0.5 g, displacement 10 mm, time 5 seconds, speed 2.0 mm Isecond.
The gel strength is expressed in force (g).
Biodegradability and ecological impact
According to the United States Environmental Protection
Agency (EPA), the Zahn-Wellens test is useful for testing the biodegradability
CA 02426478 2003-04-24
of a substance soluble in water to at least 50 mg of dissolved organic carbon
(DOC) per liter (US Environmental Protection Agency (EPA), Fate, Transport
and Transformation Test Guidelines, OPPTS 832.3200, Zahn-Wellens / EMPA
test, EPA712-C-98-084, January 1998).5 For substances that are not
5 completely soluble, it offers only a qualitative indication of whether these
substances are basically susceptible ro biological degradation or not
(Buchholz
et al., US Patent 5,789,570). An activated sludge was used in Example 27 to
evaluate the biodegradability. A technicon carbon analyzer was used to
measure the DOC and the percentage biodegradability was calculated
10 according to the DOC obtained, and reported in the equation given in
reference 4. Example 27 showed no toxicity for microorganisms and no toxic
product was detected that would destroy the aquatic fauna, particularly the
micro crustacean Daphnia magna. IV'Aineral medium was used as a blank and
the positive control was ethylene glycol, which showed 100% biodegradability
15 after 14 days.
Composition percenta~qes
Composition percentages are all related in weight by weight
(w/w) percentages.
Hypoallergenisity
20 Hypoallergenisity tests were performed by the Consumer
Product Testing Co. according to the ASTM D6355-8 norms; performed with
adherence to ICH Guideline E6 for good clinical practice and requirements
provided for in 21 CFR parts 50 and 56 in accordance to standard operating
procedures and applicable protocols. The products have been tested with sixty
(60) qualified subjects, male and female, ranging in age from 20 to 72 years.
The upper back, between the scapulae, served as the
treatment area. Approximately 0.2 g of the material was applied to the 3/4" x
3/<"
absorbent pad portion of a saline moistened adhesive dressing. Patches were
CA 02426478 2003-04-24
21
applied three times per week (e.g. Monday, Wednesday and Friday) for a total
of nine (9) applications. The site was marked to ensure the continuity of
patch
application. Following supervised removal and scoring of the first Induction
patch, participants were instructed to remove all subsequent induction patches
at home, twenty-four hours after application.
The following evaluation key was used by all participants:
0 : No visible skin reaction;
+ : Barely perceptible or spotty erytherma;
1 : Mild erytherma covering most of the test site;
2 : Moderate erytherma, possible presence of mild edema;
3 : Marked erytherma, possible edema;
4 : Severe erytherma, possible edema, vesiculation, bullae or ulceration.
ENIP~.ES 1 to 15
Synergy for FSC and CRC with two comp~nent blends
Two component blends (examples 1 to 15) comprising Guar
Gum and Starch, CMC and Starch, CMC and Guar Gum were prepared by
weighing 0, 25, 50, 75 and 100 °f° of each material. The blends
were mixed
vigorously in a 20 ml vial. The Free Swell Capacity (FSC) and Centrifuge
Retention Capacity (CRC) was measured for each of the two component
blends, and was subsequently compared with calculated additive values based
on component performances. The results are illustrated in Table I, as well as
in Figures 1 to 6.
CA 02426478 2003-04-24
22
TABLE
I:
Exa_
m tes
for
two-com
onent
blends
Exam Blends Measured S ner
1e Calculated
Guar ' StarchFSC CRC FSC CRC FSC CRC
Gum CMC
8315
l l l l l l
i
1 100 0 32.48 22.72 32.482 0.00 0.00
2.72
2 75 25 44,50 33.17 41.49_ 3.02 8.54
24.64
3 50 50 52.10 38.61 ' 26.551.61 12.06
50.49
4 25 75 61.20 45.89 i 28.471.71 17.43
59.50
0 100 68.50 30.38 i 30.380.00 0.00
68.50
6 0 100 6.20 4.04 i 4.04 0.00 0.00
6.20
7 25 75 14.00 _ 8.71 1.23 1.75
10.461
12.77
8 50 50 20.65 13.48 19.3413.381.31 0.10
9 75 25 26.10 18.03 ' 18.050.19 -0.02
25.91
100 0 32.48 22.72 32.4822.720.00 0.00
11 0 100_ _6.20 4.04 6.20 4.04 0.00 0.00
12 25 75 20.41 15.01 21.7810.63-1.37 4.39
13 50 50 34,55 25.84 37.3517.21-2.80 8.63
14 75 25 52.44 36.64 52.93_ -0.48 12.85
23.80
a 15 ~ 100 0 68.50 30.38 ~ 30 0.00 0.00
~ ~ ~ ~ 68.50 38
Gom
onents
erformances
Measured
~
I FSC CRC
_
-_ ~I
9/~
Starch 6.20 4.04
2604
Guar 32.48 22.72
Gum
CMC 68.50 30.38
Aqualon
8315
EXAMPLES 16 to 26
Synergy for FSC,CRC, AllL and viscosity with three corr~ponent blends
5 Three component blends (examples 10 to 26) were
prepared by weighing 0 to 100 % of Starch, 0 to 30 % of CMC and 0 to 70
of Guar Gum. The blends were mixed vigorously in a 20 ml vial. The FSC,
CRC, Absorption under load (AUL) and viscosity was measured for each of the
three component blends, and was subsequently compared with calculated
10 additive values based on component performances. The results are
illustrated
in Table II, as well as in Figures 7 to 10.
CA 02426478 2003-04-24
23
TABLE
Exam It
1e :
Examples
for
a
three-component
blend
Blends
Measured
Calculated
GuarCMC StarchFSC CRC AUL Visc.FSC ; AUL Visc.
Gum 8315 CRC
l I / cP I I / cP
!c
16 0 0 100 6.20 4.0417.0980 6.20 4.0417.0980
_ 17 7 3 90 __9.577.5517.98100 9.91 6.1417.78569
18 14 6 80 13.6210.8318.07160 13.628.2418.461059
19 21 9 70 18.9413.5018.54280 17.3310.3319.151548
20 28 12 60 22.7016.6718.28760 21.0312.4319.842038
21 35 15 50 27.1220._8321.23138_024.7_414.5320.532527
22 42 18 40 31.7223.72~57 216_028.4516.6321.213016
j
23 49 21 30 3_7.0825.73, 316032.16_18._7221.903506
24.05
24 56 24 20 40.5127.0223.83258035.8720.8222.593995
25 63 27 10 43.5630.1723.79336039.5822.9223.284485
I
26 70 30 0 43.3833.8825.506'10043.2925.0223.964974
Synergy
FSC CRCRCGAULVisc.
cal I 1 c
6 0.00 0.00I _0
17 _-0.341.410.00-469
I _0.00_2.590_.20-899
18 1.61 3.17-0.39'
t 1.67 4.24-0.61-1268
19 2.38 _6.30-1.56-1278
! 1 0.70-1147
20
21
'
22 3.27 7.094.36-8
56
23 4.92 2.15_
24 ~ 1.24-346
7.01 -141
4.64 5
6.20
25 3.98_1_7.250.51_
26 _ _ 0.09 _8.8_6_1.54-1125
i 1126
Com
onent
erformances
_
_ Measured
FSC CRC AUL isc.
I ~~ ~l~ ~p
-
Starch 6.20 4.0417.0980
2604
Guar 32.4822.7220.96420
Gum
CMC 68.5030.3830.9715600
A
ualon
B315
CA 02426478 2003-04-24
24
EXAMPLE 27
Biodegradability, hypoallergenisity, FSC, CRC and AIJL of three
component blend
Pregelatinized lNheat Starch (15 Kg, 50 °I°, 30-170 mesh
(147 to 589 microns)); CNIC (3.9 Kg, 13 %, 30-170 mesh (147 to 589
microns)); and guar gum (11.1 Kg, 37 %, 30-170 mesh (147 to 589 microns))
were vigorously mixed in a double action mixer (LELAND 100 DA-70, 40 Kg
capacity) over a period of 15 minutes.
FSC = 29.0 g/g
CRC = 20.3 g/g
AUL = 20.0 glg
Biodegradability: 91.1 % after 28 days.
Hypoallerginicity : Panel No. 20020142, No visibPe skin reaction (0) for all
sixty
(60) qualified subjects, on all nine (9) applications.
EXAMPLE 28
Effects on the FSC, CRC, AUL, gel strength and viscosity of ionic
polysaccharides having different viscosities
Pregeiatinized 9Nheat Starch (1000 Kg, 44.67 % (ADM));
Guar Gum Procol (900 Kg, 40.21 % (LV Lomas)); Cf~C Aqualon (114 Kg, 5.07
% {Hercules)); CMC Gabrosa (125 Kg, 5.58 % (Akzo Nobel)); and C11~C (100
Kg, 4.47 % (Amtex)) were mixed in an industrial mixer for 10 minutes.
FSC = 27.47 glg
CRC = 23.53 g/g
AUL = 21.69 g/g
Gel strength = 25.01 g
Viscosity = 2180 Centipoises {Cp)
CA 02426478 2003-04-24
E NlPL.ES 29 to 32
Effect on the ESC, CRC and AIJL of three~co'nponent blends, of
different starch based products.
Four different starch based products (44.6' %) were mixed
5 with Guar Gum (40.21 %) and CMC (15.12 %) as described in Examples 1 to
15. The different starch based products used were pregeiatinized wheat starch
(ADM), sodium carboxymethyl wheat starch crosslinked with triglycof dichloride
(Lysac Technologies Inc.), sodium maleate wheat starch crosslinked with
trigiycol dichloride (Lysac Technologies Inc.), and a hybrid of the latter two
10 (Lysac Technologies Inc.).The results are illustrated in Table III.
-TABLE III: Examples for a three-component blend with different starch based
product,
guar oeim and CMC
ExampleBlends StarchMeasured Calculated
t pe ~
Guar CMC Starch FSC CRC AUL FSC CRC AUL
Gum 8315 _
I l Ic,~I I I
29 40.21 15._1244.67_1 35.71 33.1327.20.26 26.0618.36
3
40.21 15.1244.672_ 47.88 43.5130.50_ 32.4526.95
39.96
31 40.21 15.1244.673 _38.3335.3826.2636.3928 26.10
.43
32 40.21 15.1244.674 38.31 34.6432.0436.39_ 23.57
29.32
S _ne_rg
FSC _ AUL
CRC
Ig _! l
29 1 5.35 7.078.84
30 2 7.92 1.063.55
1
31 3 1.94 6_.950.16
32 4 1.92 5.328.47
_
Com erformances
onent
Measured
FSC CRC AUL
- I l I
Starcha 1: 6.50 4.7011.47 I
t Pre
e1
2604
ADM
Starcha 2: crosslinked 19.0030.70
t Carbo with
meth TEG
fy 28.00
Starcha 3: 20.00 10.0028.81
t Maleate
crosslinked
with
TEG
Starcha 4: ked 20.00 12.0023.14
t H with
brid TEG
crosslin
Guar Starli __ 48.73 45.6822.60
Gum ht
CMC 52.00 37.0027.41
A
ualon
8315
CA 02426478 2003-04-24
26
EXAhAPLES 33 to 36
Effect on the ESC, CRC and AlJL of three-component blends, of
different starch based products
Four different starch based products (44.67 %) were mixed
with Konjac Gum (40.21 %) and CMD (15.12 %) as described in Examples 1
to 15. The different starch based products used were pregelatinized wheat
starch (ADM), sodium carboxymethyl wheat starch crosslinked with triglycol
dichloride (Lysac Technologies Inc.), sodium maleate wheat starch crosslinked
with triglycol dichloride (Lysac Technologies Inc.) and a hybrid of the latter
two
(Lysac Technologies Inc.). The resuits are illustrated in Table ~/I.
'TABLE
IV:
Examples
for
a
three-component
blend
with
different
starch
based
product,
_ kon'ac
um
and
CMC
ExampleBlends Starch Measured Calculated
t a
KonjacCMC Starch FSC CRC AUL FSC CRC AUL
B315 _
% _% 9~~ I ~ I ~I I
33 40.21 15.1244.671 32.9_929.55 21.84 29.5625.3417.16
34 40.21 15.1244.672 39.7536.92 22.21 39.1631.7325.75
35 40.21 15.1244.673 33.9831.33 32.20 35.5927.7124.90
36 40.21 34.3231.07 27.14 35.5928.6022.37
15.12 _ ergY
44.64 S CRC AUL
_ FSC
! / /
33 1 3.43 4.21 4.68
34 2 0.59 5.19 -3.54
35 3 -1.613.62 7.30
36 _4 -1.272.47 4.77
_
Component erformances
_.
_
_.
-
M easure d
_ FSC CRC AUL
l I I
Starcha 1: 6.50 4.70 11.47
Pre
e1
2604
ADM
Starcha 2: 19.00 30.70
t Carbo
meth
I
crosslinked
with
TEG
28.00
Starche 3: 20.00 10.00 28.81
typ Maleate
crosslinked
with
TEG
iStarche 4: 20.00 12.00 23.14
typ Hybrid
crosslinked
with
TEG
Konjac 46.73 43.89 19.62
Gum
(LIMAO)
_ 52.00 37.00 27.41
'CMC
Aqualon
8315
CA 02426478 2003-04-24
27
EXAN9PLES 37 to 40
Effect on the FSC, CRC and AtJL of three-corrlponent blends, of
dsfferent starch based prod~lcts
dour different starch based products (44.67 %) were mixed
with Guar Gum (40.21 %) and sodium Alginate (15.12 %) as described in
Examples 1 to 15. The different starch based products used were
pregelatinized wheat starch (ADM}, sodium carboxymethyl wheat starch
crosslinked with triglycol dichloride (Lysac Technologies Inc.), sodium
maleate
wheat starch crosslinked with triglycof dichloride (Lysac Technologies Inc.)
and
a hybrid of the latter two (Lysac Technologies Inc.). The results are
illustrated
in Table V.
TABLE
V:
Examples
for
a
three-component
blend
with
different
starch
based
product,
guar
gum
a~td
sodium
alginate
_
ExampleBlends Starch Measured
ty~ Calculated
Guar AI Starch FSC CRC AUL CRC AUL
inate FSC
c,~! g1 I I I
I
37 40.21 15.1244.6_7_ 1 35.88 33.12 21.42 24.1518.25
29
.70
38 40_.21_15.1244.672 46.95 40. _ 30.5426.84
06 26.23
39.30
39 40.21 15.1244.673 _ 39.40 _ 28.69 26.5226.00
33._51 35.73
40 40.21 15.1244.674 36.85 31.60 31.80 27.4123.47
- - _ - 35.73
S erg
FSC CRC AUL
c,~l l l
-_.
_
37 1 6.18 8.97 3.17
38 2 7.65 9.52 -0.61
39 3 3.67 6.99 2.69
40 4 1.12 4.19 8.33
Com erformances_
onent
M easured
FSC CRC
I AUL
l
I
Starcha 1: 6.50 4.70
t Pre 11.47
e1
2604
ADM
Starcha 2: 28.00 19.00
t Carbox 30.70
meth
t
crosslinked
with
TEG
Starcha 3: 20.00 10.00
t Mateate 28.81
crosslinked
with
TEG
Starcha 4: 20.00 12.00
t H 23.14
brid
crosslinked
with
TEG
Sodium 45.02 33
al .8
inate 8
Tic 26.14
Gums
___
Guar (Starlight) 48.73 _
um _
45.68
22.601
CA 02426478 2003-04-24
28
E~41UIPL.ES 41 to 44
Effect on the ESC, CRC and Al7L of three-component blends, of
different starch based products
Four different starch based products (44.67 %} were mixed
with Guar Gum {40.21 %} and I<onjac Gum (15.12 %} as described in
Examples 1 to 15. The different starch based product used were
pregelatinized wheat starch (A~M), sodium carboxymethyl wheat starch
crosslinked with triglycol dichloride (Lysac Technologies Inc.), sodium
maleate
wheat starch crossfinked with triglycol dichloride (Lysac Technologies Inc.)
and
a hybrid of the latter two {Lysac Technologies Inc.). The results are
illustrated
in Table VI.
TABLE
VI:
Examples
for
a
three-component
blend
with
different
starch
based
product,
I
uar
and
konjac
gum
_
ExampleBlends StarchMeasured Calculate
t ~e
StarchGuar Kon'ac FSC CRC AUL FSC CRC AUL
_.
/ / ~/w / I I
41 40.21 15.12 1 32.49 30.42 27.2629.5627.1017.18
44.67
42 40.21 15.12 2 43.27 40.25 27.2039.1733.4925.77
I 44.67 I
43 40.21 15.12 _ 3 36.55 34.06 31.9635.5929.4724.92
44.67
44 40.21 15.12_ 4 37.02 33.95 31.9 35.5930.3622.39
i 44.67 6
S _
ner AUL
FSC /
CRC
/
/
41 1 2.93 10.08
3.32
(
42 ~ 2 4.10 1.43
6.76
43 ~ 3 _ 7.04
0.96
4.59
44 ~ 4 1.43 9.57
; 3.59
Component erformances
p
M easured
FSC CRC
I AUL
l
I
Starcha 1: 6.50 4
t Pre .70
e1 11.47
2604
ADM
Starcha 2: 28.00 _
Carbox 19.00
meth 30.70
I
crosslinked
with
TEG
Starche 3: 20.00 10.00
typ Maleate i
crossiinked 28.81
with
TEG
~,_Starche 4: 2 12:00
typ Hybrid 0.00 i
crosslinked 23.14
with
TEG
Guar (Starlight) _ 45.68
gum 48.73 22.60
Konjacm (LIMAO) 46.73 43.89
chu 19.62
CA 02426478 2003-04-24
29
E IVIPLES 45 to 5~
Effect on the FSC, CRC and AUL of rnulti-corn~onent blends, of
different polysaccharides
Slends were prepared by mixing pregelatini~ed wheat starch
(ADM}, as the first component class (starch based product}, guar gum
(Starlight} and konjac gum (L1MA0) as the second component class
(polygalactomanan and polyglucomanan) and finally, CMC (Hercules), xanthan
(ADM), sodium alginate (Tic Gums), carrageenan (CP iCelco), pectine (Tic
Gums) and chitosan (Primex) as the third component class (ionic class) as
described in Example 1 to 15. The synergistic results on the FSC, CRC and
AUL are illustrated in Table Vli.
TABLE
VIB:
Examples
for
multi-com
onent
blends
_
Ex. I Blends _ _ Measured
Starch GuarKonjacCMC XanthanAlginateCarry-PectineFSC CRC U
ee_n_an
_ / /
%
45 40.0030.000.00 20.000.00 10.000.00 0.00 32.8929.38
23.41
'~,
46 30.0037.50_0.0022.50' 10.000.00 0.00 38.13_
0.00 34.00
23.48
~'~
47 30.0020.0020.0010.00~ 0.00 10.00 0.00 41.30.83 20.76
10.00 i
38
48 30.0020.0020.0010.00i 0.00 0.00 10.0038.86_
10.00 _
35.30
19.00
49 30.0020.0020.0010.00I 0.00 10.00 10.0042.3938.88
0.00 21.73
50 30.0020.0020.0010.000 10.000.0 10.0036.5132,28
25.10
C alculated j S
FSC CRCAUL FSC ner AUL
_ - CRC
/ ~ / / /
45 32.3825.4219.52 0.51 3.96 3.89
46 36.6929.3020.76 1.44 4.70 2.72
I
47 38.9933.1119.66 2.31 5.72 1.1_7
,48 38.5932.7318.54 0.27 2.57 0.46
'
!49 34.8529.4218.73 7.54 9.46 2.99
,
X50 35.1128.4718.79 1.40 3.81 6.31
__
Com per$ormanc~_s
onent
_
Measure d
FSC CRC AUL
~L~j /
g/
Starch 6.50 4.70 11.4
2604 7
ADM
Guar t 48.7345.68_
um Starli 22.60
h
Kon'ac 46.7343.8919.62
um LIMAO
CMC (Aqualon 5) 58.2045.9027.41
B31
Sodium ic s 47.6324.3526.73
AI inate Gum
T
Carry 45.0233.8826.14
eenan
CP KeIkoL_
Pectine 41.0230.0614.95
Tic
Gums
Xanthan 82.4667.0224.
(ADM) 20
Chitosan - 8.18 1.63 _
(Primex) 16_1
CA 02426478 2003-04-24
EX~iUIPLES 51 to 5'7
Effect on the PSC, CRC anti AUL of multi-component blends, of
different polysaccharides ~rith the presence of proteins
Blends were prepared by mixing gelling proteins such as
5 gelatin and calcium caseinate with pregelatinized wheat starch (ADM), as the
first component class (modified starch), guar gum (Starlight) and konjac gum
(LiMAO} as the second components class (polygalactomanan and
polyglucomanan) and finally, CMC (Hercules.}, xanthan (ADM}, sodium
alginate (Tic Gums), carrageenan (CP Kelco), pectine (Tic Gums) and
10 chitosan (Primex) as the third components class (ionic class) as described
in
Examples 1 to 15. The synergistic results on the CSC, CRC and AUL are
illustrated in Table Vlll.
CA 02426478 2003-04-24
31
TABLE rote6ns
Vfll:
Exam
les
for
mufti-com
onent
blends
vrith
Ex. Blends
Starch KonjacCMC XanthanAiginateCarra-PectineChitosan GelatinCasein
Guar I
geenan
% % % % % % ~
%
51 50.00 0.00 0.000.00 14.5014.50 14.501.500.00 5.00
0.00
52 .00 0.00 0.000.00 14.5014.50 0.00 0.000.00 5.00
16.00
50
53 _ 0.00 0.000.00 14.5014.50 0.00 0.005.00 0.00
50.00
16.00
54 35.00 0.00 0.000.00 0.00 0.00 0.00 0.0015.00 0.00
50.00
55 55.00 97.005.002.00 0.00 5.00 0.00 0.005.00 1.00
10.00
56 45.00 5.00 5.005.00 2.00 2.00 2.00 0.006.00 2.00
26.00
57 35.00 0.00 0.000.00 5.00 0.00 0.00 0.005.0_0 5.00
50.00 j
Measured __CaIcuBated Synergy
FSC CRCAUL FSC CRC AUL FSC CRC AUL
9~9 9~99~9 9~9 9~9 9~9 9~9 gl9 9~9
~
51 28.3819.7517.35 23.0015.1816.58 5.384.57 0.77
52 32.5325.0921.21 24.7318.1017.78 7.806.99 3.43
I
53 30.0823.9119.81 25.1118.41_ 4.975.50 1.95
17.86
54 31.2328.7822.35 28.5225.4117.83 2.713.37 4.52
55 29.5926.8419.71 23.8820.2516.06 5.716.59 3.65
_
56 31.9827.7619.27 28.4923.9717.27 3.493.79 2.00
57 32.2129.0919.90~ 29.8926.0118.26 2.323.08 1.64
~ ~
Component rmances
perfo
Measured
_
FSC CRC AUL
I
_
9~9 9~9 9~9
. _
Starch 6.50 4.70 11.47
2604
ADM
___
jGuar 48.7345.6822.60
gum
(Starlight)
_
Ko . 46.7343.8919.62
c !
um
LIMAO
CMC ~ 58.2045.9027.41
A
uafon
8315
Sodium 47.6324.3526.73
AI
inate
Tic
Gums
~Carra 45._0233.8826.14
eenan - __
CP
Kelko
Pectine 41.0230.0614.95
Tic
Gums
Xanthan 82.4667.0224_.20
ADM
Chitosan 8.18 1.63 16.14
Primex
Gelatin 12.566.15 16.80
Casein ~ 0.00 15.35
4.90
Although the present invention has been described
hereinabove by way of preferred embodiments thereof, it can be modified
without departing from the spirit and nature of the subject invention as
defined
in the appended claims.
CA 02426478 2003-04-24
32
REFERENCES
1. Beenackers A. A. C. M. et al. An experimental study on
the carboxymethylation of granular potato starch in non-aqueous media.
Carbohydr. Polym., 2001, 45, 219-226.
2. EDANA, Absorbency Against Pressure No. 442.1-99,
Recommended Test Method: Superabsorbent materials-Polyacrylate
superabsorbent powders-Absorbency Against Pressure by Gravimetric
Determination, Febr. 1999.
3. EDANA, Free Swell Capacity No. 440.1-99,
Recommended test Method: Superabsorbent materials-Polyacrylate
superabsorbent powders-Free Swell Capacity in Saline by Gravimetric
Determination, Febr. 1999.
4. EDANA, Centrifuge Retention Capacity No. 441.1-99,
Recommended Test Method: Superabsorbent materials-Polyacrylate
superabsorbent powders-Centrifuge Retention Capacity in Saline by
Gravimetric Determination, Febr. 1999.
5. US Environmental Protection Agency (EPA), Fate,
Transport and Transformation Test Guidelines, OPPTS 832.3200, Zahn-
Wellens / EMPA test, EPA712-C-98-084, January 1998.
6. ASTM D6355-98 Standard Test Method for Human
Repeat INSULT Patch Testing of Medical Gloves.
